FI20235494A1

FI20235494A1 - A binder composition, a method for producing a binder composition, its use, and an insulating wool product

Info

Publication number: FI20235494A1
Application number: FI20235494A
Authority: FI
Inventors: Nina Pykäläinen; Sanna Valkonen
Original assignee: Upm Kymmene Corp
Priority date: 2023-05-04
Filing date: 2023-05-04
Publication date: 2024-11-05
Also published as: WO2024227968A1

Abstract

A method for producing a binder composition is disclosed. The method comprises: i) polymerizing crosslinking agent and polymerizable substance in an aqueous composition by mixing and heating at a temperature of 60 – 95 °C for preparing a precomposition, wherein at least 30 weight-% of the polymerizable substance originates from lignin, and ii) mixing the precomposition with silane, wherein silane is used in an amount of 0.1 – 0.9 weight-% based on the total dry weight of the binder composition, to form a binder composition having a free formaldehyde content of at most 0.5 %.

Description

A BINDER COMPOSITION, A METHOD FOR PRODUCING A BINDER

COMPOSITION, ITS USE, AND AN INSULATING WOOL PRODUCT

TECHNICAL FIELD

The present disclosure relates to a method for producing a binder composition. The present dis- closure further relates to a binder composition and to its use. The present disclosure further relates to an insulating wool product.

BACKGROUND

An insulating wool product such as mineral wool can be produced by spaying a binder on a melted fiber matrix. Traditionally used binders for insulat- ing wool production are sodium silicates, polyesters, melamine urea formaldehyde, polyamides, furane-based resins, and others, phenolic resin (PF)-based binders.

PF-resin has a high free formaldehyde (FA) content af- fecting the emissions of the final product unless a relevant amount of urea is used. The inventors have therefore recognized the need to produce a binder com- position to be used for producing an insulating wool product in a more sustainable manner.

SUMMARY

A method for producing a binder composition e is disclosed. The method comprises:

S i) polymerizing crosslinking agent and ro polymerizable substance in an aqueous composition by < 30 mixing and heating at a temperature of 60 - 95 °C for = preparing a pre-composition, wherein at least 30

E- weight-%3 of the polymerizable substance originates

S from lignin, and 5 ii) mixing the pre-composition with silane,

O 35 wherein silane is used in an amount of 0.1 -— 0.9 weight-% based on the total dry weight of the binder composition, to form a binder composition having a free formaldehyde content of at most 0.5 %.

Further is disclosed a binder composition comprising crosslinking agent polymerized with polymerizable substance, and silane, wherein: - at least 30 weight-% of the polymerizable substance originates from lignin, - the binder composition comprises silane in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, and - the binder composition has a free formalde- hyde content of at most 0.5 %.

Further is disclosed the use of the binder composition as disclosed in the current specification for producing an insulating wool product.

Further is disclosed an insulating wool prod- uct comprising a fiber matrix and a binder composi- tion, wherein the binder composition comprises cross- linking agent polymerized with polymerizable sub- stance, and silane, wherein: - at least 30 weight-% of the polymerizable substance originates from lignin, - the binder composition comprises silane in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, and

N - the binder composition has a free formalde-

N hyde content of at most 0.5 %.

S 30 3 BRIEF DESCRIPTION OF THE DRAWINGS

E The accompanying drawings, which are included <+ to provide a further understanding of the embodiments 3 and constitute a part of this specification, & 35 illustrate embodiments and together with the

N description help to explain the principles of the above. In the drawings:

Fig. 1 illustrates the results of example 4;

Fig. 2 illustrates the results of example 5; and

Fig. 3 illustrates the results of example 6.

DETAILED DESCRIPTION

The present disclosure relates to a method for producing a binder composition. The method comprises: i) polymerizing crosslinking agent and polymerizable substance in an aqueous composition by mixing and heating at a temperature of 60 - 95 °C for preparing a pre-composition, wherein at least 30 weight-% of the polymerizable substance originates from lignin, and ii) mixing the pre-composition with silane, wherein silane is used in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, to form a binder composition having a free formaldehyde content of at most 0.5 %.

The present disclosure further relates to a binder composition comprising crosslinking agent pol- ymerized with polymerizable substance, and silane, wherein: - at least 30 weight-% of the polymerizable n substance originates from lignin,

S - the binder composition comprises silane in

O an amount of 0.1 — 0.9 weight-% based on the total dry = 30 weight of the binder composition, and © - the binder composition has a free formalde-

E hyde content of at most 0.5 %. s The binder composition may be an aqueous = binder composition. & 35 The present disclosure further relates to the

N use of the binder composition as disclosed in the cur- rent specification for producing an insulating wool product. The method may thus be used for producing a binder composition for producing an insulating wool product.

Further is disclosed an insulating wool prod- uct comprising a fiber matrix and a binder composi- tion, wherein the binder composition comprises cross- linking agent polymerized with polymerizable sub- stance, and silane, wherein: - at least 30 weight-% of the polymerizable substance originates from lignin, - the binder composition comprises silane in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, and - the binder composition has a free formalde- hyde content of at most 0.5 weight-%.

The inventors surprisingly found out that by using the binder composition as disclosed in the cur- rent specification, one is able to produce an insulat- ing wool product that exhibits a low amount of formal- dehyde emissions as well as a low amount of phenol emissions, while simultaneously having a high water- tolerance and strength. Thus, the binder composition as disclosed in the current specification has the add- ed utility of being a more environmentally friendly solution to be used for producing an insulating wool product.

In one embodiment, silane is used in an & amount of 0.2 — 0.7 weight-%, or 0.3 — 0.5 weight-%,

N based on the total dry weight of the binder composi- 3 30 tion. In one embodiment, the binder composition com-

S prises silane in an amount of 0.2 - 0.7 weight-%, or

E 0.3 — 0.5 weight-%, based on the total dry weight of 3 the binder composition. Silane has the added utility

S of promoting adhesion to achieve high strength and 2 35 good moisture resistance in an insulating wool prod-

I uct.

In one embodiment, the method comprises mix- ing in ii) the pre-composition also with a scavenger and/or a hardener. In one embodiment, the binder com- position comprises also a scavenger and/or a hardener. 5 In one embodiment, the scavenger is selected from urea, ammonia, dicyandiamide, melamine, tannin such as tannin extracts, gallic acid, sodium hydrogen sulfite (NaHS0:3), sodium sulfite (Na,S0:;), sodium meta- bisulphite (Na:S,0s), ammonium hydrogen sulfite, poly- amides, dextrose, amine, ammonia sulfite, ammonium salts, ammonium hydroxide, ammonium carbonate, ammoni- um bicarbonate, oxygenated sulfur salts, sodium sul- fite, sodium bisulfate, sodium metabisulfite, mela- mine, cyanoguanidine, guanamine, caprinoguanamine, melamine, dicyandiamine, ethyl acetoacetate, green tea catechin, lignocellulosic, tannic acid, wood bark flours, chestnut flour, fir trees flour, wheat flour, rice hus flour, hemp four, molasses, and/or charcoal.

In one embodiment, the scavenger is urea. Also, a mix- ture of at least two scavengers may be used.

In one embodiment, the hardener is selected from sulphates and/or phosphates. In one embodiment, the hardener is selected from ammonium sulphate and/or ammonium hydroxide. In one embodiment, the hardener is ammonium sulphate. In one embodiment, the hardener is selected from alkaline metal sulphate, alkaline metal phosphate, alkaline earth metal sulfates and/or alka- & line earth metal phosphates. Also, a mixture of at

N least two hardeners may be used. 3 30 In one embodiment, the method comprises mix-

S ing in ii) the pre-composition also with urea and/or

E ammonium sulphate. In one embodiment, the binder com- > position comprises also urea and/or ammonium sulphate.

S The urea may be used for producing a binder 2 35 composition with a suitably low viscosity value. The

I urea may further be used for increasing the dry solids content of the binder composition. In one embodiment,

urea is used in an amount of 0 - 9 weight-%, or 0.1 - 9 weight-%, or 0.5 — 8 weight-%, or 1 - 7 weight-%, or 2 — 6 weight-%, or 3 - 5 weight-%, based on the total wet weight of the binder composition. In one embodi- ment, the binder composition comprises urea in an amount of 0 - 9 weight-%, 0.1 - 9 weight-%, or 0.5 — 8 weight-%3, or 1 - 7 weight-%, or 2 - 6 weight-%, or 3 - 5 weight-%, based on the total wet weight of the bind- er composition. Urea may be used to decrease the vis- cosity of the binder composition so that it may be sprayed on the fiber matrix when used for producing insulating wool. The inventors surprisingly found out that, if used, only a low amount of urea may be needed to further drop the free formaldehyde content of the binder composition and thus the formaldehyde emissions of the produced insulating wool product. In one embod- iment, no urea is used for producing the binder compo- sition. In one embodiment, the binder composition com- prises no urea.

The "total wet weight” should in this speci- fication be understood, unless otherwise stated, as the weight of both the dry matter and the liquid part, e.g. water, of the binder composition.

Ammonium sulphate, when used in the binder composition for producing an insulating wool product, has the added utility of providing the insulating wool product a satisfactory tensile strength formed during & the curing process.

N In one embodiment, ammonium sulphate is used 3 30 in an amount of 0 - 15 weight-%, or 0.5 -— 15 weight-%,

S or 1 - 14 weight-%, or 2 - 13 weight-%, or 3 — 12

T weight-%3, or 4 - 11 weight-%, or 5 - 10 weight-%, or 6 > - 9 weight-%3, based on the total dry weight of the

S binder composition. In one embodiment, ammonium sul- 2 35 phate is used in an amount of 0 - 7 weight-%, or 0.5 -

S 7 weight-3, or 1 - 6 weight-%, or 2 - 5 weight-%, or 3 - 4 weight-%3, based on the total dry weight of the binder composition. In one embodiment, ammonium sul- phate is used in an amount of 5 - 15 weight-%, or 6 - 14 weight-%, or 7 - 13 weight-%, or 8 - 12 weight-%, or 9 —- 11 weight-%, based on the total dry weight of the binder composition.

In one embodiment, the binder composition comprises ammonium sulphate in an amount of 0 - 15 weight-%, or 0.5 - 15 weight-%, or 1 - 14 weight-%, or 2 — 13 weight-%, or 3 — 12 weight-%, or 4 - 11 weight- %, or 5 - 10 weight-%, or 6 — 9 weight-%, based on the total dry weight of the binder composition. In one em- bodiment, the binder composition comprises ammonium sulphate in an amount of 0 - 7 weight-%, or 0.5 — 7 weight-%, or 1 - 6 weight-%, or 2 - 5 weight-%, or 3 - 4 weight-%, based on the total dry weight of the bind- er composition. In one embodiment, the binder composi- tion comprises ammonium sulphate in an amount of 5 - 15 weight-%, or 6 - 14 weight-%, or 7 - 13 weight-%, or 8 —- 12 weight-%, or 9 - 11 weight-%, based on the total dry weight of the binder composition.

In one embodiment, no ammonium sulphate is used for producing the binder composition. In one em- bodiment, the binder composition comprises no ammonium sulphate.

The lignin used for preparing the binder com- position may be selected from a group consisting of kraft lignin, steam explosion lignin, biorefinery lig- & nin, supercritical separation lignin, hydrolysis lig-

N nin, flash precipitated lignin, biomass originating 3 30 lignin, lignin from alkaline pulping process, lignin

S from soda process, lignin from organosolv pulping, = lignin from alkali process, lignin from enzymatic hy- drolysis process, and any combination thereof. In one

S embodiment, the lignin is wood based lignin. The lig- 2 35 nin can originate from softwood, hardwood, annual

I plants or from any combination thereof.

By "kraft lignin” is to be understood in this specification, unless otherwise stated, lignin that originates from kraft black liquor. Black liquor is an alkaline aqueous solution of lignin residues, hemi cellulose, and inorganic chemicals used in a kraft pulping process. The black liquor from the pulping process comprises components originating from differ- ent softwood and hardwood species in various propor- tions. Lignin can be separated from the black liquor by different, techniques including e.g. precipitation and filtration. Lignin usually begins precipitating at pH values below 11 - 12. Different pH values can be used in order to precipitate lignin fractions with different properties. These lignin fractions differ from each other by molecular weight distribution, e.g.

Mw and Mn, polydispersity, hemicellulose and extrac- tive contents. The molar mass of lignin precipitated at a higher pH value is higher than the molar mass of lignin precipitated at a lower pH value. Further, the molecular weight distribution of lignin fraction pre- cipitated at a lower pH value is wider than of lignin fraction precipitated at a higher pH value. The pre- cipitated lignin can be purified from inorganic impu- rities, hemicellulose and wood extractives using acid- ic washing steps. Further purification can be achieved by filtration.

The term “flash precipitated lignin” should be understood in this specification as lignin that has & been precipitated from black liquor in a continuous

N process by decreasing the pH of a black liguor flow, 3 30 under the influence of an over pressure of 200 - 1000

S kPa, down to the precipitation level of lignin using a

E carbon dioxide based acidifying agent, preferably car- 3 bon dioxide, and by suddenly releasing the pressure

S for precipitating lignin. The method for producing 2 35 flash precipitated lignin is disclosed in patent ap-

I plication FI 20106073. The residence time in the above method is under 300 s. The flash precipitated lignin particles, having a particle diameter of less than 2 um, form agglomerates, which can be separated from black liquor using e.g. filtration. The advantage of the flash precipitated lignin is its higher reactivity compared to normal kraft lignin. The flash precipitat- ed lignin can be purified and/or activated if needed for the further processing.

The lignin may be derived from an alkali pro- cess. The alkali process can begin with liquidizing biomass with strong alkali followed by a neutraliza- tion process. After the alkali treatment, the lignin can be precipitated in a similar manner as presented above.

The lignin may be derived from steam explo- sion. Steam explosion is a pulping and extraction technigue that can be applied to wood and other fi- brous organic material.

By "biorefinery lignin” is to be understood in this specification, unless otherwise stated, lignin that can be recovered from a refining facility or pro- cess where biomass is converted into fuel, chemicals and other materials.

By “supercritical separation lignin” is to be understood in this specification, unless otherwise stated, lignin that can be recovered from biomass us- ing supercritical fluid separation or extraction tech- nigue. Supercritical conditions correspond to the tem- & perature and pressure above the critical point for a

N given substance. In supercritical conditions, distinct 3 30 liquid and gas phases do not exist. Supercritical wa-

S ter or liquid extraction is a method of decomposing

E and converting biomass into cellulosic sugar by em- > ploying water or liquid under supercritical condi-

S tions. The water or liquid, acting as a solvent, ex- 2 35 tracts sugars from cellulose plant matter and lignin

S remains as a solid particle.

The lignin may be derived from a hydrolysis process. The lignin derived from the hydrolysis pro- cess can be recovered from paper-pulp or wood-chemical processes.

The lignin may originate from an organosolv process. Organosolv 1s a pulping technique that uses an organic solvent to solubilize lignin and hemicellu- lose.

In one embodiment, the method comprises form- ing a binder composition having a pH value of 9 - 11, or 9.3 —- 10.5, or 9.5 - 10. In one embodiment, the binder composition has a pH value of 9 - 11, or 9.3 - 10.5, or 9.5 -— 10. The pH value may be adjusted by us- ing e.g. an alkali such as sodium hydroxide or potas- sium oxide, or an acid, e.g. a weak acid. Glycolic ac- id and weak sulphuric acid may be mentioned as exam- ples of acids that may be used. The above pH values have the added utility of stabilizing the binder com- position such that lignin may not be precipitated therefrom.

Polymerizing the crosslinking agent and the polymerizable substance in an aqueous composition may be conducted under heating at a temperature of 60 - 95 °C, or 75 — 90 °C, or 70 — 80 °C, or 70 - 90 °C. The heating in may be continued until a binder composition with a desired viscosity value is formed. In one em- bodiment, a pre-composition having a viscosity value

N of 30 — 500 mPa:s, or 40 - 400 mPa:s, or 50 — 250

N mPa:s, or 75 — 200 mPa:s, or 100 - 150 mPa:s, is 3 30 formed. The polymerization may be continued for 0.15 -

S 6 hours, or 0.25 - 5 hours, or 0.5 -— 3.5 hours.

E In one embodiment, the method comprises form- > ing a binder composition having a viscosity of 5 -— 300

S mPa:s, or 10 - 250 mPa:s, or 50 - 200 mPa:s, or 75 - 2 35 150 mPa:s. In one embodiment, the binder composition

S has a viscosity of 5 - 300 mPa:s, or 10 - 250 mPa:s, or 50 - 200 mPa:s, or 75 —- 150 mPa:s. The viscosity can be measured at a temperature of 25 °C by using a rotary viscometer (Digital Brookfield viscometer LVDV-

II+ Pro; cone spindle). When the viscosity of the binder composition is 50 - 250 mPa:s, spraying of the binder composition over the fiber matrix may be en- hanced. The viscosity of the binder composition can be adjusted by the use of the urea and water. The binder composition as disclosed in the current specification, has the added utility of having an infinite water tol- erance (water dilution capacity), whereby a high amount of water may be used without phase separation of the binder composition.

The crosslinking agent may be an aldehyde; such as formaldehyde or paraformaldehyde. In one em- bodiment, the aldehyde is prepared from bio-methanol.

The aldehyde may thus be of biobased origin. The alde- hyde may alternatively be of fossil origin. In one em- bodiment, the aldehyde is prepared from methanol.

The total amount of crosslinking agent used for producing the binder composition may be 15 - 35 weight-%, or 17 - 30 weight-%, or 20 - 27 weight-%, based on the total dry weight of the binder composi- tion. The total amount of crosslinking agent used for producing the binder composition may be 20 - 35 weight-3, or 22 - 27 weight-%, or 23 - 25 weight-%, based on the total dry weight of the binder composi- tion. The total amount of crosslinking agent used for & producing the binder composition may be 16 - 26

N weight-%3, or 18 - 24 weight-%, or 20 - 22 weight-%, 3 30 based on the total dry weight of the binder composi-

S tion. The total amount of crosslinking agent used for

T producing the binder composition may be 15 - 25 > weight-%3, or 17 - 23 weight-%, or 19 - 21 weight-%,

S based on the total dry weight of the binder composi- 2 35 tion.

I The "total dry weight” should in this speci- fication should in this specification be understood,

unless otherwise stated, as the weight of the dry mat- ter of the binder composition, i.e. excluding water.

The total amount of polymerizable substance used for producing the binder composition may be 40 - 70 weight-%, or 45 - 67 weight-%, or 47 - 65 weight-%, or 50 - 63 weight-%, based on the total dry weight of the binder composition.

The weight ratio of the crosslinking agent to the polymerizable substance may be 0.25 —- 0.55, or 0.30 — 0.50.

A catalyst may also be used in the aqueous composition. The catalyst may comprise a salt or a hy- droxide of an alkali metal or alkali earth metal. In one embodiment, the catalyst is selected from a group consisting of sodium hydroxide, potassium hydroxide, barium hydroxide, and any combination or mixture thereof. In one embodiment, the catalyst is sodium hy- droxide.

The polymerizing agent may in addition to lignin comprise a compound selected from the class of phenols. In this specification, unless otherwise stat- ed, the term "compound selected from the class of phe- nols” should be understood as meaning a fossil-based compound of phenols. I.e. phenols are compounds con- sisting of a single aromatic ring where to one or more hydroxyls (—0H) are bonded. Such a compound selected from the class of phenols may be e.g. phenol, cresol,

N or resorcinol. Such phenols are toxic compounds. In

N one embodiment, the method comprises the proviso that 3 30 no compound selected from the class of phenols is used

S for producing the binder composition. The method as

E disclosed in the current specification has the added > utility of providing a manner to produce a binder com-

S position free of materials of fossil origin. The bind- 2 35 er composition produced may thus be free of fossil-

S based phenol compound(s). The binder composition as disclosed in the current specification may thus be prepared as a non-toxic binder composition. I.e. a binder composition with reduced share of toxic or haz- ardous compounds may be prepared. The binder composi- tion as disclosed in the current specification may be prepared as a binder composition having 100 % biologi- cal origin. Thus, all the components used for prepar- ing the binder composition may be of biological origin and thus no fossil-based components may need to be used.

In one embodiment, the method comprises form- ing a binder composition having a free formaldehyde content of at most 0.4 %, or at most 0.3 3, or at most 0.2 3, or at most 0.15 %, or at most 0.1 %. In one em- bodiment, the method comprises forming a binder compo- sition having a free formaldehyde content of 0 - 0.4 %, or 0.01 - 0.3 3, or 0.03 - 0.2 &, or 0.05 - 0.15 %, or about 0.1 %.

In one embodiment, the binder composition has a free formaldehyde content of at most 0.4 %, or at most 0.5 3, or at most 0.2 3, or at most 0.15 %, or at most 0.1 %. In one embodiment, the binder composi- tion has a free formaldehyde content of 0 - 0.4 %, or 0.01 - 0.3 %, or 0.03 - 0.2 %, or 0.05 - 0.15 %, or about 0.1 %.

The free formaldehyde content may be deter- mined in accordance with standard EN-ISO 11402.

In one embodiment, the method comprises form- & ing a binder composition having a free phenol content

N of at most 1 3, or at most 0.8 3, or at most 0.6 %, or 3 30 at most 0.5 %, or at most 0.4 %. In one embodiment,

S the method comprises forming a binder composition hav-

T ing a free phenol content of 0 - 1 %, or 0.1 - 0.8 %, * or 0.2 — 0.6 %, or 0.3 - 0.5 %, or about 0.4 %.

S In one embodiment, the binder composition has 2 35 a free phenol content of at most 1 %, or at most 0.8

I %, or at most 0.6 %, or at most 0.5 %, or at most 0.4 2. In one embodiment, the binder composition has a free phenol content of 0 - 1 %, or 0.1 - 0.8 %, or 0.2 - 0.6 %, or 0.3 - 0.5 %, or about 0.4.

The free phenol content of the binder compo- sition may be determined by gas chromatography-flame ionization detector (GC-FID) method in accordance with standard SFS-EN ISO 8974:2002 with the exception that the alkaline sample solution is diluted before neu- tralization.

In one embodiment, the method comprises form- ing a binder composition exhibiting formaldehyde emis- sion of 0 — 0.3 mg/m*h, or 0 - 0.25 mg/m*h, or 0 — 0.2 mg/m’h, or 0 — 0.15 mg/m*h, or 0 - 0.1 mg/m*h, or 0 -— 0.05 mg/m?h, or 0 — 0.03 mg/m?h, or 0 — 0.01 mg/m?h. In one embodiment, the binder composition exhibits a for- maldehyde emission of 0 - 0.3 mg/m¢h, or 0 — 0.25 mg/m’h, or 0 — 0.2 mg/m’h, or 0 - 0.15 mg/m*h, or 0 -— 0.1 mg/m*h, or 0 - 0.05 mg/m*h, or 0 - 0.03 mg/m?h, or 0 — 0.01 mg/m*h.

In one embodiment, the method comprises form- ing a binder composition exhibiting phenol emission of at most 1.5 mg/m?h, or at most 1.3 mg/m?h, or at most 1 mg/m?h, or at most 0.8 mg/m?h, or at most 0.5 mg/m*h.

In one embodiment, the binder composition exhibits a phenol emission of at most 1.5 mg/m?*h, or at most 1.3 mg/m?*h, or at most 1 mg/m*h, or at most 0.8 mg/m?h, or at most 0.5 mg/m*h.

The formaldehyde emission and the phenol & emission exhibited by the binder composition may be

N measured according to standard ISO 12460-3:2015 with 3 30 modified sample size (using a mold with dimensions of

S 173 mm in length, 22 mm in width and 22 mm in height).

T As the sand as such, that used for the measurements > according to the standard, does not affect the meas-

S ured results, the measured emissions are applicable 2 35 for the binder composition.

S In one embodiment, 30 — 100 weight-%, or 40 — 99 weight-%, or 50 - 95 weight-%, or 60 —- 90 weight-%,

or 70 —- 85 weight-%, of the polymerizable substance originates from lignin.

The binder composition as disclosed in the current specification may be used for producing an in- sulating wool product. The insulating wool product may be a mineral wool product, such as glass wool product, stone wool product, or slag wool product.

The insulating wool product may thus comprise a fiber matrix and a binder composition as disclosed in the current specification.

In one embodiment, the insulating wool prod- uct comprises a fiber matrix selected from glass fi- ber, stone fiber, or cellulose fiber. In one embodi- ment, the total amount of binder composition in the insulating wool product is 1 — 10 weight-%, or 2 - 9 weight-%3, or 3 - 8 weight-%, or 4 - 7 weight-%, or 5 - 6 weight-%, based on the total weight of the insulat- ing wool product.

Further additive(s) may be combined with the binder composition when producing the insulating wool product. De-dusting oils, emulsifiers, dyes, extend- ers, and scavengers may be mentioned as examples of such additives.

The insulating wool product may be produced by spraying the binder composition over melted fiber matrix, which is pre-formed in high temperatures, e.g. at over 1000 °C. The fiber matrix of the insulating

N wool product may be in the form of a sheet, slabs,

N batts, rolls, a panel, or blown.

S 30 The method disclosed in the current specifi- 3 cation has the added utility of enabling one to pro-

E duce a binder composition having properties being ben- > eficial for producing an insulating wool product. The

S produced binder composition may exhibit a content of 2 35 free formaldehyde and content of free phenols that

I make it especially suitable to be used for producing an insulating wool product. Using the binder composi-

tion as disclosed in the current specification for the production of an insulating wool product has the added utility of providing the wool product with low emis- sions while simultaneously exhibiting a high strength.

EXAMPLES

Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings.

The description below discloses some embodiments in such a detail that a person skilled in the art is able to utilize the embodiments based on the disclosure. Not all steps or features of the embodiments are discussed in detail, as many of the steps or features will be obvious for the person skilled in the art based on this specification.

Example 1 - Preparing binder compositions

In this example different binder compositions were prepared.

The following components and their percentages were used in this example for producing the pre-compositions:

Samples with 30 weight-% of the polymerizable substance being lignin (LPF300)

N Kraft lignin 8.7 weight-%

N Phenol 20.3 weight-% 3 30 Formaldehyde 13.9 weight-3%

S NaOH 4 weight-% = The rest being water a

S Samples with 50 weight-% of the polymerizable 2 35 substance being lignin (LPF500) < Kraft lignin 15.8 weight-%

Phenol 15.8 weight-%

Formaldehyde 11.5 weight-%

NaOH 4 weight-%

The rest being water

Samples with 70 weight-% of the polymerizable substance being lignin (LPF700)

Kraft lignin 20.7 weight-%

Phenol 8.9 weight-%

Formaldehyde 9.4 weight-%

NaOH 4 weight-%

The rest being water

The above components were mixed and heated at a temperature of about 70 °C in order to polymerize the lignin, phenol, and formaldehyde, to form the pre- composition. Then silane was mixed with this formed pre-composition.

Further samples were prepared by adding vary- ing amounts of urea and/or ammonium sulphate. If urea was used, then it was added before silane. The amounts of silane, urea, and ammonium sulphate used in the different samples are indicated in the blow tables. A commercial phenol-formaldehyde resin (PF) was used as a comparative example. The prepared binder composi- tions were tested as presented in the below examples.

Fxample 2 - Measuring free formaldehyde content and & free phenol content

N

3 30 The free formaldehyde content and the free

S phenol content of prepared samples were measured as

E described in the current specification. The composi- > tion of the tested samples and their results are pre-

S sented in the below table 1. 2 35

I Table 1. Amount of urea, ammonium sulphate, and silane in the samples and the measured results

Com- mer- cial

PF LPF500|LPF500|LPF500|LPF500|LPF500

Urea, 3 | 18 | 0 | o | o | o | o

Ammonium sulphate

TT | ao | aa | ao | 20 | wo | ao

Naor | | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 -

Theoretical dry solids iin | | ao| vo] na|aol va.

Dry content (binder com- position), 1 g, 135 °c, 3 h 45.7 41.5 41.5 41.5 41.2 41.2

Free promot, © | 1.1 | 0.8 | 0.8 | 0.8 | 0.7 | 07

Free formal-

Viscosity

Brookfield, plate, 25°C, mPa s 26.0 147.0 | 147.0 | 147.0 | 149.0 | 149.0 *The free phenol content: Determined by gas chromatog- raphy-flame ionization detector (GC-FID) method in ac- cordance with standard SFS-EN ISO 8974:2002 with the exception that the alkaline sample solution is diluted before neutralization **The free formaldehyde content: Determined in accord- on ance with standard EN-ISO 11402

S ro Table 2. Amount of urea, ammonium sulphate, and silane + in the samples and the measured results © Com-

T mer- ” cial

S PF LPF500|LPF500|LPF500|LPF500|LPF500 3 Trea, 3 | 18 | 0.0 | 5.0 | 5.0 | 5.0 | 10.0]

N Ammonium

R sulphate ii | ao | aa | ao | mo | ao an

Free phenol*, 3 1.1 0.7 0.7

Dry content, 1 g, 135 °C, 3 h, % 45.7 43.2 43.2 43.2 44.8 46.7

Free formal- dehyde**, % 0.3

Viscosity

Brookfield, plate, 25°C, mPa -s 99.2 99.2 99.2 129.6 | 97.6 *The free phenol content: Determined by gas chromatog- raphy-flame ionization detector (GC-FID) method in ac- cordance with standard SFS-EN ISO 8974:2002 with the exception that the alkaline sample solution is diluted before neutralization **The free formaldehyde content: Determined in accord- ance with standard EN-ISO 11402

From the results presented in table 1 and ta- ble 2 one can see that with the binder compositions prepared have a low content of free formaldehyde and free phenol.

Example 3 - Measuring formaldehyde and phenol emis- sions n Prepared binder composition samples were used

S to prepare sandbars and the sandbar samples were test-

O ed as described in the current specification. The = 20 sandbars were prepared by mixing the binder composi- © tion samples with silica sand (grain size of 0.1 - 0.6

E mm) in a mold with dimensions of 173 mm in length, 22 <+ mm in width and 22 mm in height, and then by pressing o = the formed mixture with a suitable hydraulic press ca- & 25 pable of producing 1.6 N/mm? of specific pressure. The

N pressed sandbar mixture was then cured in an oven at a temperature of 180°C for 2 hour and 45 minutes. After the curing, the samples were tightly wrapped with a plastic wrap to prevent the loss of emissions from the material.

The formed sandbars where then analyzed for their formaldehyde and phenol emissions. As the sand as such does not affect the measured results, the measured emissions are applicable for the binder com- position. The analyses were made by unwrapping the sandbars and then putting the same into a sample rack inside a gas analysis chamber (e.g. GreCon GA 6000) with constant temperature of 60°C, airflow of 60 1/h and pressure of 1100 Pa. The samples were held within the chamber for four hours, during which the released emissions were directed into wash bottles, and then analyzed with Hach’s cuvette test method within 24 hours with Spectrophotometer (e.g. DR3900). The re- sults are presented in the below tables.

Table 3. Emissions from cured sandbars

Binder Formaldehyde Phenol osille | "yst | om * The sample contained 0.2 weight-% of silane based on the total dry weight of the binder composition, but no urea or ammonium sulphate.

From table 3 one can see that the formalde- & 25 hyde emissions as well as the phenol emissions for the

N prepared binder composition are very low.

S

3 Table 4. Emissions from cured sandbars

I Binder < on* (mg/m*h) (mg/m*h)

S [ro | 0 | oar | 0.50

S | 2PF300 | 7.5 | 0.00 | 20.48 —

S

1PFS00 | 0 | 0.00 | 20.79

—tersa0 | 7.5 | 00 | 0.56 —wersc0 | 15 | 0.06 | 0.85 —werio0 | 0 | 028 | 1.05 * all the samples contained 0.2 weight-% of silane and 4 weight-% of ammonium sulphate based on the total dry weight of the binder composition.

From table 4 one can see that with the binder compositions prepared with as low amount of urea as 7.5 welight-% one is able to prepare a binder composi- tion having the formaldehyde emission of as low as at most 0.01 mg/m?h, whereas a urea amount of 18 weight-% is needed to reduce the formaldehyde emissions to 0.075 mg/m?*h in the comparative PF sample. Also, the phenol emissions for the prepared samples were on a low level.

Example 4 - Strength of the binder compositions

In this example the effect of varving the amount of silane in the binder compositions on the dry strength of the prepared sandbars was tested.

Sandbar samples prepared with differing amounts of silane were prepared as above presented and tested for the strength of the formed sandbars.

N “LPF500” pre-composition was used as a basis for all

S the samples. The dry strength of the sandbar samples > 25 was tested according to standard EN 310:1993 Modulus

S of rupture (which is equal to the dry strength of the

S sample). The results are presented in Fig. 1. From the

E results one can see that samples with as low amount as < 0.2 weight-% or 0.5 weight-% of silane in the binder x 30 composition exhibited suitable dry strength values.

S

N Example 5 - Strength of the binder compositions

In this example the dry strength of sandbars prepared with the binder composition samples prepared in example 2 was tested. Sandbar samples were prepared as above presented. The dry strength of the sandbar samples was tested according to standard EN 310:1993

Modulus of rupture (which is equal to the dry strength of the sample). The results are presented in Fig. 2.

From the results one can see that the dry strength of sandbars prepared with the binder composition samples as disclosed in the current specification one may achieve equally good values as with the comparative commercial PF resin.

Example 6 - Strength of the binder compositions

In this example the dry strength of sandbars prepared with the binder composition samples based on pre-compositions LPF500 and LPF300 was tested. The following samples were prepared:

Table 5. Amount of urea, ammonium sulphate, and silane in the samples [OF "| upesoo | 107200] | ter300 | 187200 | 107300)

PF LPF500 | LPF300 | LPF300 | LPF300 | LPF300

AS | oa | o | o | 3 | 6 | 9

Urea | 18 | o | o | o | o | o & Sandbar samples were prepared as above

N

> 25 presented by using the different binder composition ? samples. The dry strength of the sandbar samples was

S tested according to standard EN 310:1993 Modulus of

E rupture (which is equal to the dry strength of the < sample). The results are presented in Fig. 3. x 30 From the results one can see that the dry

O strength of sandbars prepared with the binder & composition samples as disclosed in the current specification is high.

It is obvious to a person skilled in the art that with the advancement of technology, the basic idea may be implemented in various ways. The embodiments are thus not limited to the examples described above; instead, they may vary within the scope of the claims.

The embodiments described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined together to form a further embodiment. A method, a binder composition, the use, or the insulating wool product, disclosed herein, may comprise at least one of the embodiments described hereinbefore. It will be understood that the benefits and advantages described above may relate to one embodiment or may relate to several embodiments.

The embodiments are not limited to those that solve any or all of the stated problems or those that have any or all of the stated benefits and advantages. It will further be understood that reference to ‘an’ item refers to one or more of those items. The term “comprising” is used in this specification to mean including the feature (s) or act (s) followed thereafter, without excluding the presence of one or more additional features or acts.

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Claims

1. A method for producing a binder composi- tion, wherein the method comprises: i) polymerizing crosslinking agent and polymerizable substance in an aqueous composition by mixing and heating at a temperature of 60 - 95 °C for preparing a pre-composition, wherein at least 30 weight-% of the polymerizable substance originates from lignin, and ii) mixing the pre-composition with silane, wherein silane is used in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, to form a binder composition having a free formaldehyde content of at most 0.5 %.

2. The method of claim 1, wherein silane is used in an amount of 0.2 - 0.7 weight-%, or 0.3 - 0.5 weight-%, based on the total dry weight of the binder composition.

3. The method of any one of the preceding claims, wherein the method comprises mixing in ii) the pre-composition also with a scavenger and/or a harden-

er.

4. The method of any one of the preceding claims, wherein the method comprises mixing in ii) the pre-composition also with urea and/or ammonium sul- n phate.

N 5. The method of claim 4, wherein urea is a used in an amount of 0.1 - 9 weight-%, or 0.5 - 8 = 30 weight-%, or 1 - 7 weight-%, or 2 - 6 weight-%, or 3 - © 5 weight-%, based on the total wet weight of the bind- E er composition.

< 6. The method of any one of claims 4 - 5, x wherein ammonium sulphate is used in an amount of 0.5 N 35 - 15 weight-%, or 1 — 14 weight-%, or 2 - 13 weight-%, N or 3 - 12 weight-3, or 4 - 11 weight-%, or 5 - 10 weight-%, or 6 - 9 weight-%, based on the total dry weight of the binder composition.

7. The method of any one of the preceding claims, wherein the method comprises forming a binder composition having a pH value of 9 - 11, or 9.3 -

10.5, or 9.5 — 10.

8. The method of any one of the preceding claims, wherein the method comprises forming a binder composition having a viscosity of 5 — 300 mPa:s, or 10 - 250 mPa:s, or 50 — 200 mPa:s, or 75 —- 150 mPa:s.

9. The method of any one of the preceding claims, wherein the method comprises forming a binder composition having a free formaldehyde content of at most 0.4 3, or at most 0.3 3, or at most 0.2 %, or at most 0.15 %, or at most 0.1 %.

10. The method of any one of the preceding claims, wherein the method comprises forming a binder composition having a free phenol content of at most 1 %, or at most 0.8 %, or at most 0.6 %, or at most 0.5 %, or at most 0.4 %.

11. The method of any one of the preceding claims, wherein 30 - 100 weight-%, or 40 - 99 weight- 2, or 50 - 95 weight-%, or 60 —- 90 weight-%, or 70 - 85 weight-%, of the polymerizable substance originates from lignin.

12. The method of any one of the preceding claims, wherein the method comprises forming a binder & composition exhibiting formaldehyde emission of 0 -—-

N 0.3 mg/m’h, or 0 — 0.25 mg/m*h, or 0 — 0.2 mg/m*h, or O 3 30 - 0.15 mg/m?h, or 0 — 0.1 mg/m’h, or 0 —- 0.05 mg/m*h, S or 0 — 0.03 mg/m?*h, or 0 — 0.01 mg/m*h. T 13. The method of any one of the preceding > claims, wherein the method comprises forming a binder S composition exhibiting phenol emission of at most 1.5 2 35 mg/m’h, or at most 1.3 mg/m’h, or at most 1 mg/m’h, or I at most 0.8 mg/m*h, or at most 0.5 mg/m*h.

14. A binder composition, wherein the binder composition comprises crosslinking agent polymerized with polymerizable substance, and silane, wherein: - at least 30 weight-% of the polymerizable substance originates from lignin, - the binder composition comprises silane in an amount of 0.1 - 0.9 weight-% based on the total dry weight of the binder composition, and - the binder composition has a free formalde- hyde content of at most 0.5 %.

15. The binder composition of claim 14, wherein the binder composition comprises silane in an amount of 0.2 — 0.7 weight-%, or 0.3 —- 0.5 weight-%, based on the total dry weight of the binder composi- tion.

16. The binder composition of any one of claims 14 - 15, wherein the binder composition com- prises also a scavenger and/or a hardener.

17. The binder composition of any one of claims 14 - 16, wherein the binder composition com- prises also urea and/or ammonium sulphate.

18. The binder composition of claim 17, wherein binder composition comprises urea in an amount of 0.1 - 9 weight-%, or 0.5 - 8 weight-%, or 1 -— 7 weight-%, or 2 — 6 weight-%, or 3 - 5 weight-%, based on the total wet weight of the binder composition.

19. The binder composition of any one of AN claims 17 - 18, wherein the binder composition com- N prises ammonium sulphate in an amount of 0.5 - 15 3 30 weight-%, or 1 - 14 weight-%, or 2 - 13 weight-%, or 3 S - 12 weight-%, or 4 — 11 weight-%, or 5 - 10 weight-%, E or 6 — 9 weight-%, based on the total dry weight of * the binder composition. S 20. The binder composition of any one of 2 35 claims 14 — 19, wherein the binder composition has a S pH value of 9 - 11, or 9.3 — 10.5, or 9.5 - 10.

21. The binder composition of any one of claims 14 — 20, wherein the binder composition has a viscosity of 5 - 300 mPa:s, or 10 — 250 mPa:s, or 50 — 200 mPa:s, or 75 -— 150 mPa:s.

22. The binder composition of any one of claims 14 — 21, wherein the binder composition has a free formaldehyde content of at most 0.4 %, or at most

0.3 3, or at most 0.2 3, or at most 0.15 3, or at most

0.1 %.

23. The binder composition of any one of claims 14 — 22, wherein the binder composition has a free phenol content of at most 1 3, or at most 0.8 %, or at most 0.6 %, or at most 0.5 %, or at most 0.4 %.

24. The binder composition of any one of claims 14 - 23, wherein 30 - 100 weight-%, or 40 - 99 weight-%, or 50 - 95 weight-%, 60 - 90 weight-%, or 70 - 85 weight-%2, of the polymerizable substance origi- nates from lignin.

25. The binder composition of any one of claims 14 - 24, wherein the binder composition exhib- its a formaldehyde emission of 0 - 0.3 mg/m?h, or 0 -

0.25 mg/m*h, or 0 — 0.2 mg/m*h, or 0 - 0.15 mg/m?h, or 0 — 0.1 mg/m?h, or 0 — 0.05 mg/m*h, or 0 - 0.03 mg/m*h, or 0 — 0.01 mg/m?h.

26. The binder composition of any one of claims 14 — 25, wherein the binder composition exhib- its a phenol emission of at most 1.5 mg/m?h, or at & most 1.3 mg/m?h, or at most 1 mg/m*h, or at most 0.8 N mg/m?h, or at most 0.5 mg/m’h. 3 30 27. Use of the binder composition of any one S of claims 14 - 26 for producing an insulating wool x product.

28. The use of claim 27, wherein the insulat- S ing wool product comprises a fiber matrix selected 2 35 from glass fiber, stone fiber, or cellulose fiber. S 29. The use of any one of claims 27 - 28, wherein the total amount of binder composition in the insulating wool product is 1 — 10 weight-%, or 2 - 9 weight-%3, or 3 - 8 weight-%, or 4 - 7 weight-%, or 5 - 6 welght-%,, based on the total weight of the insulat- ing wool product.

30. An insulating wool product comprising a fiber matrix and a binder composition, wherein the binder composition comprises crosslinking agent pol- ymerized with polymerizable substance, and silane, wherein: - at least 30 weight-% of the polymerizable substance originates from lignin, - the binder composition comprises silane in an amount of 0.1 — 0.9 weight-% based on the total dry weight of the binder composition, and - the binder composition has a free formalde- hyde content of at most 0.5 %. O N O N LÖ ? <t O I a a <t o <t O 0 N O N