WO2025036665A1 - Compositions for fibreboards with enhanced properties upon fast-curing at low temperature - Google Patents
Compositions for fibreboards with enhanced properties upon fast-curing at low temperature Download PDFInfo
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- WO2025036665A1 WO2025036665A1 PCT/EP2024/070971 EP2024070971W WO2025036665A1 WO 2025036665 A1 WO2025036665 A1 WO 2025036665A1 EP 2024070971 W EP2024070971 W EP 2024070971W WO 2025036665 A1 WO2025036665 A1 WO 2025036665A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/603—Polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
Definitions
- compositions comprising vegetable fibers, a hyperbranched polylysine and a component having groups of the following formulae which compositions are particularly suitable for the preparation of objects such as engineered wood e.g. fibreboards.
- 2023PF30090-01 FC BACKGROUND In the context of this invention but also in the literature, polylysine refers to several types of lysine homopolymers which may differ from each other in terms of stereochemistry and link position.
- Lysine in either of its two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s central carbon atom
- Lysine which is the precursor amino acid, contains two amino groups; one at the ⁇ -carbon and one at the ⁇ -carbon. Either of these two amino groups can be the location of polymerization, resulting in ⁇ -polylysine or ⁇ -polylysine.
- Fibers or fibres; the terms are used interchangeably in the context of this invention) constitute a class of materials that are continuous filaments or are in discrete elongated pieces, similar to lengths of thread. Human uses for fibers are diverse.
- Fibers can be spun into filaments, string or rope, used as a reinforcing agent in composites into sheets to make products such as paper or felt. Fibers are often used in the manufacture of other materials. Fibers may be recycled. In the context of this invention the term ‘fiber’ includes also recycled fibers. On the basis of their origin, fibers are divided into two main categories namely natural and synthetic fibers. Synthetic fibers are also known as man-made or artificial or manufactured fibers. Natural fibers are further divided into: i) mineral fibers (e.g. asbestos, wollastonite, attapulgite, halloysite), ii) animal fibers (e.g.
- mineral fibers e.g. asbestos, wollastonite, attapulgite, halloysite
- animal fibers e.g.
- vegetable fibers are based on arrangements of cellulose (known also as ‘natural cellulose fibers’), or arrangements of cellulose with lignin (known also as ‘natural lignocellulosic fibers’), and are derived from sources of natural cellulose or natural cellulose with lignin, such as from plants which are living organisms of the kind exemplified by trees, bamboos, shrubs, herbs, grasses, ferns, and mosses, absorbing water and inorganic substances through its roots, and synthesizing nutrients in its leaves by photosynthesis using the green pigment chlorophyll.
- natural cellulose fibers known also as ‘natural cellulose fibers’
- lignin known also as ‘natural lignocellulosic fibers’
- sources of natural cellulose or natural cellulose with lignin such as from plants which are living organisms of the kind exemplified by trees, bamboos, shrubs, herbs, grasses, ferns, and mosses, absorbing water and inorganic substances through its roots, and
- Examples of vegetable fibers include but are not limited to wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf (hibiscus cannabinus) fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof.
- Synthetic also known as man-made or artificial or manufactured fibers
- Synthetic can be further divided into: i) cellulose fibers regenerated from natural resources, known also as cellulose-regenerated fibers (e.g.
- 2023PF30090-01 FC Cellulose fibers are a subset of fibers.
- Cellulose fibers are fibers of cellulose from any source, either natural or manufactured (the latter is also known as synthetic cellulose fibers). Therefore, cellulose fibers can be natural (e.g. cellulose fibers from sources of natural cellulose such as from trees (including bamboos), seaweed, or synthetic (e.g. cellulose fibers regenerated from natural cellulose such as rayon, modal, Lyocell, cellulose acetate, cellulose triacetate).
- the synthetic cellulose fibers are also known in the art as man-made cellulose fibers or as regenerated cellulose fibers or as manufactured cellulose fibers or as artificial cellulose fibers.
- synthetic cellulose fibers “man-made cellulose fibers” or “manufactured cellulose fibers” or “artificial cellulose fibers” or “regenerated cellulose fibers” are used interchangeably and these terms are used to distinguish the synthetic cellulose fibers from the natural cellulose fibers and the natural lignocellulosic fibers, the latter two being vegetable fibers.
- One of the most important type of fibers are wood (including recycled wood) fibers. There are two main types of wood: a) softwoods and b) hardwoods.
- Softwoods come from cone bearing trees.
- Exemplary softwoods include but are not limited to pine, redwood, and fir.
- Softwoods can be used for furniture and doors but are mostly used in construction for roof trusses and stud partitions.
- Hardwoods come from leaved trees. These trees may have flowers and may produce seeds such as nuts and fruit.
- Exemplary hardwoods include but are not limited to oak, beech and mahogany. Hardwoods are denser than softwoods and are stronger and more durable as well. They are used for furniture and are typically more expensive than softwoods. Wood may be recycled. In the context of this invention the term ‘wood’ includes also recycled wood.
- Engineered wood also known as mass timber, composite wood, man- made wood, or manufactured board
- engineered wood include but are not limited to plywood, densified wood (including chemically densified wood), fibreboard [the term includes low- density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, 2023PF30090-01 FC flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites.
- LDF low- density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- OSB oriented strand board
- laminated timber glulam; glued laminated timber
- laminated veneer lumber laminated veneer lumber (LVL
- Fiberboards constitute a subset of engineered wood.
- Types of fibreboards include low-density fibreboards (LDF; known also as particle boards or chip boards), medium-density fibreboards (MDF), high-density fibreboards (HDF; known also as waferboards, flakeboards).
- LDF low-density fibreboards
- MDF medium-density fibreboards
- HDF high-density fibreboards
- fibreboards with density of at most 500 kg/m 3 are viewed as LDF.
- fibreboards with density higher than 500 and at most 1000 kg/m 3 are viewed as MDF.
- fibreboards with density higher than 1000 kg/m 3 are viewed as HDF.
- fibreboards can be formed using either a wet-forming or a dry-forming process. In a wet-forming process, water is used to distribute the fibers into a mat and then pressed into a board.
- fibers from the refiner go through a dryer and blow line where an adhesive is applied and then formed into a web which is pressed into a board.
- a typical fibreboard manufacture -at an industrial scale- begins with wood chipping: fresh or recycled wood material is cut and sorted to small pieces of similar size. Chips are washed to remove things such as dirt and sand. Metal scraps such as nails can be removed with a magnet placed over a conveyor belt on which the chips move forward. In the case of, for example MDF, chips are then steamed to soften them for defibration.
- UF resins are dominantly used in the MDF industry. 2023PF30090-01 FC
- the term includes low- density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)]
- LDF low- density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- E apparent modulus of elasticity
- Both the modulus of rupture (Rb) and the apparent modulus of elasticity (E) constitute the flexural properties of an object e.g. a fibreboard.
- the internal bond strength and the flexural properties of fibreboards are critical for their consumer acceptance as well as their commercial success. Fibreboards that do not meet at least one of the above thresholds for each one of internal bond strength, Rb and E do not perform at a level acceptable by the end consumer. Fibreboards with enhanced internal bond strength and flexural properties are thus desirable.
- Enhanced flexural properties allow for more tolerance in mechanical and/or physical stresses that fibreboards are subject to during their lifetime of use including -but not limited to- their preparation, packaging, unpackaging, transport, storage and use.
- Fibreboards that suffer from poor flexural properties are usually fragile with little or no tolerance at all for mechanical and/or physical stresses. As a consequence the poor flexural properties severely limits their application and uses -if any-, and/or their lifetime -once in use- and consequently are typically rejected by the consumers.
- enhanced internal bond strength is also desirable since it ensures acceptable physical integrity and allow for more tolerance in mechanical and/or physical stresses that fibreboards are subject to during their lifetime of use.
- Fast-curing at low temperature of compositions suitable for preparing fibreboards is also very desirable since it enhances production efficiencies, increases throughput and lowers the amount of energy required to cure said compositions.
- the EP 2614117 B1 related to a multi-layer lignocellulose-containing molding.
- the EP 2614117 B1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification.
- the US 2017/198142 A1 related to aqueous curable binder compositions comprising (i) a polyphenolic macromolecular compound which bears a multitude of phenol or polyhydroxybenzene radicals, such as catechol radicals, 2023PF30090-01 FC preferably lignosulfonate salt, condensed tannins and mixtures thereof, and (ii) a polyamine functional compound comprising primary and/or secondary and/or tertiary and/or quaternary amine functional groups, and/or reaction production of (i) and (ii), the ratio of polyphenolic macromolecular compound to polyamine functional compound ranging from 98:2 to 50:50, preferably from 98:2 to 70:30 wt%, more preferably from 95:5 to 80:20 wt%.
- the US 2017/198142 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them are specified in the specification.
- the WO 2022/136612 A1 provided for a binder composition comprising component A comprising polymer(s) A1 and optionally component B comprising component B1 which is selected from the group consisting of monosaccharides, disaccharides, hydroxyacetone, glycolaldehyde and mixtures thereof, wherein polymer(s) A1 comprises at least 70 wt% poly(amino acid)s based on the total weight of the polymer(s) A1 and has(have) a total weight average molecular weight Mw, total of 800 g/mol to 10000 g/mol, wherein the binder composition comprises 60 to 100 wt% polymer(s) A1, and 0 to 40 wt% component B1, based on the total weight of the sum of polymer(s) A1 and component B1,
- the WO 2022/136612 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification.
- the WO 2022/096518 A1 disclosed a composition comprising a polylysine component and a fibrous component.
- WO 2022/096518 A1 aimed to provide for objects such as fibreboards which have enhanced flexural properties; the fibreboards of WO 2022/096518 A1 were prepared upon curing of its compositions at high temperature which was 210 o C and with a press time factor of 30 sec/mm.
- the WO 2022/096518 A1 did not -at least- disclose a composition comprising a XL-component as the latter is specified in the specification.
- the WO 2023/148578 A1 disclosed a board comprising cellulose- containing material, such as plant fibers and/or wood chips and/or wood parts, and a glue which connects these cellulose-containing materials to each other, wherein the glue is based on hyperbranched polyamides, as well as a method for making such boards and a glue for such boards.
- the WO 2023/148578 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification.
- compositions comprising a constituent-A, which constituent-A consists of a polylysine component, a XL-component, and a fibrous component which fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component (compositions of the invention).
- compositions of the invention further relates to processes for obtaining an object from the compositions of the invention.
- the invention further relates to objects such as sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood e.g. fibreboards obtained by said processes (objects of the invention).
- the invention further relates to articles comprising a) a part which is solid at 23 o C and 1 atm; and one or both of b) and c), wherein b) is a composition of the invention, and c) is an object of the invention (articles of the invention).
- the invention further relates to various uses of any one or any combination of the compositions of the invention, the objects of the invention and the articles of the invention.
- the goal of the invention is to provide for compositions that are able to fast-cure at low temperature to prepare fibreboards [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], that have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa.
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- E apparent modulus of elasticity
- compositions of the invention constitute a major technological advancement for a number of industries since the fibreboards prepared from fast-curing the compositions of the invention at low temperature have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (R b ) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa. whereas the compositions of the state-of the-art upon fast-curing at low temperature resulted either in delamination or failed to meet the requirements for the internal bond strength, Rb and E.
- the invention is as set out in the claims.
- Figure 1 is an illustration of a hyperbranched polylysine which has a DB of 0.4 and a theoretical (calculated) molecular weight of 3350.6 Da.
- Figure 2 is an illustration of a primary ammonium salt of hyperbranched polylysine wherein the anion that counters some of the primary ammonium cations (- NH3 + ) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride, and wherein the primary ammonium salt of hyperbranched polylysine of Figure 2 has a DB of 0.4 and a theoretical (calculated) molecular weight of 3569.3 Da. 2023PF30090-01 FC DETAILED DISCLOSURE OF THE INVENTION
- the specification provides definitions for certain technical terms used in the specification and/or the claims.
- lysine is meant the ⁇ -amino acid having the following formula Any reference to ‘lysine’ in this specification refers to and encompasses both lysine’s two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s carbon atom which is directly linked to the carbon atom of the carboxylic group.
- polylysine is meant in the specification a polymer consisting of (reacted) lysine molecules which are linked by peptide bonds.
- the polylysine may be linear, branched or dendrimeric.
- the degree of branching (DB) of a polylysine ranges from and including 0 up to and including 1 (or equally a polylysine has a DB of at least 0 and at most 1).
- Examples of polylysines include ⁇ -polylysines, ⁇ -polylysines, hyperbranched polylysines, dendrimeric polylysines.
- polylysine a polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the polylysine.
- ⁇ -polylysine is meant in the specification a polymer which has the following formula A: Formula A wherein n is an integer equal or higher than 2, and a degree of branching (DB) equal to 0.
- primary ammonium salt of ⁇ -polylysine is meant in the specification an ⁇ -polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the ⁇ -polylysine, and wherein the primary ammonium salt of ⁇ -polylysine has a degree of branching (DB) equal to 0.
- DB degree of branching
- ⁇ -polylysine is meant in the specification a polymer which has the following formula B: Formula B wherein k is an integer equal or higher than 2, and a degree of branching (DB) equal to 0.
- primary ammonium salt of ⁇ -polylysine is meant in the specification an ⁇ -polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH 3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the ⁇ -polylysine, and wherein the primary ammonium salt of ⁇ -polylysine has a degree of branching (DB) equal to 0.
- hyperbranched polylysine is meant in the specification a polylysine which has a degree of branching (DB) higher than 0 and at most 0.99.
- primary ammonium salt of hyperbranched polylysine is meant in the specification a hyperbranched polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the hyperbranched polylysine, and wherein the primary ammonium salt of hyperbranched polylysine has a degree of branching (DB) higher than 0 and at most 0.99.
- DB degree of branching
- dendrimeric polylysine is meant in the specification a polylysine that has a degree of branching (DB) higher than 0.99 and at most 1.
- primary ammonium salt of dendrimeric polylysine is meant in the specification a dendrimeric polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the dendrimeric polylysine and wherein the primary ammonium salt of dendrimeric polylysine has a degree of branching (DB) higher than 0.99 and at most 1.
- peptide is meant in the specification a polymeric compound other than the polylysines-X (and obviously other than the polylysine component), wherein said polymeric compound consists of one chain which has at least 2 and at most 50 amino acids linked by peptide bonds.
- protein is meant in the specification a polymeric compound other than the polylysines-X (and obviously other than the polylysine component), wherein said polymeric compound consists of at least one chain which has at least 51 amino acids linked by peptide bonds.
- acetoacetoxy group is meant in the specification an organic group which has the following formula C: Formula C
- oxirane group is meant in the specification an organic group which has the following formula OD: Formula OD
- ketone group is meant in the specification an organic group which is according to any one of the following formulae EK1 to EK2: Formula EK1 Formula EK2
- ethylenically unsaturated group is meant in the specification an organic group which is according to any one of the following formulae EU1 to EU15: Formula EU1 2023PF30090-01 FC Formula EU5 Formula EU7 2023PF30090-01 FC Formula EU11 Formula EU12 2023PF30090-01 FC Formula EU15
- vinyl unsaturated group is meant in the specification an organic group which is according to any one of the following formulae VU1 to VU2: Formula VU2 wherein in Formula VU1, X is O or NH, in Formula VU2, X is O or NH, and R is a C 1 to C 10 alkyl group.
- metal containing compound is meant in the specification a compound containing a metal atom or metal cation.
- metal containing compounds include but are not limited to organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds.
- organometallic compounds include but are not limited to organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium).
- metal complexes include but are not limited to metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium).
- alkali metals preferably potassium, sodium, lithium
- alkali earth metals preferably calcium, magnesium, barium
- alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds include but are not limited to alkali earth metal (preferably calcium, magnesium, barium) hydroxides.
- gel content referring to a polylysine
- polylysine for example any one of the polylysines-X of the polylysine component
- gel content higher than 20 % is characterized as a ‘crosslinked polylysine’
- a polylysine with a gel content of at most 20 % is characterized as a ‘non-crosslinked polylysine’.
- the gel content is determined via the Gel-Content Method described in the Examples.
- flexural properties referring to an object e.g. fibreboards
- the flexural properties are determined via the Static Bending Method as described in the Examples.
- delamination it is meant in the context of this invention a mode of failure where after heat-pressing of the corresponding composition the resulting material fractured into layers or pieces.
- the press time factor in sec/mm
- PTF the press time (that is the time from closing to opening of the press) divided by the target thickness of a fibreboard; the target thickness refers to the 2023PF30090-01 FC thickness of the fibreboard at the end of the pressing step.
- the press time was 108 sec.
- fast-curing or equally ‘fast- cured’ or equally ‘fast-cure’
- low temperature means 160 o C.
- synthetic cellulose fibers “man-made cellulose fibers” or “manufactured cellulose fibers” or “artificial cellulose fibers” or “regenerated cellulose fibers” are used interchangeably and these terms are used to distinguish the synthetic cellulose fibers from the natural cellulose fibers and the natural lignocellulosic fibers, the latter two being vegetable fibers.
- engineered wood also known as mass timber, composite wood, man-made wood, or manufactured board
- derivative wood products includes a range of derivative wood products which are manufactured by binding or fixing together the various wood elements (e.g. fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips (e.g.
- engineered wood include but are not limited to plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites.
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- OSB oriented strand board
- laminated timber glulam; glued laminated timber
- CLT cross-la
- fibreboard encompasses low- density fibreboard (LDF; known also as particle board or chip board), and medium- density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)].
- LDF low- density fibreboard
- MDF medium- density fibreboard
- HDF high-density fibreboard
- wood chips is meant in the specification chipped woody biomass in the form of pieces with a defined particle size produced by mechanical treatment with sharp tools such as knives (ISO 16559-2014; ⁇ 4.226). The particle size distribution of the wood chips is determined via oscillating screen method using sieves with apertures of 3.15 mm and above according to the ISO 17827-1:2016.
- the median value of the particle size distribution (d50) is reported and is defined as the calculated particle size of a sample where 50 % of the 2023PF30090-01 FC particle mass is below and 50 % is above. Graphically the median value is established by the intersection of the cumulative distribution curve with the 50 % line (X axis: particle/hole size (mm) and Y-axis: accumulated % of weight (%)].
- room temperature is meant herein 23 ⁇ 0.5 o C.
- standard conditions is meant in the specification room temperature and atmospheric pressure, collectively.
- the sum of all components of which the composition of the invention (or part(s) thereof) comprises may, when expressed as a weight (or other) percentage of the composition (or the same part(s) thereof), total 100 wt% allowing for rounding errors.
- the sum of the percentage for each of such components may be less than 100 wt% to allow a certain percentage for additional amount(s) of any additional component(s) that may not be explicitly described herein. All combinations of minimum and maximum values of the parameters disclosed in the specification may be used to define the parameter ranges for various preferments or embodiments of the invention.
- moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise and/or are used in some or all of the invention as described in the specification may exist as one or more different forms such as any of those in the following non- exhaustive list: stereoisomers (such as enantiomers (e.g. E and/or Z forms), diastereoisomers and/or geometric isomers); tautomers (e.g. keto and/or enol forms).
- stereoisomers such as enantiomers (e.g. E and/or Z forms), diastereoisomers and/or geometric isomers
- tautomers e.g. keto and/or enol forms.
- the invention comprises and/or uses all such forms which are effective as defined in the specification.
- the invention provides for a composition
- a constituent-A which constituent-A consists of: - a polylysine component, - a XL-component, and - a fibrous component, wherein the polylysine component selected from the group consisting of polylysines-X and mixtures thereof, and wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines, preferably the polylysines-X are selected from the group consisting of hyperbranched polylysines, wherein each one of the polylysines-X has a degree of branching determined by 1 H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.60, an apparent viscosity determined by the Rheometry Method as disclosed in the 2023PF30090-01 FC specification, of at least 400 and at most 8000 mPa.s, and a gel content determined by the Gel-Content Method as disclosed in the specification
- the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule
- the XL- groups are selected from the group consisting of groups according to the formula XL2 (herein also mentioned as XL2-groups), groups according to the formula XL3 (herein also mentioned as XL3-groups), groups according to the formula XL4 (herein also mentioned as XL4-groups), groups according to the formula XL5(herein also mentioned as XL5-groups), groups according to the formula XL6 (herein also mentioned as XL6- groups), groups according to the formula XL7 (herein also mentioned as XL7-groups), and groups according to the formula XL8 (herein also mentioned as XL8-groups), preferably the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein
- Figure 1 depicts a hyperbranched polylysine which has a DB of 0.4 and a theoretical (calculated) molecular weight of 3350.6 Da
- Figure 2 depicts a primary ammonium salt of hyperbranched polylysine wherein the anion that counters some of the primary ammonium cations (-NH 3 + ) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride, and wherein the primary ammonium salt of hyperbranched polylysine of Figure 2 has a DB of 0.4 and a theoretical (calculated) molecular weight of 3569.3 Da.
- Lysine in either of its two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s central carbon atom
- L and ‘D’ refer to the chirality at lysine’s central carbon atom
- polylysines are formed from lysine or lysine salt [L-lysine, D-lysine, or any mixture thereof of L-lysine, e.g. a racemic mixture; or L defined -lysine salt , D-lysine salt or any mixture thereof e.g.
- Hyperbranched polylysines may be prepared via various processes.
- the processes for preparing hyperbranched polylysines may be categorized in four major categories: i) processes based on the ring opening addition polymerization of e-protected L-lysine-N-carboxyanhydrides (NCAs) with a nucleophilic starter, ii) processes where derivatives of L-lysine*xHCl that are activated on the carboxyl group, are used, iii) processes involving the direct thermal addition polymerization of L-lysines, and iv) processes where in the presence of at least one catalyst selected from the group consisting of tertiary amines, basic alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides, alkanoates, chelates, organometallic compounds of metal groups IIIA to VIIIA or IB to VB in the Periodic Table of Elements, a salt of lysine with at least one acid is involved.
- NCAs e-protected L-
- Hyperbranched polylysines can be prepared by what is called the AB 2 route.
- An AB 2 molecule is a term used to refer to a trifunctional monomer containing one reactive group A and two reactive groups B; Where these groups A and B are reactive 2023PF30090-01 FC with one another, hyperbranched polymers can be produced by intermolecular reaction.
- Lysine is an example of such a trifunctional monomer where the reactive group A is the carboxyl group and each of the two reactive groups B is the amino group of the lysine and where these A and B groups in the lysine are reactive with one another; thus, an AB 2 polymerization route of lysine leads to hyperbranched polylysines.
- Hyperbranched polylysines can also be prepared as follows: a reactor, e.g. a glass-reactor equipped with a distillation set-up is charged with L-lysine in water (50 wt%).
- the reactor Upon the completion of the charge of the reactor with L-lysine in water (50 wt%), the reactor is slowly (over 2- 8 hours) heated up to 120-190 o C (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion).
- the reaction then proceeds for 2-30 hours at the desired temperature.
- L-lysine in water 50 wt%) can be added to the reactor as water is being distilled off, in order to maintain the reactor’s filling at a certain level.
- the reaction is monitored by taking samples over regular time periods, diluting the samples to 60 wt% in water, and measuring the apparent viscosity.
- the reactor that may be used in this process can be a high-pressure reactor. If a high-pressure reactor is used in this process, then said high-pressure reactor, equipped with a distillation set-up which distillation set-up is connected to the reactor via a pressure release valve, is charged with L-lysine in water (50 wt%).
- the pressure in the high-pressure reactor starts to build up while the pressure release valve is closed off and the reactor is heated up to 120-190 o C.
- the reaction then proceeds for 2-30 hours at the desired temperature.
- L-lysine in water (50 wt%) can be added to the reactor as water is being distilled off, in order to maintain the reactor’s filling at a certain level.
- the reaction is monitored by taking samples over regular time periods, diluting the samples to 60wt% in water, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If necessary, water can be added to the reaction mixture prior to discharging in order to yield a product with the desired solids content and 2023PF30090-01 FC apparent viscosity.
- the preparation of hyperbranched polylysines in agreement with the invention shown in the Examples offer examples of the processes described above in this paragraph. Another way for preparing hyperbranched polylysines, uses L-lysine hydrochloride as starting material.
- L-lysine hydrochloride 550 g, 3 mol
- NaOH 120 g, 3 mol
- a 1-L glass reactor with a distillation set-up. This reactor is heated to 120-190 o C and stirred for 2 to 30 hours.
- samples are taken every few hours, dissolved in water to a 60 wt% solids content, and the apparent viscosity measured.
- water the amount added is calculated so the reaction mixture will have a resultant solid content of 70-80 wt%) is added dropwise to the reactor and as water is added the temperature is lowered to 90 o C.
- the resultant reaction mixture in water (solid content 70-80 wt%) is then discharged at 90 o C.
- Another way for preparing hyperbranched polylysines uses L-lysine hydrochloride and L-lysine as starting materials. According to this L-lysine in water (50 wt%) (409.4 g, 1.4 mol), L-lysine hydrochloride (255.7 g, 1.4 mol), and NaOH (55.8 g,1.4 mol) were added to a 1-L glass reactor. This reactor is heated to 120-190 o C and stirred for 2 to 30 hours. In order to follow the reaction, samples are taken every few hours, dissolved in water to a 60 wt% solids content, and the apparent viscosity measured.
- a yet another process for preparing hyperbranched polylysines is based on the ring-opening addition polymerization of ⁇ -protected L-lysine-N- carboxyanhydrides (NCAs) with a nucleophilic starter.
- NCAs ⁇ -protected L-lysine-N- carboxyanhydrides
- N ⁇ ,N ⁇ -di(9-fluorenyl-methoxycarbonyl)-L-lysine (N ⁇ ,N ⁇ -diFmoc Lys) was introduced as a branching point.
- Deprotection with piperidine in dimethyl formamide (DMF) gave two new amine groups, which allowed ring-opening polymerization of TFA-Lys-NCA and Z-Lys-NCA. These reaction cycles were repeated a number of times.
- Structurally similar hyperbranched block copolymers have also been described by Birchall et al. in Chem. Commun.1998, 1335-1336.
- a-Amino acid NCAs were subjected to ring-opening polymerization with an aliphatic amine.
- N,N'- 2023PF30090-01 FC Di(benzyloxycarbonyl)-L-lysine p-nitrophenyl ester was introduced as a branching point, and after deprotection of H 2 /Pd/C had two free amine groups for the further ring opening of amino acid NCAs. These reaction cycles were repeated a number of times.
- a yet another process for preparing hyperbranched polylysines is based on derivatives of L-lysine*2HCl which are activated on the carboxyl group.
- hyperbranched polylysines were prepared in a one-pot synthesis with activation of the carboxyl group by means of N-hydroxy succinimide (NHS).
- NHS-activated L-lysine*2HCl was stirred for 23 hours in dimethyl sulfoxide (DMSO) with the addition of catalytic amounts of dimethyl aminopyridine (DMAP) and 3 equivalents of diisopropyl-ethylamine (DIEA), and the polymer was precipitated from ethyl acetate.
- DMAP dimethyl aminopyridine
- DIEA diisopropyl-ethylamine
- a yet another process for preparing hyperbranched polylysines is based the thermal addition copolymerization of amino acid mixtures. The thermal addition polymerization of free lysine is known and has been carried out under various reaction conditions.
- Plaquet and co-workers (Biochimie 1975, 57 1395-1396) polymerized L-lysine in aqueous solution at 105 o C for a period of up to 10 weeks, or else by heating at 165 o C for 8 hours. The reaction was carried out without catalyst and the yields, at below 72.5 % without exception, were very low.
- Harada (Bull. Chem. Soc. Japan 1959, 32, 1007-1008) polymerized L-lysine at 180 to 230 o C for between 30 minutes and 2 hours under a nitrogen atmosphere.
- US 8846842 B2 disclosed yet another process for preparing polylysines that does not require protective-group operations or activation of carboxyl groups and in which it is also possible to attain higher molecular weights than those known from the prior art.
- the object has been achieved by means of a process for preparing non-crosslinked hyperbranched polylysines by reacting: (A) a salt of lysine with at least one acid, (B) if appropriate, at least one amino acid other than lysine, (C) if appropriate, at least one dicarboxylic or polycarboxylic acid or copolymerizable derivatives thereof and (D) if appropriate, at least one diamine or polyamine or copolymerizable derivatives thereof, 2023PF30090-01 FC (E) if appropriate, in at least one solvent at a temperature from 120 to 200 o C in the presence of at least one catalyst (F) selected from the group consisting of (F1) tertiary amines and amidines, (F2) basic alkali metal
- Hyperbranched polylysines can, for example, be synthesized by direct thermal addition polymerization of L-lysine or ammonium salts of L-lysine. The thermal addition polymerization of lysine is carried out in the absence of solvent.
- WO 2007/060119 described the polycondensation of L-lysine hydrochloride in the presence of sodium hydroxide, water (10 wt% based on the L-lysine hydrochloride) and the catalyst dibutyltin dilaurate. The mixture was heated with stirring to an internal temperature of 150 o C.
- WO 2016/062578 A1 disclosed a process for the preparation of hyperbranched polylysines suitable for large scale production of polylysine with improved yield.
- polylysines can be prepared by a process comprising the steps of: (a) heating a boiling aqueous reaction mixture comprising lysine and water in a weight ratio of 1:10 to 3:1 within 2 to 8 hours, for example within 4 to 8 hours, to a temperature in the range from 135 to 165 o C, and (b) keeping the reaction mixture of step (a) at a temperature in a range from 135 to 165 o C at a pressure below atmospheric pressure, wherein water is removed from the mixture, and any temperature 2023PF30090-01 FC increase is less than or equal to 30 o C in 60 minutes.
- Customary technical aqueous lysine solutions can be used in the process as disclosed in WO 2016/062578 A1 and no catalyst is required.
- the mixture is in a liquid state, e.g., a melt of polylysine, not a resin.
- the aqueous starting mixture is an aqueous solution of lysine in water.
- the lysine comprised by the aqueous starting mixture can be L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, e.g. a racemic mixture.
- the aqueous starting mixture can, for example, be an aqueous solution of L-lysine in water that contains 50 wt% of L-lysine and 50 wt% of water; e.g., ADM Liquid L-Lysine, Product Code: 035101 supplied by Archer Daniels Midland, Sewon L- Lysine ® 50 percent liquid feed supplied by Paik Kwang, or BestAminoTM L-Lysine liquid feed grade supplied by CJ CheilJedang.
- Polylysine is formed from lysine in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water.
- the removal of water from the reaction mixture favors the formation of the polylysine.
- the temperature of the reaction mixture is increased continuously.
- the process as disclosed in WO 2016/062578 A1 requires that water is removed from the reaction mixture. Any means suitable for removing water may be applied in order to remove water from the reaction mixture. Water is preferably evaporated from the mixture. The water is most preferably removed from the mixture by distillation. This process requires a pressure below atmospheric pressure in the second step.
- the pressure reduction facilitates the evaporation of water and thus accelerates the polycondensation reaction.
- the weight average molecular weight and number average molecular weight of the polylysine depends on the overall duration of the process and the temperature of the reaction mixture. If the reaction mixture is kept for longer times at higher temperatures, crosslinking is more likely to occur.
- the process is carried out without a catalyst.
- the process may be carried out continuously or, preferably, batchwise.
- the process is preferably carried out in what is called a one- pot mode, in which the lysine is included in its entirety in the initial charge and the polycondensation reaction is carried out in a reactor with back-mixing.
- the primary ammonium salt of hyperbranched polylysines can for example be prepared via protonation of the amino groups of a hyperbranched polylysine with for example acidic agents e.g. protic acids, alkenylcarboxylic acids, alkylsulfonic acids.
- acidic agents e.g. protic acids, alkenylcarboxylic acids, alkylsulfonic acids.
- protonation agents the agents that may be used for the preparation of the primary ammonium salt of polylysines.
- Such protonation results in a primary ammonium salt of hyperbranched polylysine that 2023PF30090-01 FC contains in its structure at least one primary ammonium cation (-NH 3 + ) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the hyperbranched polylysine.
- the structure of the anion depends on the reactant used for the protonation of the amino groups of the hyperbranched polylysine; exemplary anions include but are not limited to halide anions (e.g. fluoride, chloride, bromide, iodide) carboxylate anions, sulfonate anions.
- the anion is selected from the group consisting of halide anions, carboxylate anions, sulfonate anions, more preferably the anion is selected from the group consisting of halide anions, and carboxylate anions, even more preferably the anion is selected from the group consisting of halide anions, for example the anion is selected from the group consisting of fluoride, chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride and bromide, for example the anion is chloride.
- the XL-component is able to react with the polylysine component.
- the members of the XL-component may be prepared via several processes. For example, in order to prepare a XL-component having at least two XL2 groups, freshly degassed 1,6- hexamethylene diisocyanate is stirred at 23 °C under nitrogen in the presence of 2 mol % of catalyst (e.g. pyridine derivate) and the XL-component having at least two XL2 groups is isolated as a highly viscous liquid; commercially available examples of such XL-components are Desmodur® N 3400 and Desmodur® XP 2840 offered by Covestro.
- catalyst e.g. pyridine derivate
- XL-component having at least two XL3.1.1 groups 222.3 g of isophorone diisocyanate (IPDI), 65 g of solvent naphtha 100 and 34 g of 1- methoxy propyl acetate are placed in a vessel; 193 g solid 3,5-dimethylpyrazole is added in portions, with stirring, at a temperature ranging from 75 to 85 o C, and stirring is continued for approximately one hour at 80 °C, until no isocyanate groups are detected; the XL-component having at least two XL3.1.1 groups is isolated as a clear, slightly yellowish solution; commercially available examples of such XL-components are: Bayhydur® BL2867, Desmodur® PL 350 and Desmodur® BL 3575/1 offered by Covestro.
- a XL-component having at least two XL6.1 groups 693.3 g of an aqueous solution of NaHSO3 (15 wt%) is mixed in a vessel with 3.22 g tetrabutylammonium bromide (TBAB); subsequently and once the mixture is homogenized, 693.3 g of isopropanol alcohol are added to the solution; 222.3 g IPDI are placed in a dry four necked flask that was purged with nitrogen and heated in an oil bath; the solution of NaHSO 3 /TBAB/IPA is placed in a dropping funnel and slowly added into the four necked flask containing the IPDI at room temperature at a rate of 2 ml/min and the mixture is left to react for approximately 3 h, in order to obtain the XL-component having at least two XL6.1 groups.
- TBAB tetrabutylammonium bromide
- XL-component 2023PF30090-01 FC having at least two XL5.1 groups 222.3 g of isophorone diisocyanate are dissolved in 350 g of Solvesso 100 by heating to 80 °C; subsequently, 4 g of dried sodium methoxide are added followed by the dropwise addition of 264 g of diethyl malonate in such a way that the reaction temperature does not exceed 90 °C; the reaction mixture is kept at 90 °C until an isocyanate content of lower than 0.5 %; the XL-component having at least two XL5.1 groups is obtained upon filtration of the reaction mixture; commercially available examples of such XL-components are: Desmodur® BL 3475 and Desmodur® BL 3370 offered by Covestro.
- XL-component having at least two XL4.1.1 groups
- 222.3 g of IPDI, 65 g of solvent naphtha 100 and 34 g of 1- methoxy propyl acetate are placed in a vessel.
- methylethylketone oxime 174 g is added in portions under stirring at about 70 o C, and stirring is continued for approximately 3.5 h at 70 °C until no isocyanate groups are detected, in order to obtain the XL- component having at least two XL4.1.1 groups; commercially available examples of such a XL-components are: Bayhydur® 2781, Baybond® XL 6366, Desmodur® BL 3175 and Desmodur® BL 4265 offered by Covestro.
- XL- component having at least two XL3.3.1 groups 222.3 g of IPDI, 65 g of solvent naphtha 100 and 34 g of 1-methoxy propyl acetate are placed in a vessel; 226 g of caprolactam is added in portions, with stirring, at 70 o C and stirring is continued for approximately 3 h at 70 °C until no isocyanate groups can be detected in order to obtain the XL-component having at least two XL3.3.1 groups; commercially available examples of such a XL- components are: Baybond® XL 825m Baybond® XL 7270, Desmodur® BL 1100/1 and Desmodur® BL 3272 offered by Covestro.
- IPDI and acetone are placed in a vessel; an equimolar amount of Imidazole with respect to the molar amount of isocyanate groups is added in portions, with stirring, at 70 o C, and stirring is continued for approximately 3 h at 70 °C until no isocyanate groups can be detected, in order to obtain the XL- component having at least two XL3.2.1 groups.
- Examples of XL-component include but are not limited to monomeric blocked diisocyanates, monomeric blocked polyisocyanates, polymeric blocked diisocyanates, polymeric blocked polyisocyanates, monomeric diuretdiones, polymeric diuretdiones, monomeric polyuretdiones, polymeric polyuretdiones, blocked isocyanate functional polyurethanes.
- the monomeric blocked diisocyanates, monomeric blocked polyisocyanates, polymeric blocked diisocyanates, polymeric blocked polyisocyanates, monomeric diuretdiones, polymeric diuretdiones, monomeric polyuretdiones, polymeric polyuretdiones, blocked isocyanate functional polyurethanes may be of one of or a combination of aliphatic, cycloaliphatic and aromatic nature.
- XL- component examples include but are not limited to Desmodur® N 3400, Desmodur® XP 2840, 2023PF30090-01 FC Bayhydur® BL2867, Desmodur® PL 350, Desmodur® BL 3575/1, Desmodur® BL 3475, Desmodur® BL 3370, Bayhydur® 2781, Baybond® XL 6366, Desmodur® BL 3175, Desmodur® BL 4265, Baybond® XL 825m, Baybond® XL 7270, Desmodur® BL 1100/1, Desmodur® BL 3272 all of them offered by Covestro.
- composition is as disclosed in A0 or in A1 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has a degree of branching determined by 1 H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.55, more preferably at least 0.30 and at most 0.50, even more preferably at least 0.30 and at most 0.45.
- degree of branching determined by 1 H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.55, more preferably at least 0.30 and at most 0.50, even more preferably at least 0.30 and at most 0.45.
- the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (- NH3 + ) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of halide anions, carboxylate anions and sulfonate anions; more preferably the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (
- each one of the polylysines-X has an apparent viscosity determined by the Rheometry Method as disclosed in the specification of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s.
- composition is as disclosed in A0 or in any one of A1 to A4 or as in any combination derived from the disclosure in this section and the entire 2023PF30090-01 FC specification including the claims, wherein each one of the polylysines-X has an amine number (abbreviated as AN) determined by the Titration Method as disclosed in the specification that is higher than its acid value (abbreviated as AV) determined by the Titration Method as disclosed in the specification.
- AN amine number
- AV acid value
- the composition is as disclosed in A0 or in any one of A1 to A5 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has a number average molecular weight (abbreviated as M n ) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da.
- M n number average molecular weight
- composition is as disclosed in A0 or in any one of A1 to A6 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da.
- Mw weight average molecular weight
- composition is as disclosed in A0 or in any one of A1 to A7 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has an amine number (abbreviated as AN) determined by the Titration Method as disclosed in the specification, of at least 200 and at most 700 mg KOH/g, preferably at least 250 and at most 600 mg KOH/g, more preferably at least 250 and at most 500 mg KOH/g, especially at least 300 and at most 400 mg KOH/g.
- AN amine number
- composition is as disclosed in A0 or in any one of A1 to A8 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has an acid value (abbreviated as AV) determined by the Titration Method as disclosed in the specification, of at least 10 and at most 150, preferably at least 10 and at most 100, for example at least 10 and at most 90, for example at least 30 and at most 150, for example at least 30 and at most 100, for example at least 30 and at most 90 mg KOH/g.
- AV acid value
- each one of the polylysines-X independently has an amine number (AN) determined by the Titration Method as disclosed in the specification, of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mg KOH/g.
- AN amine number
- each one of the polylysines-X independently has an amine number (AN) determined by the Titration Method as disclosed in the specification, of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mg KOH/g and wherein the AN is higher than the acid value (AV) determined by the Titration Method as disclosed in the specification.
- AN amine number
- each one of the polylysines-X independently has an apparent viscosity determined by the Rheometry Method as disclosed in the specification, of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s, and wherein the AN is higher
- each one of the polylysines-X independently has: - a number average molecular weight (abbreviated as M n ) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as M w ) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 5000 and at most 30000 Da, for example at least 10000 and at most 30000 Da, - apparent viscos
- each one of the polylysines-X has: - a number average molecular weight (abbreviated as Mn) determined by the Gel- Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as M w ) determined by the Gel- Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da, - a polydispersity (abbreviated as PD) calculated as the ratio of M w /M
- each one of the polylysines-X has: - a number average molecular weight (abbreviated as Mn) weight determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da, - a polydispersity calculated as the ratio of Mw/Mn, of at least 2 and at most 15, preferably at
- each one of the members of the XL- component has a number average molecular weight determined by the Gel-Permeation Chromatography Method-2 as disclosed in the specification, of at least 100 and at most 10000, for example at least 100 and at most 5000, for example at least 100 at most 4000, for example at least 100 and at most 3000, for example at least 100 and at most 2500, for example at least 100 and at most 2000, for example at least 150 and at most 5000, for example at least 150 at most 4000, for example at least 150 and at most 3000, for example at least 150 and at most 2500, for example at least 150 and at most 2000, for example at least 300 and at most 10000, for example at least 400 and at most 10000, for example at least 500 and at most 10000 Da.
- the Gel-Permeation Chromatography Method-2 as disclosed in the specification, of at least 100 and at most 10000, for example at least 100 and at most 5000, for example at least 100 at most 4000, for example at least 100 and at most 3000, for example at
- each one of the monomeric compounds of the XL-component has a number average molecular weight determined by the Gel- Permeation Chromatography Method-2 as disclosed in the specification, of at least 100 and at most 5000, for example at least 100 at most 4000, for example at least 100 and at most 3000, for example at least 100 and at most 2500, for example at least 100 and at most 2000, for example at least 150 and at most 5000, for example at least 150 at most 4000, for example at least 150 and at most 3000, for example at least 150 and at most 2500, for example at least 150 and at most 2000 Da.
- composition is as disclosed in A0 or in any one of A1 to A15 and A17 or as in any combination derived from the disclosure in this section and the 2023PF30090-01 FC entire specification including the claims, wherein each one of the polymeric compounds of the XL-component has a number average molecular weight determined by the Gel- Permeation Chromatography Method-2 as disclosed in the specification, of at least 300 and at most 20000, for example at least 300 at most 15000, for example at least 300 and at most 10000, for example at least 300 and at most 8000, for example at least 300 and at most 6000, for example at least 300 and at most 5000, for example at least 300 at most 4000, for example at least 300 and at most 3000, for example at least 300 and at most 2500, for example at least 300 and at most 2000, for example at least 500 and at most 20000, for example at least 500 at most 15000, for example at least 500 and at most 10000, for example at least at
- each one of the polymeric compounds of the XL-component is a linear polymeric compound, preferably each one of the polymeric compounds of the XL-component is a linear non-branched polymeric compound.
- each one of the polymeric compounds of the XL-component is a linear non-branched polymeric compound.
- composition is as disclosed in A0 or in any one of A1 to A18 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the XL-component is a monomeric compound having at least two XL-groups per molecule.
- XL-component is a monomeric compound having at least two XL-groups per molecule.
- the composition is as disclosed in A0 or in any one of A1 to A18 or as in any combination derived from the disclosure in this section and the entire 2023PF30090-01 FC specification including the claims, wherein the XL-component is a polymeric compound having at least two XL-groups per molecule; more preferably the XL-component is a linear polymeric compound having at least two XL-groups per molecule; even more preferably the XL-component is a linear non-branched polymeric compound having at least two XL-groups per molecule.
- the subject matter of this paragraph is mentioned in the specification as ‘A21’.
- the composition is as disclosed in A0 or in any one of A1 to A21 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein none of the monomeric compounds of the XL- component and none of the polymeric compounds of the XL-component contains Si atoms in its structure.
- the subject matter of this paragraph is mentioned in the specification as ‘A22’.
- the composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise water.
- the subject matter of this paragraph is mentioned in the specification as ‘A23’.
- the composition is as disclosed in A0 or in any one of A1 to A23 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises water in an amount determined by the Water-Content Method as disclosed in the specification, of at least 1 and at most 90, preferably at least 2 and at most 90, more preferably at least 3 and at most 90, even more preferably at least 5 and at most 90, for example at least 1 and at most 80, for example at least 2 and at most 80, for example at least 3 and at most 80, for example at least 5 and at most 80, for example at least 1 and at most 70, for example at least 2 and at most 70, for example at least 3 and at most 70, for example at least 5 and at most 70, for example at least 1 and at most 60, for example at least 2 and at most 60, for example at least 3 and at most 60, for example at least 5 and at most 60, for example at least 1 and at most 50, for example at least 2 and at most 50, for example at least 3 and at most most
- the composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises water and the aggregate amount of the constituent-A and water in the composition is higher than 10, preferably at least 20, for example at least 30, for example at least 40, for example at least 50, for example at least 60, for example at least 70, for example at least 80, for example at least 90, for example at least 92, for example at least 95, for example at least 97 for example at least 98, for example at least 99 pph of the composition, for example the composition consists of the constituent-A and water, wherein the amount of water is determined by the Water-Content Method disclosed in the specification.
- composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the constituent-A is present in an amount of at least 85 and at most 100, for example at least 87 and at most 100, for example at least 90 and at most 100, for example at least 92 and at most 100, for example at least 95 and at most 100, for example at least 97 and at most 100, for example at least 98 for example at least 99 and at most 100 wt% of the composition.
- A26 The subject matter of this paragraph is mentioned in the specification as ‘A26’.
- the composition is as disclosed in A0 or in any one of A1 to A26 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises an organic solvent in an amount of at most 50, preferably at most 40, more preferably at most 30, even more preferably at most 20, most preferably at most 10, especially at most 5, more especially at most 3 pph of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A26 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of organic solvent.
- composition is as disclosed in A0 or in any one of A1 to A28 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A and water.
- composition consists of constituent-A and water.
- A29 is mentioned in the specification as ‘A29’.
- 2023PF30090-01 FC Preferably the composition is as disclosed in A0 or in any one of A1 to A29 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A.
- A30 The subject matter of this paragraph is mentioned in the specification as ‘A30’.
- the composition is as disclosed in in A0 or in any one of A1 to A30 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-B which is selected from the group consisting of proteins and mixtures thereof. More preferably, the composition may optionally comprise the constituent-B in an amount of at most 0.95, preferably at most 0.90, more preferably at most 0.80, for example at most 0.70, for example at most 0.60, for example at most 0.50 for example at most 0.40 for example at most 0.30 for example at most 0.20 for example at most 0.10 for example at most 0.05 pph of the composition.
- the subject matter of this paragraph is mentioned in the specification as ‘A31’.
- composition is as disclosed in A0 or in any one of A1 to A30 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-B and the constituent-B is different and distinct from any other component and constituent of the composition.
- A32 The subject matter of this paragraph is mentioned in the specification as ‘A32’.
- the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition; more preferably the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of
- composition is as disclosed in claim 1 in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-C and wherein the constituent-C is different and distinct from any other component and constituent of the composition.
- A34 The subject matter of this paragraph is mentioned in the specification as ‘A34’.
- the composition is as disclosed in claim 1 or in A0 or in any one of A1 to A34 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-D which constituted-D is selected from the group consisting of: i) monosaccharides in their aldose or ketose form, ii) oligosaccharides, iii) 2023PF30090-01 FC polysaccharides, iv) monomeric or polymeric compounds that yield one or more reducing sugars in situ e.g. upon heating, and mixtures of i) to iv), and the constituent-D is different and distinct from any other component and constituent of the composition.
- a constituent-D which constituted-D is selected from the group consisting of: i) monosaccharides in their aldose or ketose form, ii) oligosaccharides, iii) 2023PF30090-01 FC polysaccharides, iv) monomeric or
- composition is as disclosed in A0 or in any one of A1 to A34 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-D and wherein the constituent-D is different and distinct from any other component and constituent of the composition.
- A36 The subject matter of this paragraph is mentioned in the specification as ‘A36’.
- the composition is as disclosed in A0 or in any one of A1 to A36 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-E which constituent-E is selected from the group consisting of peptides and mixtures thereof, and wherein the constituent-E is different and distinct from any other component and constituent of the composition, in an amount of at most 0.30 for example at most 0.20 for example at most 0.10 for example at most 0.05 wt% of the composition.
- the subject matter of this paragraph is mentioned in the specification as ‘A37’.
- composition is as disclosed in A0 or in any one of A1 to A36 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-E and wherein the constituent-E is different and distinct from any other component and constituent of the composition.
- A38 The subject matter of this paragraph is mentioned in the specification as ‘A38’.
- the composition is as disclosed in A0 or in any one of A1 to A38 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-F which constituent-F is selected from the group consisting of compounds comprising at least two acetoacetoxy groups, and mixtures thereof, and wherein the constituent-F is different and distinct from any other component and constituent of the composition.
- constituent-F is selected from the group consisting of compounds comprising at least two acetoacetoxy groups, and mixtures thereof, and wherein the constituent-F is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A39 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-F1 which constituent-F1 is selected from the group consisting of compounds comprising only one acetoacetoxy group, and mixtures thereof, and wherein the constituent-F1 is different 2023PF30090-01 FC and distinct from any other component and constituent of the composition.
- constituent-F1 is different 2023PF30090-01 FC and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A40 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-K which constituent-K is selected from the group consisting of compounds comprising at least two oxirane groups, and mixtures thereof, and wherein the constituent-K is different and distinct from any other component and constituent of the composition.
- constituent-K is selected from the group consisting of compounds comprising at least two oxirane groups, and mixtures thereof, and wherein the constituent-K is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A41 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-K1 which constituent-K1 is selected from the group consisting of compounds comprising only one oxirane group, and mixtures thereof, and wherein the constituent-K1 is different and distinct from any other component and constituent of the composition.
- constituent-K1 is selected from the group consisting of compounds comprising only one oxirane group, and mixtures thereof, and wherein the constituent-K1 is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A42 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-L which constituent-L is selected from the group consisting of compounds comprising at least two ethylenically unsaturated groups, and mixtures thereof, and wherein the constituent-L is different and distinct from any other component and constituent of the composition.
- constituent-L is selected from the group consisting of compounds comprising at least two ethylenically unsaturated groups, and mixtures thereof, and wherein the constituent-L is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A43 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-L1 which constituent-L1 is selected from the group consisting of compounds comprising only one ethylenically unsaturated group, and mixtures thereof, and wherein the constituent-L1 is different and distinct from any other component and constituent of the composition.
- constituent-L1 is selected from the group consisting of compounds comprising only one ethylenically unsaturated group, and mixtures thereof, and wherein the constituent-L1 is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A44 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-M which constituent-M is selected from the group consisting of compounds comprising at least two vinyl unsaturated groups, and mixtures thereof, and wherein the constituent-M is different and distinct from any other component and constituent of the composition.
- constituent-M is selected from the group consisting of compounds comprising at least two vinyl unsaturated groups, and mixtures thereof, and wherein the constituent-M is different and distinct from any other component and constituent of the composition.
- composition is as disclosed in A0 or in any one of A1 to A45 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-M1 which constituent-M1 is selected from the group consisting of compounds comprising only one vinyl unsaturated group, and mixtures thereof, and wherein the constituent-M1 is different and distinct from any other component and constituent of the composition.
- constituent-M1 is selected from the group consisting of compounds comprising only one vinyl unsaturated group, and mixtures thereof, and wherein the constituent-M1 is different and distinct from any other component and constituent of the composition.
- the composition is as disclosed in A0 or in any one of A1 to A46 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition optionally comprises (preferably comprises) constituent-N in an amount of at least 0.01 and at most 10, preferably at least 0.02 and at most 8, more preferably at least 0.05 and at most 5, for example at least 0.01 and at most 4, for example at least 0.03 and at most 3, for example at least 0.05 and at most 2, for example at least 0.75 and at most 2 wt% on the aggregate weight amount of the polylysine component and the XL-component, and which constituent-N is selected from the group consisting of amines, amine salts, aza compounds, metal containing compounds, and mixtures thereof; preferably the constituent-N is selected from the group consisting of amines, amine salts, aza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium
- Examples of amine salts include but are not limited to N,N- dimethylcyclohexyl ammonium acetate.
- Examples of monoaza compounds include but are not limited to 1-Azabicyclo[2.2.2]octane (known also as ABCO or quinuclidine).
- diaza compounds include but are not limited to 1,4- diazabicyclo(2,2,2)octane (DABCO), 1.8-diazabicyclo[5.4.0]undec-7-ene formate, 1,8- diazabicyclo[5.4.0]undece-1-ene (DBU), diazabicyclononane (DBN), 3,3,6,9,9- pentamethyl-2,10-diazabicyclo[4.4.0]dec-1-ene.
- DBU 1,4- diazabicyclo(2,2,2)octane
- DBU 1,8- diazabicyclo[5.4.0]undece-1-ene
- DBN diazabicyclononane
- 3,3,6,9,9- pentamethyl-2,10-diazabicyclo[4.4.0]dec-1-ene 1,4- diazabicyclo(2,2,2)octane
- DBU 1,8- diazabicyclo[5.4.0]undece-1-ene
- metal containing compounds and in particular organometallic compounds include but are not limited to dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTDA), dioctyltin maleate, monobutyltin monoacylate, monobutyl tin sulfide, monobutyltin oxide, trioctyltin laurate, bis(trioctyltin)oxide (TOTO), bis(tributyltin) oxide (TBTO), tetrabutylstannoxane diacetate Butyltin tris(-ethylhexanoate).
- DBTDL dibutyltin dilaurate
- DBTDA dibutyltin diacetate
- dioctyltin maleate monobutyltin monoacylate
- monobutyl tin sulfide monobutyltin oxide
- trioctyltin laurate bis(trioc
- metal containing compounds and in particular metal complexes include but are not limited to zinc(II)-acetylacetonate, zinc napthenate, bismuth tris(2-ethylhexanoate), aluminum dionate complex, cobalt bis(2-ethyl hexanoate), cobalt (III)-acetylacetonate, zirconium bis(2-ethyl hexanoate), zinc bis(2- ethyl hexanoate), titanium tetra(acetylacetonate), Ti tetra(ethyl acetoacetate) calcium bis(2-ethyl hexanoate), chromium tris(2-ethyl hexanoate), sodium methoxide, potassium methoxide, lithium methoxide, 4,12-dibutyl-2,6,10,14-tetramethyl-1,7,9,15-tetraoxa- 4,12-diaza-8-st
- metal containing compounds and in particular alkali metal inorganic compounds include but are not limited to LiOH, KOH, NaOH.
- metal containing compounds and in particular alkali earth metal inorganic compounds include but are not limited to Ca(OH) 2 , Mg(OH) 2 , Ba(OH) 2 .
- TAA tributylamine
- TEA triethylamine
- DABCO 1,4-diazabicyclo(2,2,2)octane
- DBTDL dibutyltin dilaurate
- zinc(II)- acetylacetonate zinc bis(2-ethyl hexanoate)
- sodium methoxide LiOH, Ca(OH) 2 , Mg(OH) 2 , are particularly preferred.
- the composition is as disclosed in A0 or in any one of A1 to A26 and in any one of A31 to A47 or as in any combination derived from the disclosure 2023PF30090-01 FC in this section and the entire specification including the claims, wherein the composition consists of constituent-A, and constituent-N.
- the subject matter of this paragraph is mentioned in the specification as ‘A48’.
- the composition is as disclosed in A0 or in any one of A1 to A28 or in any one of A31 to A47 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A, constituent-N and water.
- the subject matter of this paragraph is mentioned in the specification as ‘A49’.
- the composition is as disclosed in A0 or in any one of A1 to A49 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of formaldehyde resins.
- the subject matter of this paragraph is mentioned in the specification as ‘A50’.
- the composition is as disclosed in A0 or in any one of A1 to A50 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of urea-formaldehyde resins.
- A51 The subject matter of this paragraph is mentioned in the specification as ‘A51’.
- the composition is as disclosed in A0 or in any one of A1 to A51 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of melamine- formaldehyde resins.
- the subject matter of this paragraph is mentioned in the specification as ‘A52’.
- the composition is as disclosed in A0 or in any one of A1 to A49 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of formaldehyde resins, and free of urea-formaldehyde resins, and free of melamine-formaldehyde resins, and free of mixtures thereof.
- the subject matter of this paragraph is mentioned in the specification as ‘A53’.
- the fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component.
- both the fibrous component and the inventive compositions comprise only vegetable fibers.
- the composition is as disclosed in A0 or in any one of A1 to A53 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous component is present in an amount of at least 10 and at most 98, preferably at least 20 and at most 98, more preferably at least 30 and at most 98, most preferably at least 40 and at most 98, especially at least 2023PF30090-01 FC 50 and at most 98, more especially at least 60 and at most 98, even more especially at least 70 and at most 98, most especially at least 80 and at most 98, for example at least 85 and at most 98 wt% of the composition.
- the subject matter of this paragraph is mentioned in the specification as ‘A54’.
- the composition is as disclosed in A0 or in any one of A1 to A54 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous element comprises vegetable fibers in an amount of at least 20, preferably at least 30, more preferably at least 40, for example at least 50, for example at least 60, for example at least 70, for example at least 80, for example at least 90, for example at least 95, for example at least 96, for example at least 97, for example at least 98, for example at least 99, for example at least 99.5 wt% of the fibrous element, for example the fibrous element consists of vegetable fibers.
- the subject matter of this paragraph is mentioned in the specification as ‘A55’.
- composition is as disclosed in A0 or in any one of A1 to A55 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof.
- the vegetable fibers are selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof.
- the subject matter of this paragraph is mentioned in the specification as ‘A56’.
- the composition is as disclosed in A0 or in any one of A1 to A56 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof.
- the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers
- the composition is as disclosed in A0 or in any one of A1 to A57 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, and mixtures thereof.
- the subject matter of this paragraph is mentioned in the specification as ‘A58’.
- the composition is as disclosed in A0 or in any one of A1 to A58 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are wood fibers.
- the subject matter of this paragraph is mentioned in the specification as ‘A59’.
- the composition is as disclosed in A0 or in any one of A1 to A59 or as in any combination derived from the disclosure in this section and the entire 2023PF30090-01 FC specification including the claims, wherein the fibrous element is selected from the group consisting of fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips, shavings, flakes, lamellae, pulp, and mixtures thereof; preferably the fibrous element is selected from the group consisting of fibers, filaments, yarns, threads, staple fiber yarns, particles, chips, shavings, flakes, pulp, and mixtures thereof; more preferably the fibrous element is a wood chip.
- the fibrous element is a wood chip.
- the composition is as disclosed in A0 or in any one of A1 to A60 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous component consists of wood chips wherein the d50 which is the median value of the particle size distribution of the wood chips determined according to the ISO 17827-1:2016, is at least 1 and at most 50, preferably at least 1 and at most 40, for example at least 1 and at most 30, for example at least 1 and at most 20, for example at least 1 and at most 15, for example at least 1 and at most 10, for example at least 1 and at most 8 mm.
- the subject matter of this paragraph is mentioned in the specification as ‘A61’.
- a process for obtaining an object comprising the steps a to c: a) providing a composition as disclosed in A0 or in any one of A1 to A61 or as in any combination derived from the disclosure in this section and the entire specification including the claims; and b) subjecting the composition to heat and/or pressure and/or vacuum, preferably simultaneous heat and pressure, to form an object, and c) collecting the object.
- the subject matter of this paragraph is mentioned in the specification as ‘A62’.
- the process for obtaining an object is as disclosed in A62 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the step b is as follows: b) subjecting the composition to heat -preferably at any temperature in the range of from and including 100 up to and including 300 o C, for example in the range of from and including 100 up to and including 280 o C, for example in the range of from and including 100 up to and including 260 o C, for example in the range of from and including 100 up to and including 250 o C, for example in the range of from and including 100 up to and including 240 o C, for example in the range of from and including 100 up to and including 230 o C for example in the range of from and including 100 up to and including 220 o C for example in the range of from and including 100 up to and including 210 o C, for example in the range of from and including 110 up to and including 300 o C, 2023PF30090-01 FC for example in the range of from and including 110 up to and including 300
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood [for example plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density 2023PF30090-01 FC fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including
- the process for obtaining an object is as disclosed in any one of A62 to A63 as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites.
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-dens
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB); Most preferably the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of a fiberboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)].
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein 2023PF30090-01 FC the object is a low-density fibreboard (LDF; known also as particle board or chip board.
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a medium-density fibreboard (MDF).
- MDF medium-density fibreboard
- the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a high-density fibreboard (HDF; known also as waferboard, flakeboard)].
- HDF high-density fibreboard
- the process for obtaining an object is as disclosed in any one of A62 to A64 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood.
- the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood.
- the process for obtaining an object is as disclosed in any one of A62 to A65 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is engineered wood.
- the subject matter of this paragraph is mentioned in the specification as ‘A66’.
- the process for obtaining an object is as disclosed in any one of A62 to A66 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)].
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood [for example plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as 2023PF30090-01 FC waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trus
- engineered wood for example plywood, densified wood (including chemically dens
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I- beams), trusses (including roof and floor trusses), transparent wood composites.
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- OSB oriented strand board
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB).
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- OSB oriented strand board
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high- density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB).
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high- density fibreboard
- OSB oriented strand board
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is a fiberboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)].
- LDF low-density fibreboard
- MDF medium-density fibreboard
- HDF high-density fibreboard
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is a low-density fibreboard (LDF; known also as particle board or chip board; for example the object is a medium-density fibreboard (MDF).
- LDF low-density fibreboard
- MDF medium-density fibreboard
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is a high- density fibreboard (HDF; known also as waferboard, flakeboard)].
- HDF high- density fibreboard
- the subject matter of this paragraph is mentioned in the specification as ‘A69’.
- 2023PF30090-01 FC Preferably the object as disclosed in A68 as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood.
- the subject matter of this paragraph is mentioned in the specification as ‘A70’.
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is engineered wood.
- the subject matter of this paragraph is mentioned in the specification as ‘A71’.
- the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims is a fibreboard.
- the subject matter of this paragraph is mentioned in the specification as ‘A72’.
- an article comprising: a) a part which is solid at 23 o C and 1 atm; and one or both of b) and c), wherein b) is a composition as disclosed in A0 or in any one of A1 to A61 or as in any combination derived from the disclosure in this section and the entire specification including the claims, and c) is an object (especially engineered wood, more especially fibreboard) as disclosed in any one of A68 to A72, or as in any combination derived from the disclosure in this section and the entire specification including the claims.
- the subject matter of this paragraph is mentioned in the specification as ‘A73’.
- ligament replacement, composite structures, ceramic structures defense applications (including but not limited to ballistic protection, body armor, ballistic vests, ballistic helmets, ballistic vehicle protection, composite structures, ceramic structures), sports/recreational applications (including but not limited to toys, fencing, skates, skateboarding, snowboarding, suspension lines on sport parachutes, paragliders, kites, kite lines for kite sports, climbing equipment, composite structures, ceramic structures), architectural applications (including but not limited to windows, doors, (pseudo-)walls, cable), bottling applications, household applications (including but not limited to household appliances, whitegoods, furniture, computer housings), machinery applications (including but not limited to can and bottle handling machine parts, moving parts on weaving machines, bearings, gears, composite structures, ceramic structures, computer housings), can applications, coil applications, energy related applications (including but not limited to generators for wind, tide or solar energy), and electricity related applications (including but not limited to cabinets for electrical wire or switch boards).
- energy related applications including but not limited to generators for wind, tide or solar
- any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments in connection with any piece of disclosure in any one of A0 to A74 disclosed in this section can be combined with each other and with any other feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments of the invention as these are disclosed in the entire specification including the claims. All combinations of minimum and maximum values of the parameters disclosed in this section may be used to define the parameter ranges for various preferments and embodiments of the invention disclosed in this section.
- any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments of the invention as these are disclosed in this section, in 2023PF30090-01 FC the claims and in the entire specification can be combined with each other.
- the boundary value is included in each range for each parameter. All combinations of minimum and maximum values of the parameters disclosed in this section may be used to define the parameter ranges for the various preferments and embodiments disclosed in this section.
- D-(+)-Glucose (anhydrous, purity 99 %) was obtained from Thermo Scientific (abbreviated as glucose).
- ⁇ -Polylysine (light yellow powder with a purity of 99.4%) was supplied by Bonding Chemical.
- This polylysine is mentioned in the examples as PLL-2C and it is not according to the claimed invention.
- the temperature in the reactor was slowly (over 4 hours) raised to 105 o C (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion).
- 105 o C the temperature in the reactor reached 105 o C
- the temperature of the reactor was slowly increased to 160 o C.
- 2610 g SEWON L-Lysine® was added slowly into the reactor at the same rate that water was being distilled off.
- the temperature was maintained at 160 °C for 1 hour.
- Hyperbranched Polylysine 3 (PLL-3C) The preparation of the hyperbranched polylysine 3 (PLL-3C) was carried out as follows: 3400 g of SEWON L-Lysine® were added at room temperature, to a 5 litre high-pressure reactor equipped with a distillation set up which was connected to the reactor via a pressure release valve (herein ‘PR valve’); once all the amount of SEWON L-Lysine® was introduced into the reactor, the PR valve was closed off. Subsequently, the temperature in the reactor was slowly (over 2 hours) raised to 130 o C about 2 hours and the pressure reached 3.5 bar.
- PR valve pressure release valve
- the PR valve was then carefully opened to allow for the distillation of water; the temperature of the reactor was maintained at 130 o C up until a solids content of 82 ⁇ 1 wt.% was obtained; during this stage and in order to maintain a mass of about 3400 g in the reactor, SEWON L-Lysine® was being pumped into the reactor at the same rate that water was being distilled off. Once a solids content of 82 ⁇ 1 wt.% was obtained (at that time the pressure in the reactor dropped from 3.5 bar to 1.2 bar), then the PR valve was closed off. Subsequently, the temperature and the pressure in the reactor were raised to 190 °C and 5 ⁇ 0.5 bar, respectively.
- the temperature and the pressure in the reactor were maintained at 190 °C and 5 ⁇ 0.5 bar, respectively for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 4800 mPa.s; during this stage, water was being distilled off by periodically and carefully opening the PR valve making sure that the pressure in the reactor was maintained at 5 ⁇ 0.5 bar.
- the temperature in the reactor was then decreased to 90 oC and water was dosed into the reactor and reach a solids content of 60 ⁇ 1 wt%.
- Fontijne TP800 to form boards of 28 (L) x 34 (W) x 1.2 (T) cm (surface of 425 cm 2 ).
- the thickness of all the fibreboards prepared and tested was 12 mm ⁇ 10 %.
- the density of all the fibreboards prepared and tested was 750 kg/m 3 ⁇ 10 %.
- the weight amounts of the polylysine component shown in Table 1 were calculated on the basis of the solids content determined by the Solids-content Method as disclosed in the specification, of the polylysine component; thus the reported weight amounts of the polylysine component shown in Table 1 correspond to solids content 100 % of the polylysine component.
- the weight amounts of the XL-component shown in Table 1 were calculated on the basis of the solids content as the latter was reported by the supplier 2023PF30090-01 FC (see ⁇ 1.1); thus the reported weight amounts of the XL-component shown in Table 1 correspond to solids content 100 % of the XL-component. Determination of the M n , M w 1.1.4.
- M n , M w of the polylysines-X (‘Gel- Permeation Chromatography Method-1’)
- the number average molecular weight (M n ) and the weight average molecular weight (M w ) of a member of the polylysines-X were determined via Gel Permeation Chromatography (GPC) calibrated with a set of lysozyme from chicken egg white (CAS 12650-88-3; product number L6876; lyophilized powder, protein ⁇ 90 %, ⁇ 40000 units/mg protein; molecular weight single chain 14.3 kDa) and bovine serum albumin (CAS 9048-46-8; product number A2153; lyophilized powder, ⁇ 96 %, molecular weight 66 kDa) standards both supplied by Sigma-Aldrich and using as eluent a solution of 500 mM NaCl and 0.0425 wt% H3PO4 in MilliQ water (the solution having a pH of
- the GPC measurements were carried out on a Waters® Acquity UPLC® H-Class Bio system equipped with: i) a photodiode array (PDA) detector [Acquity TM UPLC TM (1.5 ⁇ L biocompatible cell; measurement was carried out at 225 nm); supplied by WATERS ® ]; ii) a separation module equipped with one Agilent Bio-SEC column (7.8 x 300 mm, pore size 100 ⁇ , filled with particles having particle size of 3 ⁇ m, product number: 5190-2501) supplied by Agilent. The Mn and Mw were determined with the help of suitable software for data processing (Empower TM 3, supplied by WATERS ® ). 1.1.5.
- PDA photodiode array
- M n The number average molecular weight (M n ) of a member of XL- component was determined via Gel Permeation Chromatography (GPC) calibrated with a set of polystyrene standards with a molecular weight range of from 162 up to 3.8 x10 6 Da, and using as eluent stabilized tetrahydrofuran [THF with 0.007- 0.015% w/w butyl- hydroxytoluene (BHT)] (THF) modified with 0.8 (v/v %) acetic acid at a flow rate of 1 mL/min at 40 °C.50 mg of a solid sample of a member of XL-component, were dissolved in 5 mL eluent for 16 hours at room temperature without shaking, and used for the measurement.40 ⁇ L of the solution thus prepared were injected into the system for
- amine number (AN) and the acid value (AV) (‘Titration Method’)
- the titrate consisted of 1.000 g of polylysine (sample) (the amount refers to solids content), 60.00 mL of Millipore Ultra RO water and 10.000 mL of a solution of 1.000 N HCl in water [Titripur® supplied by Merck; product number 1.09057].
- the data processing and control handling of all titrations described in this were accomplished via the use of the software Tiamo TM 2.4 supplied by Metrohm AG.
- the titration curve [pH vs. Volume of titrant (x-axis)] (abbreviated as TC) and the first derivative curve of the TC [electrical potential vs.
- volume of titrant (x-axis)] are recorded simultaneously and are plotted together in the same graph (pH on Y1-axis and electrical potential on Y2-axis, and volume of titrant on X-axis).
- the first derivative curve of the TC is known as ERC which stands for Equivalence point Recognition Criteria and is expressed in units for electrical potential (mV).
- ERC affords either 2 or 3 peaks (ERC peaks) in succession to each other. Each of these ERC peaks corresponds to a certain volume of titrant.
- ERC peaks typically the one of highest signal (delta voltage)- corresponds to the lowest volume of the titrant (V min ) (in mL) and another one ERC peak corresponds to the highest volume of the titrant (Vmax) (in mL).
- the measurements for the determination of the AN and AV were performed in duplicate and the reported values for each of the AN and AV were the average of these measurements.
- Determination of the apparent viscosity (‘Rheometry Method’) The apparent viscosity (shear stress divided by the shear rate) was determined using the rotational rheometer RheolabQC supplied by Anton Paar, connected to a water bath, controlled at 23.0 ⁇ C. This method is based on ISO 3219:1993.
- the appropriate spindle/cup combination and shear rate are chosen based on the estimated apparent viscosity.
- a Z3 spindle/cup combination which and a shear rate of 100 s -1 .
- the cup is then filled with sample (polylysine dissolved in water with a solids content of 60 ⁇ 1 %).
- the spindle is inserted into the cup, the cup is mounted in the viscometer and the spindle is connected to the instrument.
- the correct program (for all our measurements we selected the program for the Z3 spindle in combination with a shear rate of 100 s -1 ) is selected on the RheolabQC and the measurement is performed.
- Solids-content Method The solids content (wt%) was determined using a Halogen Moisture Analyzer HR73 supplied by Mettler Toledo. For this measurement, 1.00 g of sample (polylysine dissolved in water) is weighed onto a glass fiber pad which is placed on an aluminium pan and then heated at 140 o C for 30 minutes. The solids content is determined automatically based on the difference in mass before and after the heating at 140 o C.
- the degree of branching (DB) of a polylysine is determined via 1 H-NMR spectroscopy and calculated according to the equation 1: (equation 1) wherein D is equal to or higher than 0, L is equal to or higher than 0, and at least one of the D and L is higher than 0; and wherein D is the integral of the 1 H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae D1a and D1b) of any number of the following group(s) shown in Formulae D1a and D1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the D is equal to zero):
- Formula D1a Formula D1b L represents the sum of L ⁇ and L ⁇ , wherein L ⁇ is the integral of the 1 H-NMR
- the 1 H-NMR spectra were recorded at room temperature on a Bruker Ascend TM 400 Spectrometer, using deuterated methanol (also known as tetradeuteromethanol or methanol-d 4 ) as solvent. Methanol-d 4 is the preferred solvent; however, other suitable deuterated solvents may be used.
- Methanol-d 4 is the preferred solvent; however, other suitable deuterated solvents may be used.
- methanol-d 4 the chemical shifts of the 1 H-NMR peaks corresponding to: - the D-proton(s) are found at 4.15-4.40 ppm; - the L ⁇ -proton(s) are found at 3.90-4.10 ppm; and - the L ⁇ -proton(s) are found at 3.25-3.30 ppm.
- the gel content of a polylysine was determined as follows: 2023PF30090-01 FC A mixture of 10 % solids content of a polylysine in water was prepared and stored at room temperature for 24 hours. Subsequently, an amount of 3000 g of the mixture thus prepared (herein sample), was filtrated through a pre-weighed (Mf before ) filter e.g. a folded qualitative filter paper, in order to remove any insoluble fraction of average size of at least 5 micron and higher. Once the filtration was completed, the filter was washed with water, the amount of which was double of the amount of the sample.
- Mf before pre-weighed
- the filter was placed in a vacuum oven at 40 o C under a pressure of 50 mbar, for 12 hours in order to remove any water. Subsequently, the filter was weighed again (Mf after ).
- the gel content was calculated from the equation 2: (equation 2) wherein Mfafter is the mass of the filter after the removal of the water, Mf before is the mass of the filter before the filtration of the sample, and M polylysine is the mass of the polylysine in the sample (taken into account the solids content of the sample).
- the M polylysine is 30 g.
- the length (L), width (W) and the thickness (T) The length (L) of the specimens was measured with a ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen.
- the width (W) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen.
- the thickness (T) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the thickness of the specimen. 2023PF30090-01 FC 1.1.7.
- Determination of the density (d) Specimens were prepared by cutting the fibreboard prepared in one piece of 150 mm by 40 mm.
- the length (L; in m), width (W; in m) and thickness (T; in m) of the specimens were measured as mentioned above, as well as their weight (M; in Kg).
- i) the modulus of rupture (Rb) and ii) the apparent modulus of elasticity (E) were determined via static bending tests according to the ASTM D1037-12 and in particular section 9 (entitled ‘Static Bending’) of the ASTM D1037-12, subject to the following two differences from the provisions of the section 9 of the ASTM D1037-12: i) the specimens were prepared by cutting the produced panel in two pieces of 150 ⁇ 1 mm by 40 ⁇ 1 mm, and ii) each specimen was placed in a 3-point (center loading) fixture and the length of the span (L) was fixed to 100 mm.
- Table 1 summarizes the comparative and inventive compositions as well as the internal bond strength, the modulus of rupture (Rb) and the apparent modulus of elasticity (E) of the fibreboards prepared upon fast-curing (press time factor equal to 10 sec/mm) at low temperature (160 o C) of their corresponding compositions.
- the abbreviation ‘DL’ shown in Table 1 stands for delamination (for delamination see definition in the section entitled Detailed Description of the Invention). From the results shown in Table 1, it is evident that only the inventive compositions provided a solution to the technical problem.
- the resulted fibreboards had: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6 MPa, and - apparent modulus of elasticity (E) of at least 800 MPa.
- each one of the comparative compositions C1, C2 (which offers a simulation of the compositions of WO 2022/096518 A1) C3, C6 , C7, C8, C9, C10 and C11 resulted in delamination, whilst comparative compositions C4 and C5 failed to have - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6 MPa, and - apparent modulus of elasticity (E) of at least 800 MPa.
- inventive compositions I1 to I8 to the comparative compositions C2 and C5 which are outside the claimed range for the weight ratio K weight ratio K of C2 was 0.02 and the one of C5 was 6.0
- inventive composition I2 to the comparative compositions C3 and C6 which are outside the claimed range for the amount of the polylysine component in the composition the amount of polylysine component in C3 was 0.30 wt% of the composition and the one of C6 was 10.0 wt% of the composition
- compositions of the state-of the-art upon fast-curing at low temperature resulted either in delamination or in remarkably lower performance as to the required internal bond strength, modulus of rapture and apparent modulus of elasticity.
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Abstract
The invention relates to compositions comprising a constituent-A, which constituent-A consists of a polylysine component, a XL-component, and a fibrous component which fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component (compositions of the invention). The invention further relates to processes for obtaining an object from the compositions of the invention. The invention further relates to objects such as sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood e.g. fibreboards obtained by said processes (objects of the invention). The invention further relates to articles comprising a) a part which is solid at 23 oC and 1 atm; and one or both of b) and c), wherein b) is a composition of the invention, and c) is an object of the invention (articles of the invention). The invention further relates to various uses of any one or any combination of the compositions of the invention, the objects of the invention and the articles of the invention.
Description
2023PF30090-01 Foreign Countries COMPOSITIONS FOR FIBREBOARDS WITH ENHANCED PROPERTIES UPON FAST-CURING AT LOW TEMPERATURE FIELD OF THE INVENTION The invention lies in the field of compositions comprising vegetable fibers, a hyperbranched polylysine and a component having groups of the following formulae
which compositions are particularly suitable for the preparation of objects such as engineered wood e.g. fibreboards.
2023PF30090-01 FC BACKGROUND In the context of this invention but also in the literature, polylysine refers to several types of lysine homopolymers which may differ from each other in terms of stereochemistry and link position. Lysine (in either of its two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s central carbon atom) which is the precursor amino acid, contains two amino groups; one at the α-carbon and one at the ɛ-carbon. Either of these two amino groups can be the location of polymerization, resulting in α-polylysine or ɛ-polylysine. Fibers (or fibres; the terms are used interchangeably in the context of this invention) constitute a class of materials that are continuous filaments or are in discrete elongated pieces, similar to lengths of thread. Human uses for fibers are diverse. They can be spun into filaments, string or rope, used as a reinforcing agent in composites into sheets to make products such as paper or felt. Fibers are often used in the manufacture of other materials. Fibers may be recycled. In the context of this invention the term ‘fiber’ includes also recycled fibers. On the basis of their origin, fibers are divided into two main categories namely natural and synthetic fibers. Synthetic fibers are also known as man-made or artificial or manufactured fibers. Natural fibers are further divided into: i) mineral fibers (e.g. asbestos, wollastonite, attapulgite, halloysite), ii) animal fibers (e.g. silk, wool, sinew, cashmere, mohair, angora, animal hair), and iii) vegetable fibers are based on arrangements of cellulose (known also as ‘natural cellulose fibers’), or arrangements of cellulose with lignin (known also as ‘natural lignocellulosic fibers’), and are derived from sources of natural cellulose or natural cellulose with lignin, such as from plants which are living organisms of the kind exemplified by trees, bamboos, shrubs, herbs, grasses, ferns, and mosses, absorbing water and inorganic substances through its roots, and synthesizing nutrients in its leaves by photosynthesis using the green pigment chlorophyll. Examples of vegetable fibers include but are not limited to wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf (hibiscus cannabinus) fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof. Synthetic (also known as man-made or artificial or manufactured fibers) can be further divided into: i) cellulose fibers regenerated from natural resources, known also as cellulose-regenerated fibers (e.g. rayon, modal, Lyocell, cellulose acetate, cellulose triacetate), ii) inorganic fibers and iii) polymer fibers.
2023PF30090-01 FC Cellulose fibers are a subset of fibers. Cellulose fibers are fibers of cellulose from any source, either natural or manufactured (the latter is also known as synthetic cellulose fibers). Therefore, cellulose fibers can be natural (e.g. cellulose fibers from sources of natural cellulose such as from trees (including bamboos), seaweed, or synthetic (e.g. cellulose fibers regenerated from natural cellulose such as rayon, modal, Lyocell, cellulose acetate, cellulose triacetate). The synthetic cellulose fibers are also known in the art as man-made cellulose fibers or as regenerated cellulose fibers or as manufactured cellulose fibers or as artificial cellulose fibers. In the context of this invention the terms “synthetic cellulose fibers”, “man-made cellulose fibers” or “manufactured cellulose fibers” or “artificial cellulose fibers” or “regenerated cellulose fibers” are used interchangeably and these terms are used to distinguish the synthetic cellulose fibers from the natural cellulose fibers and the natural lignocellulosic fibers, the latter two being vegetable fibers. One of the most important type of fibers are wood (including recycled wood) fibers. There are two main types of wood: a) softwoods and b) hardwoods. Softwoods come from cone bearing trees. Exemplary softwoods include but are not limited to pine, redwood, and fir. Softwoods can be used for furniture and doors but are mostly used in construction for roof trusses and stud partitions. Hardwoods come from leaved trees. These trees may have flowers and may produce seeds such as nuts and fruit. Exemplary hardwoods include but are not limited to oak, beech and mahogany. Hardwoods are denser than softwoods and are stronger and more durable as well. They are used for furniture and are typically more expensive than softwoods. Wood may be recycled. In the context of this invention the term ‘wood’ includes also recycled wood. During the wood production, wood (softwoods, hardwoods) is used to manufacture timber (also known as lumber); timber is effectively wood manufactured into beams and planks. In the context of this invention the term ‘solid wood’ is used to distinguish between timber and engineered wood. Engineered wood (also known as mass timber, composite wood, man- made wood, or manufactured board) includes a range of derivative wood products which are manufactured by binding or fixing together the various wood elements (e.g. fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips (e.g. wood chips, sawdust), shavings (e.g. sawmill shavings), flakes, lamellae, pulp (e.g. wood pulp), and mixtures thereof), via various methods of fixation to form effectively a composite material. Exemplary types of engineered wood include but are not limited to plywood, densified wood (including chemically densified wood), fibreboard [the term includes low- density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard,
2023PF30090-01 FC flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites. Engineered wood products are engineered to precise design specifications, which are tested to meet national or international standards and provide uniformity and predictability in their structural performance. Engineered wood products are used in a variety of applications, from home construction to commercial buildings to industrial products. Fibreboards constitute a subset of engineered wood. Types of fibreboards (in order of increasing density) include low-density fibreboards (LDF; known also as particle boards or chip boards), medium-density fibreboards (MDF), high-density fibreboards (HDF; known also as waferboards, flakeboards). In the context of this invention fibreboards with density of at most 500 kg/m3 (preferably of at least 100 and at most 500 kg/m3) are viewed as LDF. In the context of this invention fibreboards with density higher than 500 and at most 1000 kg/m3 (preferably of at least 550 and at most 800 kg/m3) are viewed as MDF. In the context of this invention fibreboards with density higher than 1000 kg/m3 (preferably higher than 1000 and at most 1500, more preferably higher than 1000 and at most 1100 kg/m3) are viewed as HDF. In principle, fibreboards can be formed using either a wet-forming or a dry-forming process. In a wet-forming process, water is used to distribute the fibers into a mat and then pressed into a board. In the dry process, fibers from the refiner go through a dryer and blow line where an adhesive is applied and then formed into a web which is pressed into a board. A typical fibreboard manufacture -at an industrial scale- begins with wood chipping: fresh or recycled wood material is cut and sorted to small pieces of similar size. Chips are washed to remove things such as dirt and sand. Metal scraps such as nails can be removed with a magnet placed over a conveyor belt on which the chips move forward. In the case of, for example MDF, chips are then steamed to soften them for defibration. Small amount of paraffin wax is added to the steamed chips and they are transformed into fluffy fibers in a defibrator and soon afterwards sprayed with urea-formaldehyde resins (UF) or phenol-formaldehyde resins (PF). Wax prevents fibers from clumping together during storage. Chips in the case of particle boards may also be sprayed with an additional resin before the next steps. Fibers or chips are arranged into a uniform ‘mat’ on a conveyor belt. This mat is pre-compressed and then hot-pressed (simultaneous application of heat and pressure). Hot-pressing binds the fibers or chips together. The board is then cooled, trimmed, sanded and maybe veneered or laminated. UF resins are dominantly used in the MDF industry.
2023PF30090-01 FC In recent years, there is an increasing demand for compositions that are able to fast-cure at low temperature to prepare fibreboards [the term includes low- density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], that have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa. Both the modulus of rupture (Rb) and the apparent modulus of elasticity (E) constitute the flexural properties of an object e.g. a fibreboard. The internal bond strength and the flexural properties of fibreboards are critical for their consumer acceptance as well as their commercial success. Fibreboards that do not meet at least one of the above thresholds for each one of internal bond strength, Rb and E do not perform at a level acceptable by the end consumer. Fibreboards with enhanced internal bond strength and flexural properties are thus desirable. Enhanced flexural properties allow for more tolerance in mechanical and/or physical stresses that fibreboards are subject to during their lifetime of use including -but not limited to- their preparation, packaging, unpackaging, transport, storage and use. Fibreboards that suffer from poor flexural properties are usually fragile with little or no tolerance at all for mechanical and/or physical stresses. As a consequence the poor flexural properties severely limits their application and uses -if any-, and/or their lifetime -once in use- and consequently are typically rejected by the consumers. In addition, enhanced internal bond strength is also desirable since it ensures acceptable physical integrity and allow for more tolerance in mechanical and/or physical stresses that fibreboards are subject to during their lifetime of use. Fast-curing at low temperature of compositions suitable for preparing fibreboards is also very desirable since it enhances production efficiencies, increases throughput and lowers the amount of energy required to cure said compositions. The EP 2614117 B1 related to a multi-layer lignocellulose-containing molding. The EP 2614117 B1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification. The US 2017/198142 A1 related to aqueous curable binder compositions comprising (i) a polyphenolic macromolecular compound which bears a multitude of phenol or polyhydroxybenzene radicals, such as catechol radicals,
2023PF30090-01 FC preferably lignosulfonate salt, condensed tannins and mixtures thereof, and (ii) a polyamine functional compound comprising primary and/or secondary and/or tertiary and/or quaternary amine functional groups, and/or reaction production of (i) and (ii), the ratio of polyphenolic macromolecular compound to polyamine functional compound ranging from 98:2 to 50:50, preferably from 98:2 to 70:30 wt%, more preferably from 95:5 to 80:20 wt%. The US 2017/198142 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them are specified in the specification. The WO 2022/136612 A1 provided for a binder composition comprising component A comprising polymer(s) A1 and optionally component B comprising component B1 which is selected from the group consisting of monosaccharides, disaccharides, hydroxyacetone, glycolaldehyde and mixtures thereof, wherein polymer(s) A1 comprises at least 70 wt% poly(amino acid)s based on the total weight of the polymer(s) A1 and has(have) a total weight average molecular weight Mw, total of 800 g/mol to 10000 g/mol, wherein the binder composition comprises 60 to 100 wt% polymer(s) A1, and 0 to 40 wt% component B1, based on the total weight of the sum of polymer(s) A1 and component B1, wherein the weight amounts of the polymer(s) A1 and component B1 are selected such that the total weight of the sum of polymer(s) A1 and component B1 is 100 wt%. The WO 2022/136612 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification. The WO 2022/096518 A1 disclosed a composition comprising a polylysine component and a fibrous component. WO 2022/096518 A1 aimed to provide for objects such as fibreboards which have enhanced flexural properties; the fibreboards of WO 2022/096518 A1 were prepared upon curing of its compositions at high temperature which was 210 oC and with a press time factor of 30 sec/mm. The WO 2022/096518 A1 did not -at least- disclose a composition comprising a XL-component as the latter is specified in the specification. The WO 2023/148578 A1 disclosed a board comprising cellulose- containing material, such as plant fibers and/or wood chips and/or wood parts, and a glue which connects these cellulose-containing materials to each other, wherein the glue is based on hyperbranched polyamides, as well as a method for making such boards and a glue for such boards. The WO 2023/148578 A1 did not -at least- disclose a composition comprising a polylysine component and a XL-component as each one of them is specified in the specification. None of EP 2614117 B1, US 2017/198142 A1, WO 2022/136612 A1, WO 2022/096518 A1, WO 2023/148578 A1, CN 109056327, US 2012/202041 A1, WO
2023PF30090-01 FC 2022/096518 A1, WO 2020/230034 A1, WO 2008/057390 A2, WO 2008/068180 A1, WO 2016/009054 A1, WO 2016/009062 A1, WO 2022/096518, KR 102187998 B1, CN 110903786 A, WO 2010/031718 A1, WO 2008/046892 A2, WO 2009/037240 A1, US 8846842 B2, US 2007/277928 A1, US 8790632 B2, WO 2022136611 A1, WO 2022136613 A1, WO 2022136614 A1, US 2012/202041 A1, JP H 10279794 A disclosed a composition as disclosed in the specification and none of them dealt with the provision of compositions that are able to fast-cure at low temperature to prepare fibreboards [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], that have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa, and - reduced swelling in thickness, let alone provide a solution to this problem. Therefore, unless a technical solution that would enable the fast preparation of fibreboards at low temperature and at the same time ensure enhanced internal bond strength, a Rb and an E, fibreboards restrict their use in a variety of - otherwise potential- industrial uses for them. Such a desired technical solution still represents an unmet need since the solution to such a problem, is particularly challenging and complex. The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
2023PF30090-01 FC SUMMARY OF THE INVENTION The invention relates to compositions comprising a constituent-A, which constituent-A consists of a polylysine component, a XL-component, and a fibrous component which fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component (compositions of the invention). The invention further relates to processes for obtaining an object from the compositions of the invention. The invention further relates to objects such as sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood e.g. fibreboards obtained by said processes (objects of the invention). The invention further relates to articles comprising a) a part which is solid at 23 oC and 1 atm; and one or both of b) and c), wherein b) is a composition of the invention, and c) is an object of the invention (articles of the invention). The invention further relates to various uses of any one or any combination of the compositions of the invention, the objects of the invention and the articles of the invention. The goal of the invention is to provide for compositions that are able to fast-cure at low temperature to prepare fibreboards [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], that have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa. This goal was surprisingly achieved by the compositions as described in the claims and disclosed in the specification. More particularly, it has surprisingly been found that when the compositions of the invention were fast-cured at 160 oC to prepare fibreboards, the resulted fibreboards had: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and
2023PF30090-01 FC - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa. The compositions of the invention constitute a major technological advancement for a number of industries since the fibreboards prepared from fast-curing the compositions of the invention at low temperature have: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6, preferably at least 7, more preferably at least 8 MPa, and - apparent modulus of elasticity (E) of at least 800, preferably at least 900, more preferably at least 1000, even more preferably at least 1100, most preferably at least 1200 MPa. whereas the compositions of the state-of the-art upon fast-curing at low temperature resulted either in delamination or failed to meet the requirements for the internal bond strength, Rb and E. The invention is as set out in the claims. Many other variations, combinations and embodiments within the scope of the claims will be apparent to those skilled in the art. BRIEF DESCRIPTION OF THE FIGURES The specification contains two figures. The figures are offered as an illustration only and not as a definition of the limits of the present disclosure. To assist those of skill in the art in practicing the disclosed invention, reference is made to the accompanying figures: Figure 1 is an illustration of a hyperbranched polylysine which has a DB of 0.4 and a theoretical (calculated) molecular weight of 3350.6 Da. Figure 2 is an illustration of a primary ammonium salt of hyperbranched polylysine wherein the anion that counters some of the primary ammonium cations (- NH3+) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride, and wherein the primary ammonium salt of hyperbranched polylysine of Figure 2 has a DB of 0.4 and a theoretical (calculated) molecular weight of 3569.3 Da.
2023PF30090-01 FC DETAILED DISCLOSURE OF THE INVENTION The specification provides definitions for certain technical terms used in the specification and/or the claims. Any other technical term used in the specification and/or the claims that is not defined in the specification has the meaning attributed to it by one of ordinary skill in the art. By the term ‘lysine’ is meant the α-amino acid having the following formula
Any reference to ‘lysine’ in this specification refers to and encompasses both lysine’s two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s carbon atom which is directly linked to the carbon atom of the carboxylic group. The degree of branching (DB) of a polylysine is determined via 1H-NMR spectroscopy and calculated according to the equation 1: 2^ ^^ = 2^ + ^ (equation 1) wherein D is equal to or higher than 0, L is equal to or higher than 0, and at least one of the D and L is higher than 0; and wherein D is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae D1a and D1b) of any number of the following group(s) shown in Formulae D1a and D1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the D is equal to zero):
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Formula D1a Formula D1b L represents the sum of Lα and Lε, wherein Lα is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae L1a and L1b) of any number of any one of the following group(s) shown in Formulae L1a and L1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the Lα is equal to zero):
and Lε is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon indicated in bold in Formulae L2a and L2b) of any number of any one of the following group(s) shown in Formulae L2a and L2b that may be present in the polylysine (if no such methine protons are present in the polylysine, the Lε is equal to zero):
Formula L2a Formula L2b
2023PF30090-01 FC The DB ranges from and including 0 up to and including 1 (or equally the DB is at least 0 and at most 1). By ‘polylysine’ is meant in the specification a polymer consisting of (reacted) lysine molecules which are linked by peptide bonds. The polylysine may be linear, branched or dendrimeric. Obviously, the degree of branching (DB) of a polylysine ranges from and including 0 up to and including 1 (or equally a polylysine has a DB of at least 0 and at most 1). Examples of polylysines include α-polylysines, ɛ-polylysines, hyperbranched polylysines, dendrimeric polylysines. By ‘primary ammonium salt of polylysine’ is meant in the specification a polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3+) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the polylysine. By ‘α-polylysine’ is meant in the specification a polymer which has the following formula A:
Formula A wherein n is an integer equal or higher than 2, and a degree of branching (DB) equal to 0. By ‘primary ammonium salt of α-polylysine’ is meant in the specification an α-polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3+) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the α-polylysine, and wherein the primary ammonium salt of α-polylysine has a degree of branching (DB) equal to 0.
2023PF30090-01 FC By ‘ɛ -polylysine’ is meant in the specification a polymer which has the following formula B:
Formula B wherein k is an integer equal or higher than 2, and a degree of branching (DB) equal to 0. By ‘primary ammonium salt of ɛ-polylysine’ is meant in the specification an ɛ-polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3 +) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the ɛ-polylysine, and wherein the primary ammonium salt of ɛ-polylysine has a degree of branching (DB) equal to 0. By ‘hyperbranched polylysine’ is meant in the specification a polylysine which has a degree of branching (DB) higher than 0 and at most 0.99. By ‘primary ammonium salt of hyperbranched polylysine’ is meant in the specification a hyperbranched polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3+) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the hyperbranched polylysine, and wherein the primary ammonium salt of hyperbranched polylysine has a degree of branching (DB) higher than 0 and at most 0.99. By ‘dendrimeric polylysine’ is meant in the specification a polylysine that has a degree of branching (DB) higher than 0.99 and at most 1. By ‘primary ammonium salt of dendrimeric polylysine’ is meant in the specification a dendrimeric polylysine (as the latter is defined in the specification) which contains in its structure at least one primary ammonium cation (-NH3+) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the dendrimeric polylysine and wherein the primary ammonium salt of dendrimeric polylysine has a degree of branching (DB) higher than 0.99 and at most 1. By ‘peptide’ is meant in the specification a polymeric compound other than the polylysines-X (and obviously other than the polylysine component), wherein said polymeric compound consists of one chain which has at least 2 and at most 50 amino acids linked by peptide bonds.
2023PF30090-01 FC By ‘protein’ is meant in the specification a polymeric compound other than the polylysines-X (and obviously other than the polylysine component), wherein said polymeric compound consists of at least one chain which has at least 51 amino acids linked by peptide bonds. By ‘acetoacetoxy group’ is meant in the specification an organic group which has the following formula C:
Formula C By ‘oxirane group’ is meant in the specification an organic group which has the following formula OD:
Formula OD By ‘ketone group’ is meant in the specification an organic group which is according to any one of the following formulae EK1 to EK2:
Formula EK1 Formula EK2 By ‘ethylenically unsaturated group’ is meant in the specification an organic group which is according to any one of the following formulae EU1 to EU15:
Formula EU1
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Formula EU5
Formula EU7
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Formula EU11
Formula EU12
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Formula EU15 By ‘vinyl unsaturated group’ is meant in the specification an organic group which is according to any one of the following formulae VU1 to VU2:
Formula VU2 wherein in Formula VU1, X is O or NH, in Formula VU2, X is O or NH, and R is a C1 to C10 alkyl group.
2023PF30090-01 FC By the term ‘metal containing compound’ is meant in the specification a compound containing a metal atom or metal cation. Examples of metal containing compounds include but are not limited to organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds. Examples of organometallic compounds include but are not limited to organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium). Examples of metal complexes include but are not limited to metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium). Examples of alkali metal (preferably potassium, sodium, lithium) inorganic compounds include but are not limited alkali metal (preferably potassium, sodium, lithium) hydroxides. Examples of alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds include but are not limited to alkali earth metal (preferably calcium, magnesium, barium) hydroxides. By ‘gel content’ (referring to a polylysine) is meant in the specification the fraction of the polylysine which is insoluble upon storing the polylysine in water at room temperature (23 oC) for 24 hours. The gel content is determined as described in the Examples. A polylysine (for example any one of the polylysines-X of the polylysine component) with a gel content higher than 20 % is characterized as a ‘crosslinked polylysine’, whilst a polylysine (for example any one of the polylysines-X of the polylysine component) with a gel content of at most 20 % is characterized as a ‘non-crosslinked polylysine’. The gel content is determined via the Gel-Content Method described in the Examples. By the term ‘flexural properties’ (referring to an object e.g. fibreboards) is meant both the following material properties i) and ii): i) the modulus of rupture (Rb) and ii) the apparent modulus of elasticity (E). The flexural properties are determined via the Static Bending Method as described in the Examples. By the term ‘delamination’ it is meant in the context of this invention a mode of failure where after heat-pressing of the corresponding composition the resulting material fractured into layers or pieces. In the context of this invention the press time factor (in sec/mm) (abbreviated as PTF) is the press time (that is the time from closing to opening of the press) divided by the target thickness of a fibreboard; the target thickness refers to the
2023PF30090-01 FC thickness of the fibreboard at the end of the pressing step. For example, when a 12 mm fibreboard is made with a press time factor of 9 sec/mm, the press time was 108 sec. In the context of this invention, the term ‘fast-curing’ (or equally ‘fast- cured’ or equally ‘fast-cure’) means a press time factor equal to 10 sec/mm. In the context of this invention, the term ‘low temperature’ means 160 oC. In the context of this invention the terms “synthetic cellulose fibers”, “man-made cellulose fibers” or “manufactured cellulose fibers” or “artificial cellulose fibers” or “regenerated cellulose fibers” are used interchangeably and these terms are used to distinguish the synthetic cellulose fibers from the natural cellulose fibers and the natural lignocellulosic fibers, the latter two being vegetable fibers. The term ‘engineered wood’ (also known as mass timber, composite wood, man-made wood, or manufactured board) includes a range of derivative wood products which are manufactured by binding or fixing together the various wood elements (e.g. fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips (e.g. wood chips, sawdust), shavings (e.g. sawmill shavings), flakes, lamellae, pulp (e.g. wood pulp), and mixtures thereof), via various methods of fixation to form effectively a composite material. Exemplary types of engineered wood include but are not limited to plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites. The term ‘fibreboard’ as used in the specification encompasses low- density fibreboard (LDF; known also as particle board or chip board), and medium- density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)]. By the term ‘wood chips’ is meant in the specification chipped woody biomass in the form of pieces with a defined particle size produced by mechanical treatment with sharp tools such as knives (ISO 16559-2014; §4.226). The particle size distribution of the wood chips is determined via oscillating screen method using sieves with apertures of 3.15 mm and above according to the ISO 17827-1:2016. According to this standard (ISO 17827-1:2016) the median value of the particle size distribution (d50) is reported and is defined as the calculated particle size of a sample where 50 % of the
2023PF30090-01 FC particle mass is below and 50 % is above. Graphically the median value is established by the intersection of the cumulative distribution curve with the 50 % line (X axis: particle/hole size (mm) and Y-axis: accumulated % of weight (%)]. By ‘room temperature’ is meant herein 23± 0.5 oC. By ‘atmospheric pressure’ is meant in the specification pressure of 1 atm (1 atm= 101325 Pa). By ‘standard conditions’ is meant in the specification room temperature and atmospheric pressure, collectively. By ‘lower than’ is meant in the specification that the relevant maximum boundary value is not included in the range. By ‘higher than’ is meant in the specification that the relevant minimum boundary value is not included in the range. By ‘rpm’ is meant revolutions per minute. The decimal separator in numbers (also known as the radix character) is indicated with a period (‘.’). By ‘pph’ is meant in the specification weight parts per one hundred weight parts. The wavy lines shown in any one of the formulae shown in the specification and relate to the XL-component signify that the molecular structure beyond the point indicated by the wavy line, is not specified. Every constituent and every component of the compositions of the invention is different and distinct from any other component and constituent of the composition of the invention. The total sum of any quantities expressed as percentages, in the specification including the claims, cannot (allowing for rounding errors) exceed 100 wt% of the composition. For example the sum of all components of which the composition of the invention (or part(s) thereof) comprises may, when expressed as a weight (or other) percentage of the composition (or the same part(s) thereof), total 100 wt% allowing for rounding errors. However where a list of components is non-exhaustive the sum of the percentage for each of such components may be less than 100 wt% to allow a certain percentage for additional amount(s) of any additional component(s) that may not be explicitly described herein. All combinations of minimum and maximum values of the parameters disclosed in the specification may be used to define the parameter ranges for various preferments or embodiments of the invention. For all upper and lower boundaries of any parameters given herein, the boundary value is included in each range for each parameter. All combinations of
2023PF30090-01 FC minimum and maximum values of the parameters described herein may be used to define the parameter ranges for various embodiments and preferences of the invention. Unless otherwise explicitly stated, any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments of the invention as these are disclosed in the entire specification including the claims can be combined with each other. Unless the context indicates otherwise, the plural forms of the terms in the specification are construed as including the singular form and vice versa. Certain moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise and/or are used in some or all of the invention as described in the specification may exist as one or more different forms such as any of those in the following non- exhaustive list: stereoisomers (such as enantiomers (e.g. E and/or Z forms), diastereoisomers and/or geometric isomers); tautomers (e.g. keto and/or enol forms). The invention comprises and/or uses all such forms which are effective as defined in the specification. This section (Detailed Disclosure of the Invention) together with the claims provides for the disclosure of the invention as well as for explicit preferments and embodiments of the claimed invention; thus, the disclosure presented in this section, along with these explicit preferments and embodiments disclosed in this section are within the scope of the claimed invention. The invention provides for a composition as described in claim 1. The subject matter of this paragraph is mentioned in the specification as ‘A0’. More particularly, the invention provides for a composition comprising a constituent-A, which constituent-A consists of: - a polylysine component, - a XL-component, and - a fibrous component, wherein the polylysine component selected from the group consisting of polylysines-X and mixtures thereof, and wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines, preferably the polylysines-X are selected from the group consisting of hyperbranched polylysines, wherein each one of the polylysines-X has a degree of branching determined by 1H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.60, an apparent viscosity determined by the Rheometry Method as disclosed in the
2023PF30090-01 FC specification, of at least 400 and at most 8000 mPa.s, and a gel content determined by the Gel-Content Method as disclosed in the specification, of at most 4.0, preferably at most 3.0, more preferably at most 2.0, even more preferably at most 1.0, even more preferably at most 0.5, for example at most 0.4, for example at most 0.3, for example at most 0.2, for example at most 0.1, for example at most 0.05, for example at most 0.04, for example at most 0.03, for example at most 0.02, for example at most 0.015 %, for example the gel content is 0.0 %. and the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL- groups are selected from the group consisting of groups according to the formula XL2 (herein also mentioned as XL2-groups), groups according to the formula XL3 (herein also mentioned as XL3-groups), groups according to the formula XL4 (herein also mentioned as XL4-groups), groups according to the formula XL5(herein also mentioned as XL5-groups), groups according to the formula XL6 (herein also mentioned as XL6- groups), groups according to the formula XL7 (herein also mentioned as XL7-groups), and groups according to the formula XL8 (herein also mentioned as XL8-groups), preferably the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3, groups according to the formula XL4, groups according to the formula XL5, and groups according to the formula XL6,
Formula XL3
2023PF30090-01 FC
Formula XL7
Formula XL8 more preferably the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1 (herein also mentioned as XL3.1-groups), groups according to the formula XL3.2 (herein also mentioned as XL3.2-groups), groups according to the formula XL3.3 (herein also mentioned as XL3.3-groups), groups according to the formula XL4.1 (herein also mentioned as XL4.1-groups), groups according to the formula XL5.1 (herein also mentioned as XL5.1-groups), groups
2023PF30090-01 FC according to the formula XL6, groups according to the formula XL7, groups according to the formula XL8; even more preferably the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL- groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1, groups according to the formula XL3.2, groups according to the formula XL3.3, groups according to the formula XL4.1, groups according to the formula XL5.1, and groups according to the formula XL6,
Formula XL3.3
Formula XL4.1
2023PF30090-01 FC
Formula XL8 most preferably the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1.1 (herein also mentioned as XL3.1.1- groups), groups according to the formula XL3.2.1 (herein also mentioned as XL3.2.1- groups), groups according to the formula XL3.3.1 (herein also mentioned as XL3.3.1- groups), groups according to the formula XL4.1.1 (herein also mentioned as XL4.1.1- groups), groups according to the formula XL5.1, groups according to the formula XL6.1 (herein also mentioned as XL6.1-groups), groups according to the formula XL6.2 (herein also mentioned as XL6.2-groups), and groups according to the formula XL6.3 (herein also mentioned as XL6.3-groups),
2023PF30090-01 FC
Formula XL4.1.1
2023PF30090-01 FC
Formula XL6.3 especially the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1.1, groups according to the formula XL3.2.1.2 (herein also mentioned as XL3.2.1.2-groups), groups according to the formula XL3.3.1, groups according to the formula XL4.1.1, groups according to the formula XL5.1, groups according to the formula XL6.1, groups according to the formula XL6.2, and groups according to the formula XL6.3
2023PF30090-01 FC
Formula XL5.1
2023PF30090-01 FC
Formula XL6.3 and the fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component, and wherein the constituent-A is present in an amount of at least 10 and at most 100, preferably at least 20 and at most 100, more preferably at least 30 and at most 100, even more preferably at least 40 and at most 100, for example at least 50 and at most 100, for example at least 60 and at most 100, for example at least 70 and at most 100, for example at least 80 and at most 100 wt% of the composition, and wherein the polylysine component is present in an amount of at least 0.5 and at most 9.0, for example at least 0.5 and at most 8.0, for example at least 0.5 and at most 7.0, for example at least 0.5 and at most 6.0, for example at least 0.75 and at most 9.0, for example at least 0.75 and at most 8.0, for example at least 0.75 and at most 7.0, for example at least 0.75 and at most 6.0, for example at least 1.0 and at most 9.0, for example at least 1.0 and at most 8.0, for example at least 1.25 and at most 9.0, for
2023PF30090-01 FC example at least 1.25 and at most 8.0, for example at least 1.25 and at most 7.0, for example at least 1.25 and at most 6.0, for example at least 1.50 and at most 9.0, for example at least 1.50 and at most 8.0, for example at least 1.50 and at most 7.0, for example at least 1.50 and at most 6.0, for example at least 1.75 and at most 9.0, for example at least 1.75 and at most 8.0, for example at least 1.75 and at most 7.0, for example at least 1.75 and at most 6.0, for example at least 2.0 and at most 9.0, for example at least 2.0 and at most 8.0, for example at least 2.0 and at most 7.0, for example at least 2.0 and at most 6.0, for example at least 2.25 and at most 9.0, for example at least 2.25 and at most 8.0, for example at least 2.25 and at most 7.0, for example at least 2.25 and at most 6.0, for example at least 2.5 and at most 9.0, for example at least 2.5 and at most 8.0, for example at least 2.5 and at most 7.0, for example at least 2.5 and at most 6.0, for example at least 2.75 and at most 9.0, for example at least 2.75 and at most 8.0, for example at least 2.75 and at most 7.0, for example at least 2.75 and at most 6.0, for example at least 3.0 and at most 9.0, for example at least 3.0 and at most 8.0, for example at least 3.0 and at most 7.0, for example at least 3.0 and at most 6.0, for example at least 3.5 and at most 9.0, for example at least 3.5 and at most 8.0, for example at least 3.5 and at most 7.0, for example at least 3.5 and at most 6.0, for example at least 4.0 and at most 9.0, for example at least 4.0 and at most 8.0, for example at least 4.0 and at most 7.0, for example at least 4.0 and at most 6.0 wt% of the composition, and wherein the weight ratio K as the weight amount of the XL-component divided by the weight amount of the polylysine component is at least 0.10 and at most 5.0, preferably at least 0.10 and at most 4.0, for example at least 0.10 and at most 3.0, for example at least 0.10 and at most 2.0, for example at least 0.10 and at most 1.5, for example at least 0.10 and at most 1.0, for example at least 0.20 and at most 5.0, preferably at least 0.20 and at most 4.0, for example at least 0.20 and at most 3.0, for example at least 0.20 and at most 2.0, for example at least 0.20 and at most 1.5, for example at least 0.20 and at most 1.0, for example at least 0.30 and at most 5.0, preferably at least 0.30 and at most 4.0, for example at least 0.30 and at most 3.0, for example at least 0.30 and at most 2.0, for example at least 0.30 and at most 1.5, for example at least 0.30 and at most 1.0, for example at least 0.40 and at most 5.0, preferably at least 0.40 and at most 4.0, for example at least 0.40 and at most 3.0, for example at least 0.40 and at most 2.0, for example at least 0.40 and at most 1.5, for example at least 0.40 and at most 1.0, for example at least 0.50 and at most 5.0, preferably at least 0.50 and at most 4.0, for example at least 0.50 and at most 3.0, for example at least 0.50 and at most 2.0, for example at least 0.50 and at most 1.5, for example at least 0.50 and at most 1.0, and
2023PF30090-01 FC wherein the wavy lines shown in any one of the formulae relating to the XL-component signify that the molecular structure beyond the point indicated by the wavy line, is not specified. The subject matter of this paragraph is mentioned in the specification as ‘A1’. For illustration, Figure 1 depicts a hyperbranched polylysine which has a DB of 0.4 and a theoretical (calculated) molecular weight of 3350.6 Da while Figure 2 depicts a primary ammonium salt of hyperbranched polylysine wherein the anion that counters some of the primary ammonium cations (-NH3 +) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride, and wherein the primary ammonium salt of hyperbranched polylysine of Figure 2 has a DB of 0.4 and a theoretical (calculated) molecular weight of 3569.3 Da. Lysine (in either of its two enantiomeric forms, namely D- and L-lysine; ‘L’ and ‘D’ refer to the chirality at lysine’s central carbon atom) which is the precursor amino acid, contains two amino groups; one at the α-carbon and one at the ɛ-carbon. Either of these two amino groups can be the location of polymerization. In principle polylysines are formed from lysine or lysine salt [L-lysine, D-lysine, or any mixture thereof of L-lysine, e.g. a racemic mixture; or L defined -lysine salt , D-lysine salt or any mixture thereof e.g. a racemic mixture) in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water. The removal of water from the reaction mixture favors the polylysine formation. Hyperbranched polylysines may be prepared via various processes. In principle the processes for preparing hyperbranched polylysines may be categorized in four major categories: i) processes based on the ring opening addition polymerization of e-protected L-lysine-N-carboxyanhydrides (NCAs) with a nucleophilic starter, ii) processes where derivatives of L-lysine*xHCl that are activated on the carboxyl group, are used, iii) processes involving the direct thermal addition polymerization of L-lysines, and iv) processes where in the presence of at least one catalyst selected from the group consisting of tertiary amines, basic alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides, alkanoates, chelates, organometallic compounds of metal groups IIIA to VIIIA or IB to VB in the Periodic Table of Elements, a salt of lysine with at least one acid is involved. The following paragraphs in this section provide for some examples of processes for preparing hyperbranched polylysines e.g. hyperbranched polylysines reading on the claimed invention. Hyperbranched polylysines can be prepared by what is called the AB2 route. An AB2 molecule is a term used to refer to a trifunctional monomer containing one reactive group A and two reactive groups B; Where these groups A and B are reactive
2023PF30090-01 FC with one another, hyperbranched polymers can be produced by intermolecular reaction. Lysine is an example of such a trifunctional monomer where the reactive group A is the carboxyl group and each of the two reactive groups B is the amino group of the lysine and where these A and B groups in the lysine are reactive with one another; thus, an AB2 polymerization route of lysine leads to hyperbranched polylysines. Hyperbranched polylysines can also be prepared as follows: a reactor, e.g. a glass-reactor equipped with a distillation set-up is charged with L-lysine in water (50 wt%). Upon the completion of the charge of the reactor with L-lysine in water (50 wt%), the reactor is slowly (over 2- 8 hours) heated up to 120-190 oC (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion). When the desired reaction temperature has been reached, the reaction then proceeds for 2-30 hours at the desired temperature. Optionally, L-lysine in water (50 wt%) can be added to the reactor as water is being distilled off, in order to maintain the reactor’s filling at a certain level. The reaction is monitored by taking samples over regular time periods, diluting the samples to 60 wt% in water, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If necessary, water can be added to the reaction mixture prior to discharging in order to yield a product with the desired solids content and apparent viscosity. The reactor that may be used in this process can be a high-pressure reactor. If a high-pressure reactor is used in this process, then said high-pressure reactor, equipped with a distillation set-up which distillation set-up is connected to the reactor via a pressure release valve, is charged with L-lysine in water (50 wt%). Upon charging the high-pressure reactor with L-lysine in water (50 wt%), the pressure in the high-pressure reactor starts to build up while the pressure release valve is closed off and the reactor is heated up to 120-190 oC. The pressure in the reactor is preferably maintained between 1-6 bar (1 bar= 100000 Pa) during the reaction; this preferred pressure range is also maintained during the reaction when the pressure release valve is being carefully and periodically opened and closed to allow for the distillation of water and some pressure release. When the desired reaction temperature has been reached, the reaction then proceeds for 2-30 hours at the desired temperature. Optionally, L-lysine in water (50 wt%) can be added to the reactor as water is being distilled off, in order to maintain the reactor’s filling at a certain level. The reaction is monitored by taking samples over regular time periods, diluting the samples to 60wt% in water, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If necessary, water can be added to the reaction mixture prior to discharging in order to yield a product with the desired solids content and
2023PF30090-01 FC apparent viscosity. The preparation of hyperbranched polylysines in agreement with the invention shown in the Examples offer examples of the processes described above in this paragraph. Another way for preparing hyperbranched polylysines, uses L-lysine hydrochloride as starting material. The polymerisation of L-lysine hydrochloride was performed as follows: L-lysine hydrochloride (550 g, 3 mol) and NaOH (120 g, 3 mol) are added to a 1-L glass reactor with a distillation set-up. This reactor is heated to 120-190 oC and stirred for 2 to 30 hours. In order to follow the reaction, samples are taken every few hours, dissolved in water to a 60 wt% solids content, and the apparent viscosity measured. To discharge, water (the amount added is calculated so the reaction mixture will have a resultant solid content of 70-80 wt%) is added dropwise to the reactor and as water is added the temperature is lowered to 90 oC. The resultant reaction mixture in water (solid content 70-80 wt%) is then discharged at 90 oC. Another way for preparing hyperbranched polylysines, uses L-lysine hydrochloride and L-lysine as starting materials. According to this L-lysine in water (50 wt%) (409.4 g, 1.4 mol), L-lysine hydrochloride (255.7 g, 1.4 mol), and NaOH (55.8 g,1.4 mol) were added to a 1-L glass reactor. This reactor is heated to 120-190 oC and stirred for 2 to 30 hours. In order to follow the reaction, samples are taken every few hours, dissolved in water to a 60 wt% solids content, and the apparent viscosity measured. To discharge, water (the amount added is calculated so the reaction mixture will have a resultant solid content of 70-80 wt%) is added dropwise to the reactor and as water is added the temperature is lowered to 90 oC. The resultant reaction mixtures in water (solid content 70-80 wt%) is then discharged at 90 oC. A yet another process for preparing hyperbranched polylysines is based on the ring-opening addition polymerization of ɛ-protected L-lysine-N- carboxyanhydrides (NCAs) with a nucleophilic starter. Examples of this process were disclosed by Klok et al., in WO 2003/064452 and in Macromolecules 2002, 35, 8718- 8723 and by Rodriguez-Hernandez et al. in Biomacromolecules 2003, 4, 249-258. According to the latter, a mixture of Ne-trifluoroacetyl-L-lysine-NCA (TFA-Lys-NCA) and Z-lysine-NCA were subjected to ring-opening polymerization with an aliphatic amine. In a separate coupling step Nα,Nɛ-di(9-fluorenyl-methoxycarbonyl)-L-lysine (Nα,Nɛ-diFmoc Lys) was introduced as a branching point. Deprotection with piperidine in dimethyl formamide (DMF) gave two new amine groups, which allowed ring-opening polymerization of TFA-Lys-NCA and Z-Lys-NCA. These reaction cycles were repeated a number of times. Structurally similar hyperbranched block copolymers have also been described by Birchall et al. in Chem. Commun.1998, 1335-1336. a-Amino acid NCAs were subjected to ring-opening polymerization with an aliphatic amine. N,N'-
2023PF30090-01 FC Di(benzyloxycarbonyl)-L-lysine p-nitrophenyl ester was introduced as a branching point, and after deprotection of H2/Pd/C had two free amine groups for the further ring opening of amino acid NCAs. These reaction cycles were repeated a number of times. A yet another process for preparing hyperbranched polylysines is based on derivatives of L-lysine*2HCl which are activated on the carboxyl group. According to this process hyperbranched polylysines were prepared in a one-pot synthesis with activation of the carboxyl group by means of N-hydroxy succinimide (NHS). NHS-activated L-lysine*2HCl was stirred for 23 hours in dimethyl sulfoxide (DMSO) with the addition of catalytic amounts of dimethyl aminopyridine (DMAP) and 3 equivalents of diisopropyl-ethylamine (DIEA), and the polymer was precipitated from ethyl acetate. A yet another process for preparing hyperbranched polylysines is based the thermal addition copolymerization of amino acid mixtures. The thermal addition polymerization of free lysine is known and has been carried out under various reaction conditions. Plaquet and co-workers (Biochimie 1975, 57 1395-1396) polymerized L-lysine in aqueous solution at 105 oC for a period of up to 10 weeks, or else by heating at 165 oC for 8 hours. The reaction was carried out without catalyst and the yields, at below 72.5 % without exception, were very low. Harada (Bull. Chem. Soc. Japan 1959, 32, 1007-1008) polymerized L-lysine at 180 to 230 oC for between 30 minutes and 2 hours under a nitrogen atmosphere. Rohlfing and co-workers (Archives of Biochemistry and Biophysics 1969, 130, 441-448) polymerized L-lysine (free base) under a nitrogen atmosphere at between 186 and 192 oC. WO 00/71600 described the condensation of L-lysine monohydrate in a pressure apparatus. Fox et al. (BioSystems 1976, 8, 40-44) used not only L-lysine but also L-lysine*HCl as starting monomers for the thermal polymerization at 195 oC. L-Lysine*HCl was brought to reaction with the addition of orthophosphoric acid at 195 oC. US 8846842 B2 disclosed yet another process for preparing polylysines that does not require protective-group operations or activation of carboxyl groups and in which it is also possible to attain higher molecular weights than those known from the prior art. The object has been achieved by means of a process for preparing non-crosslinked hyperbranched polylysines by reacting: (A) a salt of lysine with at least one acid, (B) if appropriate, at least one amino acid other than lysine, (C) if appropriate, at least one dicarboxylic or polycarboxylic acid or copolymerizable derivatives thereof and (D) if appropriate, at least one diamine or polyamine or copolymerizable derivatives thereof,
2023PF30090-01 FC (E) if appropriate, in at least one solvent at a temperature from 120 to 200 oC in the presence of at least one catalyst (F) selected from the group consisting of (F1) tertiary amines and amidines, (F2) basic alkali metal salts, alkaline earth metal salts or quaternary ammonium salts, and (F3) alkoxides, alkanoates, chelates or organometallic compounds of metals from groups IIIA to VIIIA or IB to VB in the Periodic Table of the Elements. With this process it is possible to prepare non-crosslinked hyperbranched polylysines having a weight average molecular weight Mw of up to 750000 Da. Hyperbranched polylysines can, for example, be synthesized by direct thermal addition polymerization of L-lysine or ammonium salts of L-lysine. The thermal addition polymerization of lysine is carried out in the absence of solvent. WO 2007/060119 described the polycondensation of L-lysine hydrochloride in the presence of sodium hydroxide, water (10 wt% based on the L-lysine hydrochloride) and the catalyst dibutyltin dilaurate. The mixture was heated with stirring to an internal temperature of 150 oC. After a reaction time of 5 hours, water was distilled off under reduced pressure (200 mbar), and after the major amount of water was removed the temperature was slowly raised to 180 oC and the pressure was reduced to 10 mbar. After 8 hours, 240 g of water distillate had been collected. Hennon et al. (Biochimie 1971, 53, 215-223) described the preparation of a brown resin starting from an aqueous solution of lysine (50 wt%). The solution was concentrated by evaporation at 105 oC to 110 oC and then kept at 165 oC to 170 oC while it was agitated by directing a weak preheated nitrogen stream through it. The brown resin was obtained after 8 hours at 165 to 170 oC. Ho et al. described the synthesis of polylysine by thermally heating an aqueous lysine solution for two days at 160 oC. The obtained polylysine had a degree of branching between 0.50 and 0.54. When using microwave assisted heating at 200 oC, the obtained polylysine had a degree of branching between 0.30 and 0.32. US 2013/0123148 disclosed the preparation of polylysine by heating an aqueous lysine solution in the presence of catalytical amounts of dibutyltin dilaurate. According to the examples of US 2013/0123148, the obtained polylysines had a degree of branching above 0.30. WO 2016/062578 A1 disclosed a process for the preparation of hyperbranched polylysines suitable for large scale production of polylysine with improved yield. According to the WO 2016/062578 A1 polylysines can be prepared by a process comprising the steps of: (a) heating a boiling aqueous reaction mixture comprising lysine and water in a weight ratio of 1:10 to 3:1 within 2 to 8 hours, for example within 4 to 8 hours, to a temperature in the range from 135 to 165 oC, and (b) keeping the reaction mixture of step (a) at a temperature in a range from 135 to 165 oC at a pressure below atmospheric pressure, wherein water is removed from the mixture, and any temperature
2023PF30090-01 FC increase is less than or equal to 30 oC in 60 minutes. Customary technical aqueous lysine solutions can be used in the process as disclosed in WO 2016/062578 A1 and no catalyst is required. At the end of the second step, the mixture is in a liquid state, e.g., a melt of polylysine, not a resin. Preferably, the aqueous starting mixture is an aqueous solution of lysine in water. The lysine comprised by the aqueous starting mixture can be L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, e.g. a racemic mixture. The aqueous starting mixture can, for example, be an aqueous solution of L-lysine in water that contains 50 wt% of L-lysine and 50 wt% of water; e.g., ADM Liquid L-Lysine, Product Code: 035101 supplied by Archer Daniels Midland, Sewon L- Lysine® 50 percent liquid feed supplied by Paik Kwang, or BestAmino™ L-Lysine liquid feed grade supplied by CJ CheilJedang. Polylysine is formed from lysine in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water. The removal of water from the reaction mixture favors the formation of the polylysine. In general, the temperature of the reaction mixture is increased continuously. The process as disclosed in WO 2016/062578 A1 requires that water is removed from the reaction mixture. Any means suitable for removing water may be applied in order to remove water from the reaction mixture. Water is preferably evaporated from the mixture. The water is most preferably removed from the mixture by distillation. This process requires a pressure below atmospheric pressure in the second step. The pressure reduction facilitates the evaporation of water and thus accelerates the polycondensation reaction. According to the WO 2016/062578 A1 the weight average molecular weight and number average molecular weight of the polylysine depends on the overall duration of the process and the temperature of the reaction mixture. If the reaction mixture is kept for longer times at higher temperatures, crosslinking is more likely to occur. Preferably, the process is carried out without a catalyst. The process may be carried out continuously or, preferably, batchwise. The process is preferably carried out in what is called a one- pot mode, in which the lysine is included in its entirety in the initial charge and the polycondensation reaction is carried out in a reactor with back-mixing. Also suitable, however, are reaction regimes in a multistage reactor system, a stirred-tank cascade, or in a tube reactor. The primary ammonium salt of hyperbranched polylysines can for example be prepared via protonation of the amino groups of a hyperbranched polylysine with for example acidic agents e.g. protic acids, alkenylcarboxylic acids, alkylsulfonic acids. In the context of this specification the agents that may be used for the preparation of the primary ammonium salt of polylysines are called ‘protonation agents’. Such protonation, results in a primary ammonium salt of hyperbranched polylysine that
2023PF30090-01 FC contains in its structure at least one primary ammonium cation (-NH3 +) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the hyperbranched polylysine. The structure of the anion depends on the reactant used for the protonation of the amino groups of the hyperbranched polylysine; exemplary anions include but are not limited to halide anions (e.g. fluoride, chloride, bromide, iodide) carboxylate anions, sulfonate anions. Preferably the anion is selected from the group consisting of halide anions, carboxylate anions, sulfonate anions, more preferably the anion is selected from the group consisting of halide anions, and carboxylate anions, even more preferably the anion is selected from the group consisting of halide anions, for example the anion is selected from the group consisting of fluoride, chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride and bromide, for example the anion is chloride. The XL-component is able to react with the polylysine component. The members of the XL-component may be prepared via several processes. For example, in order to prepare a XL-component having at least two XL2 groups, freshly degassed 1,6- hexamethylene diisocyanate is stirred at 23 °C under nitrogen in the presence of 2 mol % of catalyst (e.g. pyridine derivate) and the XL-component having at least two XL2 groups is isolated as a highly viscous liquid; commercially available examples of such XL-components are Desmodur® N 3400 and Desmodur® XP 2840 offered by Covestro. For example, in order to prepare a XL-component having at least two XL3.1.1 groups, 222.3 g of isophorone diisocyanate (IPDI), 65 g of solvent naphtha 100 and 34 g of 1- methoxy propyl acetate are placed in a vessel; 193 g solid 3,5-dimethylpyrazole is added in portions, with stirring, at a temperature ranging from 75 to 85 oC, and stirring is continued for approximately one hour at 80 °C, until no isocyanate groups are detected; the XL-component having at least two XL3.1.1 groups is isolated as a clear, slightly yellowish solution; commercially available examples of such XL-components are: Bayhydur® BL2867, Desmodur® PL 350 and Desmodur® BL 3575/1 offered by Covestro. For example, in order to prepare a XL-component having at least two XL6.1 groups, 693.3 g of an aqueous solution of NaHSO3 (15 wt%) is mixed in a vessel with 3.22 g tetrabutylammonium bromide (TBAB); subsequently and once the mixture is homogenized, 693.3 g of isopropanol alcohol are added to the solution; 222.3 g IPDI are placed in a dry four necked flask that was purged with nitrogen and heated in an oil bath; the solution of NaHSO3/TBAB/IPA is placed in a dropping funnel and slowly added into the four necked flask containing the IPDI at room temperature at a rate of 2 ml/min and the mixture is left to react for approximately 3 h, in order to obtain the XL-component having at least two XL6.1 groups. For example, in order to prepare a XL-component
2023PF30090-01 FC having at least two XL5.1 groups, 222.3 g of isophorone diisocyanate are dissolved in 350 g of Solvesso 100 by heating to 80 °C; subsequently, 4 g of dried sodium methoxide are added followed by the dropwise addition of 264 g of diethyl malonate in such a way that the reaction temperature does not exceed 90 °C; the reaction mixture is kept at 90 °C until an isocyanate content of lower than 0.5 %; the XL-component having at least two XL5.1 groups is obtained upon filtration of the reaction mixture; commercially available examples of such XL-components are: Desmodur® BL 3475 and Desmodur® BL 3370 offered by Covestro. For example, in order to obtain a XL-component having at least two XL4.1.1 groups, 222.3 g of IPDI, 65 g of solvent naphtha 100 and 34 g of 1- methoxy propyl acetate are placed in a vessel. 174 g of methylethylketone oxime is added in portions under stirring at about 70 oC, and stirring is continued for approximately 3.5 h at 70 °C until no isocyanate groups are detected, in order to obtain the XL- component having at least two XL4.1.1 groups; commercially available examples of such a XL-components are: Bayhydur® 2781, Baybond® XL 6366, Desmodur® BL 3175 and Desmodur® BL 4265 offered by Covestro. For example, in order to prepare XL- component having at least two XL3.3.1 groups, 222.3 g of IPDI, 65 g of solvent naphtha 100 and 34 g of 1-methoxy propyl acetate are placed in a vessel; 226 g of caprolactam is added in portions, with stirring, at 70 oC and stirring is continued for approximately 3 h at 70 °C until no isocyanate groups can be detected in order to obtain the XL-component having at least two XL3.3.1 groups; commercially available examples of such a XL- components are: Baybond® XL 825m Baybond® XL 7270, Desmodur® BL 1100/1 and Desmodur® BL 3272 offered by Covestro. For example, in order to prepare a XL- component having at least two XL3.2.1 groups, IPDI and acetone are placed in a vessel; an equimolar amount of Imidazole with respect to the molar amount of isocyanate groups is added in portions, with stirring, at 70 oC, and stirring is continued for approximately 3 h at 70 °C until no isocyanate groups can be detected, in order to obtain the XL- component having at least two XL3.2.1 groups. Examples of XL-component include but are not limited to monomeric blocked diisocyanates, monomeric blocked polyisocyanates, polymeric blocked diisocyanates, polymeric blocked polyisocyanates, monomeric diuretdiones, polymeric diuretdiones, monomeric polyuretdiones, polymeric polyuretdiones, blocked isocyanate functional polyurethanes. The monomeric blocked diisocyanates, monomeric blocked polyisocyanates, polymeric blocked diisocyanates, polymeric blocked polyisocyanates, monomeric diuretdiones, polymeric diuretdiones, monomeric polyuretdiones, polymeric polyuretdiones, blocked isocyanate functional polyurethanes may be of one of or a combination of aliphatic, cycloaliphatic and aromatic nature. Specific examples of XL- component include but are not limited to Desmodur® N 3400, Desmodur® XP 2840,
2023PF30090-01 FC Bayhydur® BL2867, Desmodur® PL 350, Desmodur® BL 3575/1, Desmodur® BL 3475, Desmodur® BL 3370, Bayhydur® 2781, Baybond® XL 6366, Desmodur® BL 3175, Desmodur® BL 4265, Baybond® XL 825m, Baybond® XL 7270, Desmodur® BL 1100/1, Desmodur® BL 3272 all of them offered by Covestro. Preferably the composition is as disclosed in A0 or in A1 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has a degree of branching determined by 1H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.55, more preferably at least 0.30 and at most 0.50, even more preferably at least 0.30 and at most 0.45. The subject matter of this paragraph is mentioned in the specification as ‘A2’. Preferably the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (- NH3+) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of halide anions, carboxylate anions and sulfonate anions; more preferably the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3+) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of halide anions and carboxylate anions; more preferably the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3 +) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of halide anions; even more preferably the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3 +)
2023PF30090-01 FC present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of fluoride, chloride, bromide and iodide; most preferably, the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3 +) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of chloride, bromide and iodide; especially, the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3+) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of chloride and bromide; more especially, the composition is as disclosed in A0 or in any one of A1 to A2 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (-NH3+) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride. The subject matter of this paragraph is mentioned in the specification as ‘A3’. Preferably the composition is as disclosed in A0 or in any one of A1 to A3 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has an apparent viscosity determined by the Rheometry Method as disclosed in the specification of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s. The subject matter of this paragraph is mentioned in the specification as ‘A4’. Preferably the composition is as disclosed in A0 or in any one of A1 to A4 or as in any combination derived from the disclosure in this section and the entire
2023PF30090-01 FC specification including the claims, wherein each one of the polylysines-X has an amine number (abbreviated as AN) determined by the Titration Method as disclosed in the specification that is higher than its acid value (abbreviated as AV) determined by the Titration Method as disclosed in the specification. The subject matter of this paragraph is mentioned in the specification as ‘A5’. Preferably the composition is as disclosed in A0 or in any one of A1 to A5 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has a number average molecular weight (abbreviated as Mn) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da. The subject matter of this paragraph is mentioned in the specification as ‘A6’. Preferably the composition is as disclosed in A0 or in any one of A1 to A6 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da. The subject matter of this paragraph is mentioned in the specification as ‘A7’. Preferably the composition is as disclosed in A0 or in any one of A1 to A7 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has an amine number (abbreviated as AN) determined by the Titration Method as disclosed in the specification, of at least 200 and at most 700 mg KOH/g, preferably at least 250 and at most 600 mg KOH/g, more preferably at least 250 and at most 500 mg KOH/g, especially at least 300 and at most 400 mg KOH/g. The subject matter of this paragraph is mentioned in the specification as ‘A8’. Preferably the composition is as disclosed in A0 or in any one of A1 to A8 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has an acid value (abbreviated as AV) determined by the Titration Method as disclosed in the specification, of at least 10 and at most 150, preferably at least 10 and at most 100, for example at least 10 and at most 90, for example at least 30 and at most 150, for example at least 30 and at most 100, for example at least 30 and at most 90 mg KOH/g. The subject matter of this paragraph is mentioned in the specification as ‘A9’.
2023PF30090-01 FC Preferably the composition is as disclosed in A0 or in any one of A1 to A9 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X independently has an amine number (AN) determined by the Titration Method as disclosed in the specification, of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mg KOH/g. The subject matter of this paragraph is mentioned in the specification as ‘A10’. Preferably the composition is as disclosed in A0 or in any one of A1 to A10 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X independently has an amine number (AN) determined by the Titration Method as disclosed in the specification, of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mg KOH/g and wherein the AN is higher than the acid value (AV) determined by the Titration Method as disclosed in the specification. The subject matter of this paragraph is mentioned in the specification as ‘A11’. Preferably the composition is as disclosed in A0 or in any one of A1 to A11 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X independently has an apparent viscosity determined by the Rheometry Method as disclosed in the specification, of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s, and wherein the AN is higher than the acid value (AV) determined by the Titration Method as disclosed in the specification. The subject matter of this paragraph is mentioned in the specification as ‘A12’.
2023PF30090-01 FC Preferably the composition is as disclosed in A0 or in any one of A1 to A12 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X independently has: - a number average molecular weight (abbreviated as Mn) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 5000 and at most 30000 Da, for example at least 10000 and at most 30000 Da, - apparent viscosity determined by the Rheometry Method, of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s. The subject matter of this paragraph is mentioned in the specification as ‘A13’. Preferably the composition is as disclosed in A0 or in any one of A1 to A13 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has: - a number average molecular weight (abbreviated as Mn) determined by the Gel- Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as Mw) determined by the Gel- Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da, - a polydispersity (abbreviated as PD) calculated as the ratio of Mw/Mn, of at least 2 and at most 15, preferably at least 2 and at most 10, more preferably at least 3 and at most 8,
2023PF30090-01 FC - an apparent viscosity determined by the Rheometry Method as disclosed in the specification, of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s, - an amine number (abbreviated as AN) determined by the Titration Method as disclosed in the specification, of at least 200 and at most 700 mg KOH/g, preferably at least 250 and at most 600 mg KOH/g, more preferably at least 250 and at most 500 mg KOH/g, especially at least 300 and at most 400 mg KOH/g. The subject matter of this paragraph is mentioned in the specification as ‘A14’. Preferably the composition is as disclosed in A0 or in any one of A1 to A14 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polylysines-X has: - a number average molecular weight (abbreviated as Mn) weight determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 at most 6000 Da, - a weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 10000 and at most 30000 Da, - a polydispersity calculated as the ratio of Mw/Mn, of at least 2 and at most 15, preferably at least 2 and at most 10, more preferably at least 3 and at most 8, - an apparent viscosity determined by the Rheometry Method as disclosed in the specification of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa.s,
2023PF30090-01 FC - an amine number determined by the Titration Method as disclosed in the specification, of at least 200 and at most 700 mg KOH/g, preferably at least 250 and at most 600 mg KOH/g, more preferably at least 250 and at most 500 mg KOH/g, especially at least 300 and at most 400 mg KOH/g, - an acid value determined by the Titration Method as disclosed in the specification, of at least 10 and at most 150 mg KOH/g, preferably at least 30 and at most 100, more preferably at least 40 and at most 90 mg KOH/g, and - a gel content of at most 3.0, preferably at most 2.0, more preferably at most 1.0, even more preferably at most 0.5, most preferably at most 0.1, especially at most 0.05, more especially a gel content of 0.0 %. The subject matter of this paragraph is mentioned in the specification as ‘A15’. Preferably the composition is as disclosed in A0 or in any one of A1 to A15 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the members of the XL- component has a number average molecular weight determined by the Gel-Permeation Chromatography Method-2 as disclosed in the specification, of at least 100 and at most 10000, for example at least 100 and at most 5000, for example at least 100 at most 4000, for example at least 100 and at most 3000, for example at least 100 and at most 2500, for example at least 100 and at most 2000, for example at least 150 and at most 5000, for example at least 150 at most 4000, for example at least 150 and at most 3000, for example at least 150 and at most 2500, for example at least 150 and at most 2000, for example at least 300 and at most 10000, for example at least 400 and at most 10000, for example at least 500 and at most 10000 Da. The subject matter of this paragraph is mentioned in the specification as ‘A16’. Preferably the composition is as disclosed in A0 or in any one of A1 to A16 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the monomeric compounds of the XL-component has a number average molecular weight determined by the Gel- Permeation Chromatography Method-2 as disclosed in the specification, of at least 100 and at most 5000, for example at least 100 at most 4000, for example at least 100 and at most 3000, for example at least 100 and at most 2500, for example at least 100 and at most 2000, for example at least 150 and at most 5000, for example at least 150 at most 4000, for example at least 150 and at most 3000, for example at least 150 and at most 2500, for example at least 150 and at most 2000 Da. The subject matter of this paragraph is mentioned in the specification as ‘A17’. Preferably the composition is as disclosed in A0 or in any one of A1 to A15 and A17 or as in any combination derived from the disclosure in this section and the
2023PF30090-01 FC entire specification including the claims, wherein each one of the polymeric compounds of the XL-component has a number average molecular weight determined by the Gel- Permeation Chromatography Method-2 as disclosed in the specification, of at least 300 and at most 20000, for example at least 300 at most 15000, for example at least 300 and at most 10000, for example at least 300 and at most 8000, for example at least 300 and at most 6000, for example at least 300 and at most 5000, for example at least 300 at most 4000, for example at least 300 and at most 3000, for example at least 300 and at most 2500, for example at least 300 and at most 2000, for example at least 500 and at most 20000, for example at least 500 at most 15000, for example at least 500 and at most 10000, for example at least 500 and at most 8000, for example at least 500 and at most 6000, for example at least 500 and at most 5000, for example at least 500 at most 4000, for example at least 500 and at most 3000, for example at least 500 and at most 2500, for example at least 500 and at most 2000, for example at least 750 and at most 20000, for example at least 750 at most 15000, for example at least 750 and at most 10000, for example at least 750 and at most 8000, for example at least 750 and at most 6000, for example at least 750 and at most 5000, for example at least 750 at most 4000, for example at least 750 and at most 3000, for example at least 750 and at most 2500, for example at least 750 and at most 2000, for example at least 1000 and at most 20000, for example at least 1000 at most 15000, for example at least 1000 and at most 10000, for example at least 1000 and at most 8000, for example at least 1000 and at most 6000, for example at least 1000 and at most 5000, for example at least 1000 at most 4000, for example at least 1000 and at most 3000, for example at least 1000 and at most 2500, for example at least 1000 and at most 2000 Da. The subject matter of this paragraph is mentioned in the specification as ‘A18’. Preferably the composition is as disclosed in A0 or in any one of A1 to A18 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein each one of the polymeric compounds of the XL-component is a linear polymeric compound, preferably each one of the polymeric compounds of the XL-component is a linear non-branched polymeric compound. The subject matter of this paragraph is mentioned in the specification as ‘A19’. Preferably the composition is as disclosed in A0 or in any one of A1 to A18 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the XL-component is a monomeric compound having at least two XL-groups per molecule. The subject matter of this paragraph is mentioned in the specification as ‘A20’. Preferably the composition is as disclosed in A0 or in any one of A1 to A18 or as in any combination derived from the disclosure in this section and the entire
2023PF30090-01 FC specification including the claims, wherein the XL-component is a polymeric compound having at least two XL-groups per molecule; more preferably the XL-component is a linear polymeric compound having at least two XL-groups per molecule; even more preferably the XL-component is a linear non-branched polymeric compound having at least two XL-groups per molecule. The subject matter of this paragraph is mentioned in the specification as ‘A21’. Preferably the composition is as disclosed in A0 or in any one of A1 to A21 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein none of the monomeric compounds of the XL- component and none of the polymeric compounds of the XL-component contains Si atoms in its structure. The subject matter of this paragraph is mentioned in the specification as ‘A22’. Preferably the composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise water. The subject matter of this paragraph is mentioned in the specification as ‘A23’. Preferably the composition is as disclosed in A0 or in any one of A1 to A23 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises water in an amount determined by the Water-Content Method as disclosed in the specification, of at least 1 and at most 90, preferably at least 2 and at most 90, more preferably at least 3 and at most 90, even more preferably at least 5 and at most 90, for example at least 1 and at most 80, for example at least 2 and at most 80, for example at least 3 and at most 80, for example at least 5 and at most 80, for example at least 1 and at most 70, for example at least 2 and at most 70, for example at least 3 and at most 70, for example at least 5 and at most 70, for example at least 1 and at most 60, for example at least 2 and at most 60, for example at least 3 and at most 60, for example at least 5 and at most 60, for example at least 1 and at most 50, for example at least 2 and at most 50, for example at least 3 and at most 50, for example at least 5 and at most 50, for example at least 1 and at most 40, for example at least 2 and at most 40, for example at least 3 and at most 40, for example at least 5 and at most 40, for example at least 1 and at most 30, for example at least 2 and at most 30, for example at least 3 and at most 30, for example at least 5 and at most 30, for example at least 1 and at most 20, for example at least 2 and at most 20, for example at least 3 and at most 20, for example at least 5 and at most 20, for example at least 1 and at most 15, for example at least 2 and at most 15, for example at least 3 and at most 15, for example at least 5 and at most 15, for example at least 1 and at most 10, for example at least 2 and at most 10, for example at least 3 and at most
2023PF30090-01 FC 10, for example at least 5 and at most 10 pph of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A24’. Preferably the composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises water and the aggregate amount of the constituent-A and water in the composition is higher than 10, preferably at least 20, for example at least 30, for example at least 40, for example at least 50, for example at least 60, for example at least 70, for example at least 80, for example at least 90, for example at least 92, for example at least 95, for example at least 97 for example at least 98, for example at least 99 pph of the composition, for example the composition consists of the constituent-A and water, wherein the amount of water is determined by the Water-Content Method disclosed in the specification. The subject matter of this paragraph is mentioned in the specification as ‘A25’. Preferably the composition is as disclosed in A0 or in any one of A1 to A22 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the constituent-A is present in an amount of at least 85 and at most 100, for example at least 87 and at most 100, for example at least 90 and at most 100, for example at least 92 and at most 100, for example at least 95 and at most 100, for example at least 97 and at most 100, for example at least 98 for example at least 99 and at most 100 wt% of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A26’. Preferably the composition is as disclosed in A0 or in any one of A1 to A26 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition comprises an organic solvent in an amount of at most 50, preferably at most 40, more preferably at most 30, even more preferably at most 20, most preferably at most 10, especially at most 5, more especially at most 3 pph of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A27’. Preferably the composition is as disclosed in A0 or in any one of A1 to A26 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of organic solvent. The subject matter of this paragraph is mentioned in the specification as ‘A28’ Preferably the composition is as disclosed in A0 or in any one of A1 to A28 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A and water. The subject matter of this paragraph is mentioned in the specification as ‘A29’.
2023PF30090-01 FC Preferably the composition is as disclosed in A0 or in any one of A1 to A29 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A. The subject matter of this paragraph is mentioned in the specification as ‘A30’. Preferably the composition is as disclosed in in A0 or in any one of A1 to A30 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-B which is selected from the group consisting of proteins and mixtures thereof. More preferably, the composition may optionally comprise the constituent-B in an amount of at most 0.95, preferably at most 0.90, more preferably at most 0.80, for example at most 0.70, for example at most 0.60, for example at most 0.50 for example at most 0.40 for example at most 0.30 for example at most 0.20 for example at most 0.10 for example at most 0.05 pph of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A31’. Preferably the composition is as disclosed in A0 or in any one of A1 to A30 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-B and the constituent-B is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A32’. Preferably the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition; more preferably the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most
2023PF30090-01 FC 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition and wherein the constituent-C is a tannin, a lignosulfonate salt or a mixture thereof, and wherein the composition is free of any polyphenolic macromolecular compound other than a tannin, a lignosulfonate salt and any mixture of any combination of a tannin, and lignosulfonate salt; even more preferably the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition, and wherein the constituent-C is a condensed tannin, a lignosulfonate salt or a mixture thereof, and wherein the composition is free of any polyphenolic macromolecular compound other than a condensed tannin, a lignosulfonate salt and any mixture of any combination of a condensed tannin, and lignosulfonate salt; most preferably the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition, and wherein the constituent-C is a lignosulfonate salt or a mixture of lignosulfonate salts, and wherein the composition is free of any polyphenolic macromolecular compound other than a lignosulfonate salt and mixtures of lignosulfonate salts; especially the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a
2023PF30090-01 FC constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition, and wherein the constituent-C is calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate or a mixture thereof, and wherein the composition is free of any polyphenolic macromolecular compound other than calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate and a mixture thereof; more especially, the composition is as disclosed in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, more especially at most 0.13, and wherein the constituent-C is different and distinct from any other component and constituent of the composition, and wherein the constituent-C is magnesium lignosulfonate, and wherein the composition is free of any polyphenolic macromolecular compound other than magnesium lignosulfonate. The subject matter of this paragraph is mentioned in the specification as ‘A33’. Preferably the composition is as disclosed in claim 1 in A0 or in any one of A1 to A32 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-C and wherein the constituent-C is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A34’. Preferably the composition is as disclosed in claim 1 or in A0 or in any one of A1 to A34 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-D which constituted-D is selected from the group consisting of: i) monosaccharides in their aldose or ketose form, ii) oligosaccharides, iii)
2023PF30090-01 FC polysaccharides, iv) monomeric or polymeric compounds that yield one or more reducing sugars in situ e.g. upon heating, and mixtures of i) to iv), and the constituent-D is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A35’. Preferably the composition is as disclosed in A0 or in any one of A1 to A34 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-D and wherein the constituent-D is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A36’. Preferably the composition is as disclosed in A0 or in any one of A1 to A36 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition may optionally comprise a constituent-E which constituent-E is selected from the group consisting of peptides and mixtures thereof, and wherein the constituent-E is different and distinct from any other component and constituent of the composition, in an amount of at most 0.30 for example at most 0.20 for example at most 0.10 for example at most 0.05 wt% of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A37’. Preferably the composition is as disclosed in A0 or in any one of A1 to A36 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-E and wherein the constituent-E is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A38’. Preferably the composition is as disclosed in A0 or in any one of A1 to A38 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-F which constituent-F is selected from the group consisting of compounds comprising at least two acetoacetoxy groups, and mixtures thereof, and wherein the constituent-F is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A39’. Preferably the composition is as disclosed in A0 or in any one of A1 to A39 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-F1 which constituent-F1 is selected from the group consisting of compounds comprising only one acetoacetoxy group, and mixtures thereof, and wherein the constituent-F1 is different
2023PF30090-01 FC and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A40’. Preferably the composition is as disclosed in A0 or in any one of A1 to A40 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-K which constituent-K is selected from the group consisting of compounds comprising at least two oxirane groups, and mixtures thereof, and wherein the constituent-K is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A41’. Preferably the composition is as disclosed in A0 or in any one of A1 to A41 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-K1 which constituent-K1 is selected from the group consisting of compounds comprising only one oxirane group, and mixtures thereof, and wherein the constituent-K1 is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A42’. Preferably the composition is as disclosed in A0 or in any one of A1 to A42 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-L which constituent-L is selected from the group consisting of compounds comprising at least two ethylenically unsaturated groups, and mixtures thereof, and wherein the constituent-L is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A43’. Preferably the composition is as disclosed in A0 or in any one of A1 to A43 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-L1 which constituent-L1 is selected from the group consisting of compounds comprising only one ethylenically unsaturated group, and mixtures thereof, and wherein the constituent-L1 is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A44’. Preferably the composition is as disclosed in A0 or in any one of A1 to A44 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-M which constituent-M is selected from the group consisting of compounds comprising at least two vinyl unsaturated groups, and mixtures thereof, and wherein the constituent-M is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A45’.
2023PF30090-01 FC Preferably the composition is as disclosed in A0 or in any one of A1 to A45 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of constituent-M1 which constituent-M1 is selected from the group consisting of compounds comprising only one vinyl unsaturated group, and mixtures thereof, and wherein the constituent-M1 is different and distinct from any other component and constituent of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A46’. Preferably the composition is as disclosed in A0 or in any one of A1 to A46 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition optionally comprises (preferably comprises) constituent-N in an amount of at least 0.01 and at most 10, preferably at least 0.02 and at most 8, more preferably at least 0.05 and at most 5, for example at least 0.01 and at most 4, for example at least 0.03 and at most 3, for example at least 0.05 and at most 2, for example at least 0.75 and at most 2 wt% on the aggregate weight amount of the polylysine component and the XL-component, and which constituent-N is selected from the group consisting of amines, amine salts, aza compounds, metal containing compounds, and mixtures thereof; preferably the constituent-N is selected from the group consisting of amines, amine salts, aza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; more preferably the constituent-N is selected from the group consisting of amines, amine salts, aza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; even more preferably the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, metal containing compounds, and mixtures thereof; for examples the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, aza compounds, metal containing compounds, and mixtures thereof; for examples the constituent-N is selected
2023PF30090-01 FC from the group consisting of tertiary amines, amine salts, aza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, aza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, metal containing compounds, and mixtures thereof; for examples the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; for example the composition comprises constituent-N which constituent-N is selected from the group consisting of amines, amine salts, aza compounds, metal containing compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), and mixtures thereof; preferably the constituent-N is selected from the group consisting of amines, amine salts, aza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; more preferably the constituent-N is selected from the group consisting of amines, amine salts, aza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium,
2023PF30090-01 FC cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; even more preferably the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, metal containing compounds tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for examples the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, aza compounds, metal containing compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for examples the constituent-N is selected from the group consisting of tertiary amines, amine salts, aza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium,
2023PF30090-01 FC sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, aza compounds, organometallic compounds of organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, metal containing compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for examples the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkali earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof; for example the constituent-N is selected from the group consisting of tertiary amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminium, chromium, alkali metals (preferably potassium, sodium, lithium), alkali earth metals (preferably calcium, magnesium, barium), alkali metal (preferably potassium, sodium, lithium) hydroxides, alkali earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof; examples of amines include but are not limited to tributylamine (TBA), triethylamine (TEA), pyridine, dimethyl amino pyridine, triphenylamine, 1,2-dimethyl-1,4,5,6-
2023PF30090-01 FC tetrahydropyrimidine. Examples of amine salts include but are not limited to N,N- dimethylcyclohexyl ammonium acetate. Examples of monoaza compounds include but are not limited to 1-Azabicyclo[2.2.2]octane (known also as ABCO or quinuclidine). Examples of diaza compounds include but are not limited to 1,4- diazabicyclo(2,2,2)octane (DABCO), 1.8-diazabicyclo[5.4.0]undec-7-ene formate, 1,8- diazabicyclo[5.4.0]undece-1-ene (DBU), diazabicyclononane (DBN), 3,3,6,9,9- pentamethyl-2,10-diazabicyclo[4.4.0]dec-1-ene. Examples of metal containing compounds and in particular organometallic compounds include but are not limited to dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTDA), dioctyltin maleate, monobutyltin monoacylate, monobutyl tin sulfide, monobutyltin oxide, trioctyltin laurate, bis(trioctyltin)oxide (TOTO), bis(tributyltin) oxide (TBTO), tetrabutylstannoxane diacetate Butyltin tris(-ethylhexanoate). Examples of metal containing compounds and in particular metal complexes include but are not limited to zinc(II)-acetylacetonate, zinc napthenate, bismuth tris(2-ethylhexanoate), aluminum dionate complex, cobalt bis(2-ethyl hexanoate), cobalt (III)-acetylacetonate, zirconium bis(2-ethyl hexanoate), zinc bis(2- ethyl hexanoate), titanium tetra(acetylacetonate), Ti tetra(ethyl acetoacetate) calcium bis(2-ethyl hexanoate), chromium tris(2-ethyl hexanoate), sodium methoxide, potassium methoxide, lithium methoxide, 4,12-dibutyl-2,6,10,14-tetramethyl-1,7,9,15-tetraoxa- 4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-dibutyl-2,2,10,10-tetramethyl-1,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-dimethyl-1,7,9,15-tetraoxa- 4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-diethyl-1,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadecane, 4,12-dibutyl-1,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadecane, 4,12-diethyl-2,6,10,14-tetramethyl-1,7,9,15-tetraoxa- 4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-diethyl-2,2,10,10-tetramethyl-1,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 2,4,6,10,12,14-hexamethyl- 1,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 2,2,4,10,10,12- hexamethyl-1,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane. Examples of metal containing compounds and in particular alkali metal inorganic compounds include but are not limited to LiOH, KOH, NaOH. Examples of metal containing compounds and in particular alkali earth metal inorganic compounds include but are not limited to Ca(OH)2, Mg(OH)2, Ba(OH)2. Dimethyl amino pyridine, tributylamine (TBA), triethylamine (TEA), 1,4-diazabicyclo(2,2,2)octane (DABCO), dibutyltin dilaurate (DBTDL), zinc(II)- acetylacetonate, zinc bis(2-ethyl hexanoate), sodium methoxide, LiOH, Ca(OH)2, Mg(OH)2, are particularly preferred. The subject matter of this paragraph is mentioned in the specification as ‘A47’. Preferably the composition is as disclosed in A0 or in any one of A1 to A26 and in any one of A31 to A47 or as in any combination derived from the disclosure
2023PF30090-01 FC in this section and the entire specification including the claims, wherein the composition consists of constituent-A, and constituent-N. The subject matter of this paragraph is mentioned in the specification as ‘A48’. Preferably the composition is as disclosed in A0 or in any one of A1 to A28 or in any one of A31 to A47 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition consists of constituent-A, constituent-N and water. The subject matter of this paragraph is mentioned in the specification as ‘A49’. Preferably the composition is as disclosed in A0 or in any one of A1 to A49 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of formaldehyde resins. The subject matter of this paragraph is mentioned in the specification as ‘A50’. Preferably the composition is as disclosed in A0 or in any one of A1 to A50 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of urea-formaldehyde resins. The subject matter of this paragraph is mentioned in the specification as ‘A51’. Preferably the composition is as disclosed in A0 or in any one of A1 to A51 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of melamine- formaldehyde resins. The subject matter of this paragraph is mentioned in the specification as ‘A52’. Preferably the composition is as disclosed in A0 or in any one of A1 to A49 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the composition is free of formaldehyde resins, and free of urea-formaldehyde resins, and free of melamine-formaldehyde resins, and free of mixtures thereof. The subject matter of this paragraph is mentioned in the specification as ‘A53’. The fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component. Thus, both the fibrous component and the inventive compositions comprise only vegetable fibers. Preferably the composition is as disclosed in A0 or in any one of A1 to A53 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous component is present in an amount of at least 10 and at most 98, preferably at least 20 and at most 98, more preferably at least 30 and at most 98, most preferably at least 40 and at most 98, especially at least
2023PF30090-01 FC 50 and at most 98, more especially at least 60 and at most 98, even more especially at least 70 and at most 98, most especially at least 80 and at most 98, for example at least 85 and at most 98 wt% of the composition. The subject matter of this paragraph is mentioned in the specification as ‘A54’. Preferably the composition is as disclosed in A0 or in any one of A1 to A54 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous element comprises vegetable fibers in an amount of at least 20, preferably at least 30, more preferably at least 40, for example at least 50, for example at least 60, for example at least 70, for example at least 80, for example at least 90, for example at least 95, for example at least 96, for example at least 97, for example at least 98, for example at least 99, for example at least 99.5 wt% of the fibrous element, for example the fibrous element consists of vegetable fibers. The subject matter of this paragraph is mentioned in the specification as ‘A55’. Preferably the composition is as disclosed in A0 or in any one of A1 to A55 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof. The subject matter of this paragraph is mentioned in the specification as ‘A56’. Preferably the composition is as disclosed in A0 or in any one of A1 to A56 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof. The subject matter of this paragraph is mentioned in the specification as ‘A57’. Preferably the composition is as disclosed in A0 or in any one of A1 to A57 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, and mixtures thereof. The subject matter of this paragraph is mentioned in the specification as ‘A58’. Preferably the composition is as disclosed in A0 or in any one of A1 to A58 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the vegetable fibers are wood fibers. The subject matter of this paragraph is mentioned in the specification as ‘A59’. Preferably the composition is as disclosed in A0 or in any one of A1 to A59 or as in any combination derived from the disclosure in this section and the entire
2023PF30090-01 FC specification including the claims, wherein the fibrous element is selected from the group consisting of fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips, shavings, flakes, lamellae, pulp, and mixtures thereof; preferably the fibrous element is selected from the group consisting of fibers, filaments, yarns, threads, staple fiber yarns, particles, chips, shavings, flakes, pulp, and mixtures thereof; more preferably the fibrous element is a wood chip. The subject matter of this paragraph is mentioned in the specification as ‘A60’. Preferably the composition is as disclosed in A0 or in any one of A1 to A60 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the fibrous component consists of wood chips wherein the d50 which is the median value of the particle size distribution of the wood chips determined according to the ISO 17827-1:2016, is at least 1 and at most 50, preferably at least 1 and at most 40, for example at least 1 and most 30, for example at least 1 and at most 20, for example at least 1 and at most 15, for example at least 1 and at most 10, for example at least 1 and at most 8 mm. The subject matter of this paragraph is mentioned in the specification as ‘A61’. In an embodiment of the invention, there is provided a process for obtaining an object wherein the process comprises the steps a to c: a) providing a composition as disclosed in A0 or in any one of A1 to A61 or as in any combination derived from the disclosure in this section and the entire specification including the claims; and b) subjecting the composition to heat and/or pressure and/or vacuum, preferably simultaneous heat and pressure, to form an object, and c) collecting the object. The subject matter of this paragraph is mentioned in the specification as ‘A62’. Preferably the process for obtaining an object is as disclosed in A62 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the step b is as follows: b) subjecting the composition to heat -preferably at any temperature in the range of from and including 100 up to and including 300 oC, for example in the range of from and including 100 up to and including 280 oC, for example in the range of from and including 100 up to and including 260 oC, for example in the range of from and including 100 up to and including 250 oC, for example in the range of from and including 100 up to and including 240 oC, for example in the range of from and including 100 up to and including 230 oC for example in the range of from and including 100 up to and including 220 oC for example in the range of from and including 100 up to and including 210 oC, for example in the range of from and including 110 up to and including 300 oC,
2023PF30090-01 FC for example in the range of from and including 110 up to and including 280 oC, for example in the range of from and including 110 up to and including 260 oC, for example in the range of from and including 110 up to and including 250 oC, for example in the range of from and including 110 up to and including 240 oC, for example in the range of from and including 110 up to and including 230 oC, for example in the range of from and including 110 up to and including 220 oC, for example in the range of from and including 110 up to and including 210 oC, for example in the range of from and including 120 up to and including 300 oC, for example in the range of from and including 120 up to and including 280 oC, for example in the range of from and including 120 up to and including 260 oC, for example in the range of from and including 120 up to and including 250 oC, for example in the range of from and including 120 up to and including 240 oC, for example in the range of from and including 120 up to and including 230 oC, for example in the range of from and including 120 up to and including 220 oC, for example in the range of from and including 120 up to and including 210 oC, for example in the range of from and including 130 up to and including 300 oC, for example in the range of from and including 130 up to and including 280 oC, for example in the range of from and including 130 up to and including 260 oC, for example in the range of from and including 130 up to and including 250 oC, for example in the range of from and including 130 up to and including 240 oC, for example in the range of from and including 130 up to and including 230 oC, for example in the range of from and including 130 up to and including 220 oC, for example in the range of from and including 130 up to and including 210 oC, for example in the range of from and including 140 up to and including 300 oC, for example in the range of from and including 140 up to and including 280 oC, for example in the range of from and including 140 up to and including 260 oC, for example in the range of from and including 140 up to and including 250 oC, for example in the range of from and including 140 up to and including 240 oC, for example in the range of from and including 140 up to and including 230 oC for example in the range of from and including 140 up to and including 220 oC for example in the range of from and including 140 up to and including 210 oC, for example in the range of from and including 150 up to and including 300 oC, for example in the range of from and including 150 up to and including 280 oC, for example in the range of from and including 150 up to and including 260 oC, for example in the range of from and including 150 up to and including 250 oC, for example in the range of from and including 150 up to and including 240 oC, for example in the range of from and including 150 up to and including 230 oC, for example in the range of from and including 150 up to and including 220 oC, for example in the range of from and including 150 up to and including 210 oC, for example in the range of from and including 160 up to and including 300 oC, for example in the range of from and including 160 up to
2023PF30090-01 FC and including 280 oC, for example in the range of from and including 160 up to and including 260 oC, for example in the range of from and including 160 up to and including 250 oC, for example in the range of from and including 160 up to and including 240 oC, for example in the range of from and including 160 up to and including 230 oC, for example in the range of from and including 160 up to and including 220 oC, for example in the range of from and including 160 up to and including 210 oC, for example in the range of from and including 100 up to and including 160 oC, for example in the range of from and including 110 up to and including 160 oC, for example in the range of from and including 120 up to and including 160 oC, for example in the range of from and including 130 up to and including 160 oC, for example in the range of from and including 140 up to and including 160 oC, for example in the range of from and including 150 up to and including 160 oC, for example at 100 oC, for example at 110 oC, for example at 120 oC, for example at 130 oC, for example at 140 oC, for example at 150 oC, for example at 160 oC, for example at 170 oC, for example at 180 oC, for example at 190 oC, for example at 200 oC, for example at 210 oC, for example at 220 oC, for example at 240 oC, for example at 250 oC, for example at 260 oC, for example at 270 oC, for example at 280 oC, for example at 290 oC, for example at 300 oC, and/or pressure -for example at any pressure in the range of from an including 120 up to and including 105 kPa- and/or vacuum -for example at any vacuum in the range of from an including 10-10 up to and including 90 kPa-, for a time enough -for example for at least 1 sec and at most 60 min, more for example at least 2 sec and at most 30 min, for example at least 3 sec and at most 20 min, for example at least 4 sec and at most 10 min, for example at least 5 sec and at most 8 min, for example at least 10 sec and at most 6 min, for example at least 10 sec and at most 5 min, for example at least 10 sec and at most 3 min, for example at least 10 sec and at most 2 min, for example at least 30 sec and at most 5 min for example at least 30 sec and at most 3 min for example at least 30 sec and at most 2 min, for example at least 60 sec and at most 5 min, for example at least 60 sec and at most 3 min for example at least 60 sec and at most 2 min- to form an object; for example subjecting the composition to simultaneous heat and pressure in any combination of temperature and pressure ranges disclosed just above for any time range disclosed just above to form an object. The subject matter of this paragraph is mentioned in the specification as ‘A63’. Preferably the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood [for example plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density
2023PF30090-01 FC fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I- beams), trusses (including roof and floor trusses), transparent wood composites]. More preferably the process for obtaining an object is as disclosed in any one of A62 to A63 as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites. Even more preferably the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB); Most preferably the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB). Especially the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of a fiberboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)]. the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein
2023PF30090-01 FC the object is a low-density fibreboard (LDF; known also as particle board or chip board. For example the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a medium-density fibreboard (MDF). For example the process for obtaining an object is as disclosed in any one of A62 to A63 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a high-density fibreboard (HDF; known also as waferboard, flakeboard)]. The subject matter of this paragraph is mentioned in the specification as ‘A64’. Preferably the process for obtaining an object is as disclosed in any one of A62 to A64 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood. The subject matter of this paragraph is mentioned in the specification as ‘A65’. Preferably the process for obtaining an object is as disclosed in any one of A62 to A65 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is engineered wood. The subject matter of this paragraph is mentioned in the specification as ‘A66’. Preferably the process for obtaining an object is as disclosed in any one of A62 to A66 or as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is a fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)]. The subject matter of this paragraph is mentioned in the specification as ‘A67’. In an embodiment of the invention, there is provided an object obtained by a process as disclosed in any one of A62 to A67 or as in any combination derived from the disclosure in this section and the entire specification including the claims. The subject matter of this paragraph is mentioned in the specification as ‘A68’. Preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood [for example plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as
2023PF30090-01 FC waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites]. More preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I- beams), trusses (including roof and floor trusses), transparent wood composites. Even more preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB). Most preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is selected from the group consisting of fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high- density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB). Especially the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is a fiberboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)]. For example the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is a low-density fibreboard (LDF; known also as particle board or chip board; for example the object is a medium-density fibreboard (MDF). For example the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is a high- density fibreboard (HDF; known also as waferboard, flakeboard)]. The subject matter of this paragraph is mentioned in the specification as ‘A69’.
2023PF30090-01 FC Preferably the object as disclosed in A68 as in any combination derived from the disclosure in this section and the entire specification including the claims, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood. The subject matter of this paragraph is mentioned in the specification as ‘A70’. Preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is engineered wood. The subject matter of this paragraph is mentioned in the specification as ‘A71’. Preferably the object as disclosed in A68 or as in any combination derived from the disclosure in this section and the entire specification including the claims, is a fibreboard. The subject matter of this paragraph is mentioned in the specification as ‘A72’. In an embodiment of the invention, there is provided an article comprising: a) a part which is solid at 23 oC and 1 atm; and one or both of b) and c), wherein b) is a composition as disclosed in A0 or in any one of A1 to A61 or as in any combination derived from the disclosure in this section and the entire specification including the claims, and c) is an object (especially engineered wood, more especially fibreboard) as disclosed in any one of A68 to A72, or as in any combination derived from the disclosure in this section and the entire specification including the claims. The subject matter of this paragraph is mentioned in the specification as ‘A73’. In an embodiment of the invention, there is provided use of any one or any combination of i) to iii): i) a composition as disclosed in A0 or in any one of A1 to A61 or as in any combination derived from the disclosure in this section and the entire specification including the claims; ii) an object as disclosed in any one of A68 to A72, or as in any combination derived from the disclosure in this section and the entire specification including the claims; iii) an article according as disclosed in A73, or as in any combination derived from the disclosure in this section and the entire specification including the claims; in absorbents, 3D-printing, automotive applications (including but not limited to car parts, agricultural machines, composite structures, ceramic structures), marine applications (including but not limited to ships, boats, parts for ships and boats), aerospace applications (including but not limited to planes, helicopters, composite structures, ceramic structures, parts for planes, helicopters), medical items (including but not limited
2023PF30090-01 FC to artificial joints, meshes, woven or non-woven sheets, tapes, ribbons, bands, cables, tube-like products for e.g. ligament replacement, composite structures, ceramic structures), defense applications (including but not limited to ballistic protection, body armor, ballistic vests, ballistic helmets, ballistic vehicle protection, composite structures, ceramic structures), sports/recreational applications (including but not limited to toys, fencing, skates, skateboarding, snowboarding, suspension lines on sport parachutes, paragliders, kites, kite lines for kite sports, climbing equipment, composite structures, ceramic structures), architectural applications (including but not limited to windows, doors, (pseudo-)walls, cable), bottling applications, household applications (including but not limited to household appliances, whitegoods, furniture, computer housings), machinery applications (including but not limited to can and bottle handling machine parts, moving parts on weaving machines, bearings, gears, composite structures, ceramic structures, computer housings), can applications, coil applications, energy related applications (including but not limited to generators for wind, tide or solar energy), and electricity related applications (including but not limited to cabinets for electrical wire or switch boards). The subject matter of this paragraph is mentioned in the specification as ‘A74’. Further preferments and embodiments of the invention and preferred features thereof are given in the claims and in the Examples. Unless otherwise explicitly stated, any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferment described in the entire specification can be combined with each other. Unless otherwise explicitly stated, any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments in connection with any piece of disclosure in any one of A0 to A74 disclosed in this section can be combined with each other and with any other feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments of the invention as these are disclosed in the entire specification including the claims. All combinations of minimum and maximum values of the parameters disclosed in this section may be used to define the parameter ranges for various preferments and embodiments of the invention disclosed in this section. Unless otherwise explicitly stated, any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferments, and embodiments of the invention as these are disclosed in this section, in
2023PF30090-01 FC the claims and in the entire specification can be combined with each other. For all upper and lower boundaries of any parameters given in this section, the boundary value is included in each range for each parameter. All combinations of minimum and maximum values of the parameters disclosed in this section may be used to define the parameter ranges for the various preferments and embodiments disclosed in this section.
2023PF30090-01 FC EXAMPLES & METHODS The invention is explained in more detail with reference to the following non-limiting examples which are by way of illustration only. Chemicals, raw materials and other materials used in the examples SEWON L-Lysine® (50 wt% of L-lysine in water, Lot No.181224) was supplied by Daesang and it was used as supplied. Bayhydur® BL 2867, (abbreviated as BL 2867) is a reactive, blocked, aliphatic polyisocyanate (solid content 38 w/w % in water, viscosity at 23°C (D=40 s-1): < 99.9 mPa.s; pH at 20°C: 6.5-8.5; NCO content (blocked, calculated on solid resin):11.5 ± 0.5 %; equivalent weight 960; density at 20°C: 1.07 kg/l; BL 2867 is a XL-component which is a polymeric compound having at least two XL3.1 groups per molecule). D-(+)-Glucose, (anhydrous, purity 99 %) was obtained from Thermo Scientific (abbreviated as glucose). ε-Polylysine (light yellow powder with a purity of 99.4%) was supplied by Bonding Chemical. The ε-Polylysine had a Mn of 21301 Da, a Mw of 22061 Da and a polydispersity (PD) (=Mw/Mn) of 1.04, determined by the GPC-Method described in this specification, and an apparent viscosity determined by the Rheometry Method described in this specification, of 32480 mPa.s. This polylysine is mentioned in the examples as PLL-2C and it is not according to the claimed invention. Wood chips with a water content of 2.7 wt.%, density of 240 kg/m3 and a d50 (median value of the particle size distribution of the wood chips; according to the ISO 17827- 1:2016) of 4.5 mm, were used to prepare the objects (fibreboards; FB) shown in the Examples. Preparation of a polylysine component 1.1.1. Hyperbranched polylysine 1 (abbreviated as PLL-1) The preparation of the hyperbranched polylysine 1 (PLL-1 ) was carried out as follows: 6254 g of SEWON L-Lysine® were added at room temperature, to a 10 litre glass reactor equipped with a distillation set up. Subsequently, the temperature in the reactor was slowly (over 4 hours) raised to 105 oC (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion). Once the temperature in the reactor reached 105oC, the distillation of water starts. The temperature of the reactor was slowly increased to 160 oC. At the moment that the reaction reached 130°C, 2610 g SEWON L-Lysine® was added slowly into the reactor at the same rate that water was being distilled off. Subsequently, when temperature reached 160 °C, the temperature was maintained at 160 °C for 1 hour. After 1 hour at
2023PF30090-01 FC 160°C, vacuum was applied slowly to 100 mbar for as long as the apparent viscosity determined by the Rheometry Method as disclosed in the specification, of the content of the reactor reached 1300 mPa.s. Once the apparent viscosity of 1300 mPa.s was achieved, the temperature in the reactor was then decreased to 90 oC and water was dosed into the reactor and reach a solids content of 60 ±1 wt%. The end product -the hyperbranched polylysine 1 (PLL-1)- was obtained as a brown solution in water. Characterization of the hyperbranched polylysine 1 (PLL-1): DB: 0.43 [D = 18.2 (integral at 4.15-4.40 ppm); Lα = 9.3 (integral at 3.90- 4.10 ppm); Lε = 47.4 (integral at 3.25-3.30 ppm)], gel content: 0.0 %; Mn: 2250 Da, Mw: 10609 Da, polydispersity (PD) (=Mw/Mn): 4.72, amine number (AN): 386 mg KOH/g, acid value (AV): 33 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 1300 mPa.s. 1.1.2. Hyperbranched Polylysine 3 (PLL-3C) The preparation of the hyperbranched polylysine 3 (PLL-3C) was carried out as follows: 3400 g of SEWON L-Lysine® were added at room temperature, to a 5 litre high-pressure reactor equipped with a distillation set up which was connected to the reactor via a pressure release valve (herein ‘PR valve’); once all the amount of SEWON L-Lysine® was introduced into the reactor, the PR valve was closed off. Subsequently, the temperature in the reactor was slowly (over 2 hours) raised to 130 oC about 2 hours and the pressure reached 3.5 bar. Once the temperature in the reactor reached 130 oC, the PR valve was then carefully opened to allow for the distillation of water; the temperature of the reactor was maintained at 130 oC up until a solids content of 82 ± 1 wt.% was obtained; during this stage and in order to maintain a mass of about 3400 g in the reactor, SEWON L-Lysine® was being pumped into the reactor at the same rate that water was being distilled off. Once a solids content of 82 ± 1 wt.% was obtained (at that time the pressure in the reactor dropped from 3.5 bar to 1.2 bar), then the PR valve was closed off. Subsequently, the temperature and the pressure in the reactor were raised to 190 °C and 5±0.5 bar, respectively. At this stage, the temperature and the pressure in the reactor were maintained at 190 °C and 5±0.5 bar, respectively for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 4800 mPa.s; during this stage, water was being distilled off by periodically and carefully opening the PR valve making sure that the pressure in the reactor was maintained at 5±0.5 bar. Once the apparent viscosity of 4800 mPa.s was achieved, the temperature in the reactor was then decreased to 90 oC and water was dosed into the reactor and reach a solids content of 60 ±1 wt%. The end
2023PF30090-01 FC product -the hyperbranched polylysine 3 (PLL-3C)- was obtained as a brown solution in water. Characterization of the hyperbranched polylysine 4 (PLL-4): DB: 0.27 [D = 12.45 (integral at 4.15-4.40 ppm); Lα = 19.38 (integral at 3.90- 4.10 ppm); Lε = 42.76 (integral at 3.25-3.30 ppm)], gel content: 5.0 %, Mn: n.m. Da (insoluble), Mw: n.m. Da (insoluble), polydispersity (PD) (=Mw/Mn): n.m., amine number (AN): 213 mg KOH/g, acid value (AV): 52 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 4900 mPa.s. This polylysine is not according to the claimed invention. 1.1.3. Preparation of the comparative and inventive fibreboards The comparative and inventive compositions shown in Table 1 were prepared by initially hand-mixing the polylysine component and the XL-component in a container for 60 sec. The fibrous component was placed into a planetary mixer without affecting any mixing at this time. Subsequently, the mixture of the polylysine component and the XL-component was added over a period of 60 sec to the planetary mixer which contained the fibrous component under mixing. Once the addition of the mixture of the polylysine component and the XL-component was completed, then the mixing continued for another 3 min. The comparative and inventive objects i.e. fibreboards, were prepared by subjecting their corresponding compositions to simultaneous heating (160 oC) and pressure [50 kg/cm2= 4903.325 kPa)] (hot-pressed) in a way to achieve a press time factor of 10 sec/mm, using a suitable hot-press (e.g. Fontijne TP800) to form boards of 28 (L) x 34 (W) x 1.2 (T) cm (surface of 425 cm2). The thickness of all the fibreboards prepared and tested was 12 mm ± 10 %. The density of all the fibreboards prepared and tested was 750 kg/m3 ± 10 %. The weight amounts of the polylysine component shown in Table 1 were calculated on the basis of the solids content determined by the Solids-content Method as disclosed in the specification, of the polylysine component; thus the reported weight amounts of the polylysine component shown in Table 1 correspond to solids content 100 % of the polylysine component. The weight amounts of the XL-component shown in Table 1 were calculated on the basis of the solids content as the latter was reported by the supplier
2023PF30090-01 FC (see § 1.1); thus the reported weight amounts of the XL-component shown in Table 1 correspond to solids content 100 % of the XL-component. Determination of the Mn, Mw 1.1.4. Determination of the Mn, Mw of the polylysines-X (‘Gel- Permeation Chromatography Method-1’) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of a member of the polylysines-X were determined via Gel Permeation Chromatography (GPC) calibrated with a set of lysozyme from chicken egg white (CAS 12650-88-3; product number L6876; lyophilized powder, protein ≥ 90 %, ≥ 40000 units/mg protein; molecular weight single chain 14.3 kDa) and bovine serum albumin (CAS 9048-46-8; product number A2153; lyophilized powder, ≥96 %, molecular weight 66 kDa) standards both supplied by Sigma-Aldrich and using as eluent a solution of 500 mM NaCl and 0.0425 wt% H3PO4 in MilliQ water (the solution having a pH of 2.2) at a flow rate of 0.8 mL/min at 40 oC.75 mg of sample dissolved in 1.425 ml of eluent were used for the measurement; the injection volume was 20 μL. The GPC measurements were carried out on a Waters® Acquity UPLC® H-Class Bio system equipped with: i) a photodiode array (PDA) detector [AcquityTM UPLCTM (1.5 μL biocompatible cell; measurement was carried out at 225 nm); supplied by WATERS®]; ii) a separation module equipped with one Agilent Bio-SEC column (7.8 x 300 mm, pore size 100 Å, filled with particles having particle size of 3 µm, product number: 5190-2501) supplied by Agilent. The Mn and Mw were determined with the help of suitable software for data processing (EmpowerTM 3, supplied by WATERS®). 1.1.5. Determination of the Mn of the members of XL-component (‘Gel-Permeation Chromatography Method-2’) The number average molecular weight (Mn) of a member of XL- component was determined via Gel Permeation Chromatography (GPC) calibrated with a set of polystyrene standards with a molecular weight range of from 162 up to 3.8 x106 Da, and using as eluent stabilized tetrahydrofuran [THF with 0.007- 0.015% w/w butyl- hydroxytoluene (BHT)] (THF) modified with 0.8 (v/v %) acetic acid at a flow rate of 1 mL/min at 40 °C.50 mg of a solid sample of a member of XL-component, were dissolved in 5 mL eluent for 16 hours at room temperature without shaking, and used for the measurement.40 µL of the solution thus prepared were injected into the system for the measurement. The GPC measurements were carried out on a Waters Alliance system
2023PF30090-01 FC equipped with: i) a Waters Alliance 2414 refractive index detector at 40 ºC, and ii) a Waters Alliance 2695 separation module equipped with two consecutive PL-gel columns of Mixed-C type with I/d = 300/7.5 mm and filled with particles having a particle size of 20 micron (supplied by Agilent). Determination of the polydispersity (PD) Upon determining the Mn and Mw via the Gel-Permeation Chromatography Method-1 of a member of polylysines-X, the polydispersity PD for said member of the polylysines-X was calculated according to the following equation: PD= Mw/Mn. Determination of the amine number (AN) and the acid value (AV) (‘Titration Method’) The amine number (AN) and the acid value (AV) were determined by back-titrimetric analysis using the titrator 808 Titrando (supplied by Metrohm AG) with the 814 USB sample processor (supplied by Metrohm AG), and two electrodes one for the measurement of the pH (pH glass electrode supplied by Metrohm AG with product No.6.0150.100) and a reference electrode (conductivity measuring cell c=0.8 cm-1 with Pt1000 (fixed cable) supplied by Metrohm AG with product No.6.9303.110) equipped with a pH meter and titrating the titrate with a solution of 1.000 N KOH in water was used. The titrate consisted of 1.000 g of polylysine (sample) (the amount refers to solids content), 60.00 mL of Millipore Ultra RO water and 10.000 mL of a solution of 1.000 N HCl in water [Titripur® supplied by Merck; product number 1.09057]. The data processing and control handling of all titrations described in this were accomplished via the use of the software TiamoTM 2.4 supplied by Metrohm AG. The titration curve [pH vs. Volume of titrant (x-axis)] (abbreviated as TC) and the first derivative curve of the TC [electrical potential vs. Volume of titrant (x-axis)] are recorded simultaneously and are plotted together in the same graph (pH on Y1-axis and electrical potential on Y2-axis, and volume of titrant on X-axis). The first derivative curve of the TC is known as ERC which stands for Equivalence point Recognition Criteria and is expressed in units for electrical potential (mV). The ERC affords either 2 or 3 peaks (ERC peaks) in succession to each other. Each of these ERC peaks corresponds to a certain volume of titrant. One of these ERC peaks -typically the one of highest signal (delta voltage)- corresponds to the lowest volume of the titrant (Vmin) (in mL) and another one ERC peak corresponds to the highest volume of the titrant (Vmax) (in mL). The amine number (AN) is determined according to the following formula:
2023PF30090-01 FC Amine number (mg KOH/g sample) = 56.1 * (Vmax - Vmin) wherein Vmin and Vmax are as explained above. The acid value (AV) is determined according to the following formula: Acid value (mg KOH/g sample) = 56.1 * [Vmin- [10.00 - (Vmax - Vmin)]] wherein Vmin, Vmax are as explained above. The measurements for the determination of the AN and AV were performed in duplicate and the reported values for each of the AN and AV were the average of these measurements. Determination of the apparent viscosity (‘Rheometry Method’) The apparent viscosity (shear stress divided by the shear rate) was determined using the rotational rheometer RheolabQC supplied by Anton Paar, connected to a water bath, controlled at 23.0 ˚C. This method is based on ISO 3219:1993. For this measurement, the appropriate spindle/cup combination and shear rate are chosen based on the estimated apparent viscosity. For all our experiments we used a Z3 spindle/cup combination which and a shear rate of 100 s-1. The cup is then filled with sample (polylysine dissolved in water with a solids content of 60 ± 1 %). The spindle is inserted into the cup, the cup is mounted in the viscometer and the spindle is connected to the instrument. The correct program (for all our measurements we selected the program for the Z3 spindle in combination with a shear rate of 100 s-1) is selected on the RheolabQC and the measurement is performed. Determination of the solids content (‘Solids-content Method’) The solids content (wt%) was determined using a Halogen Moisture Analyzer HR73 supplied by Mettler Toledo. For this measurement, 1.00 g of sample (polylysine dissolved in water) is weighed onto a glass fiber pad which is placed on an aluminium pan and then heated at 140 oC for 30 minutes. The solids content is determined automatically based on the difference in mass before and after the heating at 140 oC. Determination of the water content (‘Water-Content Method’) The amount of water contained in an entity for example in a composition, or in a polylysine component, or in a fibrous element or in wood chips, is determined by drying said entity at 120 oC for 24 hours under reduced pressure (50 mbar) in a Thermo Scientific® VacuTherm vacuum oven supplied by Thermo Fischer Scientific. The amount of water contained in the entity was calculated according to the following equation:
2023PF30090-01 FC Water (pph or wt% of the entity) = [1- (M2/M1)] x 100 wherein M1: the mass of the entity prior to drying. M2: the mass of the entity upon drying (measured within 5 minutes after removing the sample from the oven). Determination of the degree of branching The degree of branching (DB) of a polylysine is determined via 1H-NMR spectroscopy and calculated according to the equation 1:
(equation 1) wherein D is equal to or higher than 0, L is equal to or higher than 0, and at least one of the D and L is higher than 0; and wherein D is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae D1a and D1b) of any number of the following group(s) shown in Formulae D1a and D1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the D is equal to zero):
Formula D1a Formula D1b L represents the sum of Lα and Lε, wherein Lα is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae L1a and L1b) of any number of any one of the following group(s) shown in Formulae L1a and L1b that may
2023PF30090-01 FC be present in the polylysine (if no such methine protons are present in the polylysine, the Lα is equal to zero):
and Lε is the integral of the 1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon indicated in bold in Formulae L2a and L2b) of any number of any one of the following group(s) shown in Formulae L2a and L2b that may be present in the polylysine (if no such methine protons are present in the polylysine, the Lε is equal to zero):
The DB ranges from and including 0 up to and including 1. The 1H-NMR spectra were recorded at room temperature on a Bruker AscendTM 400 Spectrometer, using deuterated methanol (also known as tetradeuteromethanol or methanol-d4) as solvent. Methanol-d4 is the preferred solvent; however, other suitable deuterated solvents may be used. In the case of methanol-d4 the chemical shifts of the 1H-NMR peaks corresponding to: - the D-proton(s) are found at 4.15-4.40 ppm; - the Lα-proton(s) are found at 3.90-4.10 ppm; and - the Lε-proton(s) are found at 3.25-3.30 ppm. Determination of the gel content (‘Gel-Content Method’) The gel content of a polylysine was determined as follows:
2023PF30090-01 FC A mixture of 10 % solids content of a polylysine in water was prepared and stored at room temperature for 24 hours. Subsequently, an amount of 3000 g of the mixture thus prepared (herein sample), was filtrated through a pre-weighed (Mfbefore) filter e.g. a folded qualitative filter paper, in order to remove any insoluble fraction of average size of at least 5 micron and higher. Once the filtration was completed, the filter was washed with water, the amount of which was double of the amount of the sample. Subsequently, the filter was placed in a vacuum oven at 40 oC under a pressure of 50 mbar, for 12 hours in order to remove any water. Subsequently, the filter was weighed again (Mfafter). The gel content was calculated from the equation 2:
(equation 2) wherein Mfafter is the mass of the filter after the removal of the water, Mfbefore is the mass of the filter before the filtration of the sample, and Mpolylysine is the mass of the polylysine in the sample (taken into account the solids content of the sample). Thus, in 3000 g of sample having 10 % solids content, the Mpolylysine is 30 g. Methods for determining properties of the fibreboards 1.1.6. Determination of the length (L), width (W) and the thickness (T) The length (L) of the specimens was measured with a ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen. The width (W) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen. The thickness (T) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the thickness of the specimen.
2023PF30090-01 FC 1.1.7. Determination of the density (d) Specimens were prepared by cutting the fibreboard prepared in one piece of 150 mm by 40 mm. The length (L; in m), width (W; in m) and thickness (T; in m) of the specimens were measured as mentioned above, as well as their weight (M; in Kg). The density (d; in Kg/m3 ) of a specimen was calculated according to the following equation and the average of 2 calculations -corresponding to two different specimens of the fibreboard- was recorded as the density of the fibreboard: d= M / ( L x W x T). 1.1.8. Determination of the flexural properties (Static Bending Method) The assessment of the flexural properties i.e. i) the modulus of rupture (Rb) and ii) the apparent modulus of elasticity (E) were determined via static bending tests according to the ASTM D1037-12 and in particular section 9 (entitled ‘Static Bending’) of the ASTM D1037-12, subject to the following two differences from the provisions of the section 9 of the ASTM D1037-12: i) the specimens were prepared by cutting the produced panel in two pieces of 150 ± 1 mm by 40 ± 1 mm, and ii) each specimen was placed in a 3-point (center loading) fixture and the length of the span (L) was fixed to 100 mm. The static bending tests were carried out on objects prepared upon subjecting their corresponding compositions to simultaneous heat (210 oC) and pressure (9 Kg/cm2= = 882.6 kPa) for 5 min. In §9.7 of the ASTM D1037-12, the modulus of rupture (Rb) and the apparent modulus of elasticity (E) are defined and calculated according to the following two equations:
^^ ∆^ ^ = 4^^^ ∆^ wherein b= width of specimen measured in dry conditions (in mm); d= thickness of specimen measured in dry conditions (in mm); ∆^^ ∆^ = slope of straight line portion of the load-deflection curve (in N/mm);
2023PF30090-01 FC Pmax = maximum load (in N); L = length of span (in mm); Rb = modulus of rupture (kPa); E = apparent modulus of elasticity (kPa). The static bending tests were carried out on ZMART.PRO 1445 supplied by Zwick/Roell, at a constant rate of speed of 3 mm/min and with the load applied to the center of each specimen. The test was continued until rupture of the specimen, while recording all force vs. deflection data. From the data obtained, one can calculate the modulus of rupture (Rb) and apparent modulus of elasticity (E), according to the equations provided in §9.7 of the ASTM D1037-12 and which are offered above for convenience. 1.1.9. Determination of the internal bond strength The assessment of the internal bond strength was determined according to NEN-EN 319:1993.
2023PF30090-01 FC 1.1.10. Results & Discussion Table 1 summarizes the comparative and inventive compositions as well as the internal bond strength, the modulus of rupture (Rb) and the apparent modulus of elasticity (E) of the fibreboards prepared upon fast-curing (press time factor equal to 10 sec/mm) at low temperature (160 oC) of their corresponding compositions. The abbreviation ‘DL’ shown in Table 1 stands for delamination (for delamination see definition in the section entitled Detailed Description of the Invention). From the results shown in Table 1, it is evident that only the inventive compositions provided a solution to the technical problem. More particularly, when the inventive compositions were fast-cured at 160 oC to prepare fibreboards, the resulted fibreboards had: - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6 MPa, and - apparent modulus of elasticity (E) of at least 800 MPa. Each one of the comparative compositions C1, C2 (which offers a simulation of the compositions of WO 2022/096518 A1) C3, C6 , C7, C8, C9, C10 and C11 resulted in delamination, whilst comparative compositions C4 and C5 failed to have - internal bond strength of at least 0.2 MPa, - modulus of rupture (Rb) of at least 6 MPa, and - apparent modulus of elasticity (E) of at least 800 MPa. The results shown in Table 1, also demonstrate the criticality and purposiveness of all the features of the inventive compositions and in particular the ranges associated with the amount of the polylysine component in the composition and the one associated with the weight ratio K, the type of polylysine component as well as the gel content of the polylysine component, and their combination. More specifically, upon comparing: a) the inventive compositions I1 to I8 to the comparative compositions C2 and C5 which are outside the claimed range for the weight ratio K (weight ratio K of C2 was 0.02 and the one of C5 was 6.0), it becomes evident the criticality and purposiveness of the weight ratio K; b) the inventive composition I2 to the comparative compositions C3 and C6 which are outside the claimed range for the amount of the polylysine component in the composition (the amount of polylysine component in C3 was 0.30 wt% of the composition and the one of C6 was 10.0 wt% of the composition), it becomes evident the criticality and purposiveness of the amount of the polylysine component in the composition;
2023PF30090-01 FC c) the inventive composition I2 to the comparative compositions C7 which C7 was formulated with ε-polylysine (which is a linear polylysine, thus not a hyperbranched polylysine, let alone a hyperbranched polylysine as claimed) it becomes evident the criticality and purposiveness of the type of polylysine component in the composition; d) the inventive composition I2 to the comparative composition C8 which C8 was formulated with a polylysine component which had a gel content outside the claimed range (the gel content of the C8 was 5 %, it becomes evident the criticality and purposiveness of the gel content of the polylysine component; e) all the inventive compositions to all the comparative compositions it becomes evident the criticality and purposiveness of the combination of all the features of the claimed invention amongst them -but not limited to- the type of polylysine, the amount of the polylysine component, the weight ratio K and the gel content of the polylysine component. Thus, only the inventive compositions provided a solution to the technical problem and by achieving so the compositions of the invention constitute a major technological advancement in the field of fibreboards whereas the compositions of the state-of the-art upon fast-curing at low temperature resulted either in delamination or in remarkably lower performance as to the required internal bond strength, modulus of rapture and apparent modulus of elasticity.
2023PF30090-01 FC Composition Properties of fibreboard Amount of Amount of Amount of XL- Internal Apparent fibrous polylysine Modulus of Index XL- component Polylysine Weight Bond Modulus of component component Rupture No. component (wt% of the component Ratio K Strength Elasticity (wt% of the (wt% of the (MPa) composition) (MPa) (MPa) composition) composition) C1 94.20 BL2867 5.80 x x n.a. DL DL DL C2 94.20 x x PLL-1 5.80 n.a. DL DL DL C3 99.61 BL2867 0.09 PLL-1 0.30 0.30 DL DL DL C4 94.20 BL2867 0.11 PLL-1 5.69 0.02 0.12 5.1 710 I1 94.20 BL2867 0.97 PLL-1 4.83 0.20 0.40 7.4 1250 I2 94.20 BL2867 1.34 PLL-1 4.46 0.30 0.41 8.4 1310 I3 94.20 BL2867 1.93 PLL-1 3.87 0.50 0.42 8.6 1410 I4 94.20 BL2867 2.90 PLL-1 2.90 1.00 0.45 9.1 1510 I5 94.20 BL2867 3.87 PLL-1 1.93 2.00 0.49 8.6 1410 I6 94.20 BL2867 4.35 PLL-1 1.45 3.00 0.45 8.9 1120 I7 94.20 BL2867 4.64 PLL-1 1.16 4.00 0.33 6.5 980 I8 94.20 BL2867 4.83 PLL-1 0.97 5.00 0.31 6.4 970 C5 94.20 BL2867 4.97 PLL-1 0.83 6.00 0.12 5.4 730 C6 87.00 BL2867 3.00 PLL-1 10.00 0.30 DL DL DL C7 94.20 BL2867 1.34 PLL-2C 4.46 0.30 DL DL DL C8 94.20 BL2867 1.34 PLL-3C 4.46 0.30 0.10 5.4 750 C9 94.20 Glucose 0.58 PLL-1 5.22 0.11 DL DL DL C10 94.20 Glucose 1.45 PLL-1 4.35 0.33 DL DL DL C11 94.20 Glucose 2.61 PLL-1 3.19 0.82 DL DL DL
Claims
2023PF30090-01 FC CLAIMS 1. A composition comprising a constituent-A, which constituent-A consists of: - a polylysine component, - a XL-component, and - a fibrous component, wherein the polylysine component selected from the group consisting of polylysines-X and mixtures thereof, and wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines, wherein each one of the polylysines-X has a degree of branching determined by 1H-NMR spectroscopy as disclosed in the specification, of at least 0.30 and at most 0.60, an apparent viscosity determined by the Rheometry Method as disclosed in the specification, of at least 400 and at most 8000 mPa.s, and a gel content determined by the Gel-Content Method as disclosed in the specification, of at most 4.0 %; and the XL-component is selected from the group consisting of monomeric or polymeric compounds each of which has at least two XL-groups per molecule wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3, groups according to the formula XL4, groups according to the formula XL5, groups according to the formula XL6, groups according to the formula XL7, and groups according to the formula XL8
Formula XL3
2023PF30090-01 FC
Formula XL7
Formula XL8 and the fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein
2023PF30090-01 FC the composition is free of any fibers other than the vegetable fibers of the fibrous component, and wherein the constituent-A is present in an amount of at least 10 and at most 100 wt% of the composition, and wherein the polylysine component is present in an amount of at least 0.5 and at most 9.0 wt% of the composition, and wherein the weight ratio K defined as the weight amount of the XL-component divided by the weight amount of the polylysine component is at least 0.10 and at most 5, and wherein the wavy lines shown in any one of the formulae relating to the XL-component signify that the molecular structure beyond the point indicated by the wavy line, is not specified. 2. The composition as claimed in claim 1, wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1, groups according to the formula XL3.2, groups according to the formula XL3.3, groups according to the formula XL4.1, groups according to the formula XL5.1, groups according to the formula XL6, groups according to the formula XL7, groups according to the formula XL8
Formula XL3.1
2023PF30090-01 FC
Formula XL5.1
Formula XL7
2023PF30090-01 FC
Formula XL8 3. The composition as claimed in claim 1, wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1.1, groups according to the formula XL3.2.1, groups according to the formula XL3.3.1, groups according to the formula XL4.1.1, groups according to the formula XL5.1, groups according to the formula XL6.1, groups according to the formula XL6.2, groups according to the formula XL6.3
2023PF30090-01 FC Formula XL3.3.1
Formula XL6.3 4. The composition as claimed in claim 1 wherein the XL-groups are selected from the group consisting of groups according to the formula XL2, groups according to the formula XL3.1.1, groups according to the formula XL3.2.1.2, groups according to the formula XL3.3.1, groups according to the formula XL4.1.1,
2023PF30090-01 FC groups according to the formula XL5.1, groups according to the formula XL6.1, groups according to the formula XL6.2, groups according to the formula XL6.3
Formula XL4.1.1
2023PF30090-01 FC
5. The composition as claimed in any one of the preceding claims, wherein each one of the polylysines-X has an apparent viscosity of at least 400 and at most 4000, for example at least 400 and at most 2500, for example at least 400 and at most 2000 mPa.s. 6. The composition as claimed in any one of the claims 1 to 4, wherein each one of the polylysines-X has: - a number average molecular weight (abbreviated as Mn) weight determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 1100 and at most 10000 Da, - a weight average molecular weight (abbreviated as Mw) determined by the Gel-Permeation Chromatography Method-1 as disclosed in the specification, of at least 3000 and at most 50000 Da, - a polydispersity calculated as the ratio of Mw/Mn, of at least 2 and at most 15,
2023PF30090-01 FC - an apparent viscosity of at least 400 and at most 8000, for example at least 400 and at most 4000, for example at least 400 and at most 2500, for example at least 400 and at most 2000 mPa.s, - an amine number determined by the Titration Method as disclosed in the specification, of at least 200 and at most 700 mg KOH/g, - an acid value determined by the Titration Method as disclosed in the specification, of at least 10 and at most 150 mg KOH/g, and - a gel content determined by the Gel-Content Method as disclosed in the specification, of at most 3.0, preferably at most 2.0, more preferably at most 1.0, even more preferably at most 0.5, most preferably a gel content of 0.0 %. 7. The composition as claimed in any one of the preceding claims, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines. 8. The composition as claimed in any one of the preceding claims, wherein the constituent-A is present in an amount of at least 20 and at most 100, more preferably at least 40 and at most 100, for example at least 60 and at most 100, for example at least 80 and at most 100 wt% of the composition. 9. The composition as claimed in any one of the preceding claims, wherein the polylysine component is present in an amount of at least 0.5 and at most 8.0, preferably at least 0.5 and at most 7.0, more preferably at least 0.5 and at most 6.0 wt% of the composition. 10.The composition as claimed in any one of the preceding claims, wherein the weight ratio K is at least 0.20 and at most 5.0, preferably at least 0.20 and at most 4.0, more preferably at least 0.20 and at most 3.0, 11.The composition as claimed in any one of the preceding claims, wherein the composition may optionally comprise a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds each of which is a macromolecular compound that bears a multitude of phenol or polyhydroxybenzene radicals, and mixtures thereof, in an amount such that the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40. 12.The composition as claimed in any one of the preceding claims, wherein the composition is free of any one or any combination of constituent-B, constituent- D, constituent-E, constituent-F, constituent-F1, constituent-K, constituent-K1, constituent-L, constituent-L1, constituent-M, and constituent-M1, wherein each
2023PF30090-01 FC one of these constituents is different and distinct from any other component and constituent of the composition, and wherein constituent-B is selected from the group consisting of proteins and mixtures thereof, and wherein constituent-D is selected from the group consisting of: i) monosaccharides in their aldose or ketose form, ii) oligosaccharides, iii) polysaccharides, iv) monomeric or polymeric compounds that yield one or more reducing sugars in situ, and mixtures of i) to iv), and wherein constituent-E is selected from the group consisting of peptides and mixtures thereof, and wherein constituent-F is selected from the group consisting of compounds comprising at least two acetoacetoxy groups, and mixtures thereof, and wherein constituent-F1 is selected from the group consisting of compounds comprising only one acetoacetoxy group, and mixtures thereof, and wherein constituent-K is selected from the group consisting of compounds comprising at least two oxirane groups, and mixtures thereof, and wherein constituent-K1 is selected from the group consisting of compounds comprising only one oxirane group, and mixtures thereof, and wherein constituent-L is selected from the group consisting of compounds comprising at least two ethylenically unsaturated groups, and mixtures thereof, and wherein constituent-L1 is selected from the group consisting of compounds comprising only one ethylenically unsaturated group, and mixtures thereof, and wherein constituent-M is selected from the group consisting of compounds comprising at least two vinyl unsaturated groups, and mixtures thereof, and wherein constituent-M1 is selected from the group consisting of compounds comprising only one vinyl unsaturated group, and mixtures thereof. 13. The composition as claimed in any one of the preceding claims, wherein the composition optionally comprises constituent-N in an amount of at least 0.01 and at most 10, preferably at least 0.02 and at most 8, more preferably at least 0.05 and at most 5, for example at least 0.01 and at most 4, for example at least 0.03 and at most 3, for example at least 0.05 and at most 2, for example at least 0.75 and at most 2 wt% on the aggregate weight amount of the polylysine component and the XL-component, and which constituent-N is selected from the group consisting of amines, amine salts, aza compounds, metal containing compounds, and mixtures thereof. 14.The composition as claimed in any one of the preceding claims, wherein the vegetable fibers are selected from the group consisting of natural lignocellulosic fibers. 15.A process for obtaining an object wherein the process comprises the steps of:
2023PF30090-01 FC - providing a composition as claimed in any one of the preceding claims 1 to 14; and - subjecting the composition to heat and/or pressure and/or vacuum, preferably simultaneous heat and pressure, to form an object, and - collecting the object. 16.An object obtained by a process as claimed in claim 15. 17.The object as claimed in claim 16, wherein the object is a fibreboard. 18.An article comprising: a) a part which is solid at 23 oC and 1 atm; and one or both of b) and c), wherein b) is a composition as claimed in any one of claims 1-14, and c) is an object as claimed in any one the claims 16 to 17. 19.Use of any one or any combination of the i) to iii): i) a composition as claimed in any one of the claims 1 to 14; ii) an object as claimed in any one of claims 16 to 17; iii) an article as claimed in claim 18; in absorbents, 3D-printing, automotive applications, marine applications, aerospace applications, medical items, defense applications, sports/recreational applications, architectural applications, bottling applications, household applications, machinery applications, can applications, coil applications, energy related applications, and electricity related applications.
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EP23191954.9 | 2023-08-17 |
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PCT/EP2024/070971 WO2025036665A1 (en) | 2023-08-17 | 2024-07-24 | Compositions for fibreboards with enhanced properties upon fast-curing at low temperature |
PCT/EP2024/070972 WO2025036666A1 (en) | 2023-08-17 | 2024-07-24 | Compositions for fibreboards with enhanced properties upon fast-curing at low temperature |
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