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WO2024254663A1 - Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée par extrusion réactive avec des anhydrides, et composite thermoplastique - Google Patents

Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée par extrusion réactive avec des anhydrides, et composite thermoplastique Download PDF

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Publication number
WO2024254663A1
WO2024254663A1 PCT/BR2024/050251 BR2024050251W WO2024254663A1 WO 2024254663 A1 WO2024254663 A1 WO 2024254663A1 BR 2024050251 W BR2024050251 W BR 2024050251W WO 2024254663 A1 WO2024254663 A1 WO 2024254663A1
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Prior art keywords
cellulose
pulp
process according
thermoplastic composite
thermoplastic
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PCT/BR2024/050251
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English (en)
Portuguese (pt)
Inventor
Antonio José Felix De CARVALHO
Talita Rocha RIGOLIN
Bruna Papa SPADAFORA
Laura De Araujo HSIA
Original Assignee
Suzano S.A.
Universidade De São Paulo - Usp
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Priority claimed from BR102023011657-4A external-priority patent/BR102023011657A2/pt
Application filed by Suzano S.A., Universidade De São Paulo - Usp filed Critical Suzano S.A.
Publication of WO2024254663A1 publication Critical patent/WO2024254663A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/02—Small extruding apparatus, e.g. handheld, toy or laboratory extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present invention belongs to the field of thermoplastic composite materials and relates to a process for preparing a thermoplastic composite from cellulose pulp modified via reactive extrusion (REX) with long-chain anhydrides, and to a thermoplastic composite prepared from said process.
  • Said thermoplastic composite presents good cellulose fiber dispersion characteristics and better mechanical properties compared to the synthetic thermoplastic polymer.
  • the modification of the cellulose pulp by reactive extrusion with anhydrides is carried out before obtaining the composite with the thermoplastic polymer and, thus, the good dispersion of the fibers also provides better reinforcement of the composite material.
  • thermoplastic composites consisting of high-quality materials from renewable sources has been intensified, in which the replacement of synthetic polymers with natural polymers is particularly advantageous.
  • Lignocellulosic materials can be used as fillers or as reinforcing agents in thermoplastic composites, and such materials have become important in polymer matrices due to their advantages over other inorganic or synthetic materials.
  • Eucalyptus or pine cellulose fibers can be subdivided into chemical, semi-chemical bleached and unbleached cellulose pulp, and have several advantages, such as low density, natural and renewable origin, low cost, and good mechanical properties.
  • chemical cellulose pulp is a commodity, composed mainly of cellulose and comes from a natural and renewable source, favoring interest in its use in a more sustainability-oriented approach.
  • cellulose is an attractive candidate for the development of materials due to its biocompatibility, biodegradability and possibility of chemical modification.
  • cellulose fiber has excellent properties, such as lightness, high mechanical strength, high modulus of elasticity and low linear thermal expansion, and its use in obtaining reinforced thermoplastic composites is strategic.
  • reinforced polymer composites with improved properties can replace conventional materials such as metals, plastics and wood in many types of applications, for example, the construction, packaging, automotive, furniture and aerospace industries.
  • cellulose fiber is highly hydrophilic and therefore has low affinity for hydrophobic resins (such as polypropylene, polyethylene and the like), so that simple mechanical mixing through an extruder or similar method may not generate composites with good dispersion of the fibers and therefore with satisfactory mechanical properties.
  • hydrophobic resins such as polypropylene, polyethylene and the like
  • thermoplastic composite material that combines a hydrophilic element and a hydrophobic element is still a challenge.
  • a composite containing cellulose fiber and a thermoplastic resin with a hydrophobic character such as polypropylene, polyethylene and similar, represents a great challenge due to the low dispersion property of the cellulose fiber, which makes it very difficult to form a composite with adequate properties.
  • hydrophilic cellulose pulp so as to use it as a mechanical reinforcement in hydrophobic thermoplastic resins.
  • An alternative is to modify the cellulose pulp fibers by exchanging the pulp water for long-chain anhydride (e.g., alkenyl succinic anhydride - ASA), which provides a hydrophobic characteristic and increases the matrix/fiber interaction.
  • long-chain anhydride e.g., alkenyl succinic anhydride - ASA
  • thermoplastic composite that combines two materials with different characteristics.
  • the present invention relates to a new and inventive process for modifying cellulose pulp fibers via reactive extrusion (REX) in the presence of an aprotic solvent with the swelling capacity of cellulose for the preparation of thermoplastic composite materials that present good dispersion characteristics, as well as improved mechanical properties in relation to the thermoplastic polymer, while reducing the amount of swelling solvent and aprotic solvent used.
  • the present invention also relates to a thermoplastic composite prepared from said process.
  • the present invention discloses a process for preparing thermoplastic composites of modified cellulose pulp via reactive extrusion in the presence of an aprotic solvent that has the capacity to swell cellulose, and the thermoplastic composite prepared from said process, for coating and modifying cellulose fibers, so that it presents good dispersion of fibers in the apolar matrix, without the presence of fiber agglomerates, in addition to good mechanical properties.
  • the process of the present invention allows reducing the amount of swelling solvent or aprotic solvent used in relation to other processes.
  • the modifying agent is from the class of anhydrides of the alkenyl succinic anhydride - ASA type (or similar reagent) while the swelling solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP) and dihydrolevoglucosenone (Cyrene).
  • NMP N-methyl-2-pyrrolidone
  • Cyrene dihydrolevoglucosenone
  • the invention relates to a process for treating cellulose fibers via reactive extrusion with anhydrides, in which the cellulose fibers are modified so as to facilitate subsequent dispersion in a thermoplastic polymer, thus forming a composite containing cellulose and the thermoplastic polymer, with a reduction in the amount of solvents used.
  • One embodiment of the invention relates to a process for preparing thermoplastic composite from modified cellulose pulp via reactive extrusion with anhydrides, which comprises the following steps: a) dewatering the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) by pressing and filtration; b) adding isopropanol or another solvent miscible in water and easily removable; c) pressing and filtering the mixture to eliminate excess liquid; d) repeating the process of adding isopropanol, pressing and filtration at least twice more; e) add an aprotic solvent to the resulting material until the cellulose/aprotic solvent ratio is 1:1 by mass or greater; f) evaporate the isopropanol in a vessel with stirring under a nitrogen flow and application of vacuum; g) obtain a composition with 50% pulp in aprotic solvent and a residual water in relation to the cellulose of less than 5%; h) add ASA anhydride and K2CO3 in the ASA
  • the aprotic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP) and dihydrolevoglucosenone (Cyrene).
  • NMP N-methyl-2-pyrrolidone
  • Cyrene dihydrolevoglucosenone
  • thermoplastic composite of cellulose pulp modified by reactive extrusion with anhydrides in which the fibers of the treated cellulose pulp present a better dispersion characteristic in relation to an untreated pulp, and, furthermore, have a degree of defibrillation controlled by the extrusion conditions in the reaction phase with ASA and also, but to a lesser extent, during composting with the thermoplastic matrix.
  • the present invention relates to a new and inventive process for preparing thermoplastic composite materials and to a thermoplastic composite obtained from said process, in which said process consists of modifying the cellulose pulp via reactive extrusion in the presence of an aprotic solvent that has the capacity to swell the cellulose.
  • thermoplastic composite presents an increased modulus of elasticity, good dispersion characteristics, as well as improved mechanical properties in relation to the synthetic thermoplastic polymer, in which the cellulose present in the composite acts as a reinforcing agent in the thermoplastic matrix.
  • the process of the present invention uses reduced amounts of anhydride and swelling agent in relation to processes known in the state of the art, in addition to allow the optimization of the washing process with a smaller number of steps or solvents in all phases of the process.
  • FIG. 1 is an illustrative flowchart of the process of preparing a thermoplastic composite material from bleached Kraft eucalyptus pulp modified via reactive extrusion (REX) with anhydrides.
  • REX reactive extrusion
  • FIG. 2 is a representative image of bleached Kraft Eucalyptus pulp modified with alkenyl succinic anhydride (ASA) via REX.
  • ASA alkenyl succinic anhydride
  • FIGS. 3A-3C present optical micrograph images of ASA-modified bleached Kraft eucalyptus pulp.
  • FIG. 4A is a representative image of a composite injection molded specimen with bleached Kraft eucalyptus pulp modified via the conventional method with excess ASA.
  • FIG. 4B is a representative image of a composite injection molded specimen with bleached eucalyptus Kraft pulp modified under reactive extrusion (REX) conditions with reduced amounts of ASA, solvents, and other reagents.
  • REX reactive extrusion
  • FIG. 5A is an illustrative image of a 0.5 mm thick thin film pressed from the specimen of FIG. 4A without prior filtration, i.e., with bleached Kraft eucalyptus pulp modified via the conventional method with excess ASA.
  • FIG. 5B is an illustrative image of a 0.5 mm thick thin film pressed from the specimen of FIG. 4B without prior filtration, i.e., with bleached Kraft eucalyptus pulp modified under reactive extrusion (REX) conditions with reduced amounts of ASA, solvents and other reagents.
  • REX reactive extrusion
  • composite materials represent the union or combination of two different materials with the aim of forming a new material with specific characteristics and properties of the materials used.
  • hydrophilic compounds cellulose
  • hydrophobic compounds thermoplastic polymers
  • the inventors of the present invention were unexpectedly able to obtain a method that can be used to prepare a thermoplastic composite with better dispersion characteristics, which can be observed from pressed films with 0.5 mm thickness where the reduction of agglomerates in test specimens with pulp modified via conventional method with excess of ASA in relation to test specimens with pulp modified in reactive extrusion (REX) conditions with reduced amounts of ASA, solvents and other reagents indicates good dispersion, and better processing, in addition to more desirable mechanical properties of specific polymers and ensuring the use of a smaller amount of alkenyl succinic anhydride (ASA) and also of the swelling agent (NMP).
  • ASA alkenyl succinic anhydride
  • NMP swelling agent
  • the process of the present invention also provides for the optimization of the washing process, with a smaller number of steps or solvents in all phases of the process.
  • treated pulp treated cellulose pulp
  • modified pulp modified cellulose pulp
  • the cellulose fiber is selected from the group consisting of cellulose pulp, microfibrillated cellulose (MFC) and nanofibrillated cellulose (NFC), originating from hardwood (short fiber), such as eucalyptus or softwood (long fiber), such as pine.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • pulp treatment cellulose treatment
  • fiber treatment pulp treatment
  • fiber modification fiber modification
  • cellulose modification cellulose modification
  • the present invention relates to a process for preparing a thermoplastic composite from modified cellulose pulp via reactive extrusion (REX) with long-chain anhydrides, and to a thermoplastic composite prepared from said process.
  • REX reactive extrusion
  • the process comprises modifying cellulose in the form of chemical pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) via reactive extrusion (REX) in the presence of a aprotic solvent with the swelling capacity of cellulose for the preparation of thermoplastic composite materials that present good dispersion characteristics, as well as improved mechanical properties in relation to the thermoplastic polymer, and its subsequent use as reinforcement in composites with thermoplastic resin.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • REX reactive extrusion
  • thermoplastic composite presents good dispersion characteristics of cellulose fibers, better mechanical properties, increased modulus of elasticity, in addition to presenting processing benefits in relation to the synthetic thermoplastic polymer, while reducing the amount of swelling solvent and aprotic solvent used.
  • thermoplastic composites of cellulose pulp As indicated herein, the prior art already presents thermoplastic composites of cellulose pulp. However, it fails to disclose or suggest an environmentally friendly product, in which the cellulose pulp (or microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC)) is modified via a reactive extrusion process with anhydrides in the presence of a reduced amount of an aprotic solvent with the swelling capacity of cellulose, so as to allow a better dispersion of the cellulose fibers in the polymeric matrix.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • thermoplastic composite that combines bleached Kraft eucalyptus cellulose pulp, i.e. a highly hydrophilic component, with a thermoplastic polymer, a hydrophobic component, without the problems of incompatibility and difficulty in dispersion known in the state of the art, and with an optimization of the washing process by reducing the number of steps or solvents in all phases of the process.
  • ASA alkenyl succinic anhydride
  • thermoplastic composite from modified cellulose pulp via reactive extrusion (REX) with ASA
  • REX reactive extrusion
  • ASA alkenyl succinic anhydride
  • This process uses a raw material from a renewable source as reinforcement, which guarantees an environmentally friendly character of the process of the present invention in relation to processes already existing in the state of the art and which use a non-renewable raw material, such as, for example, glass fibers, talc, among others.
  • the process for preparing thermoplastic composite from modified cellulose pulp via reactive extrusion with anhydrides comprises the following steps: a) dewatering the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) by pressing and filtration; b) adding isopropanol or another solvent miscible in water and easily removable; c) pressing and filtering the mixture to eliminate excess liquid; d) repeating the process of adding isopropanol, pressing and filtration at least twice more; e) adding an aprotic solvent to the resulting material until the cellulose/aprotic solvent ratio is 1:1 by mass or greater; f) evaporating the isopropanol in a vessel with stirring under a nitrogen flow and applying a vacuum; g) obtaining a composition with 50% pulp in aprotic solvent and a residual water in relation to the cellulose of less than 5%; h) add ASA anhydride and K2CO3 in the m
  • the aprotic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP) and dihydrolevoglucosenone (Cyrene).
  • NMP N-methyl-2-pyrrolidone
  • Cyrene dihydrolevoglucosenone
  • the aprotic solvent is N-methyl-2-pyrrolidone (NMP).
  • a compatibilizer is used in step m).
  • the compatibilizer is from the class of polypropylene copolymers functionalized with maleic anhydride with an acidity of 37 - 45 mg KOH/g corresponding to 8 - 12% maleic anhydride, such as, for example, Licocene 6452.
  • Compatibilizing agents with other maleic anhydride contents including copolymers with styrene, acrylate and ethylene can also be used, since they have the same function.
  • compatibilizers are: Orevac CA 100(PP-g-MA), Synthomer G-3015, Epolene E25, E-43 and E-43P, Orevac 18732 RBP, among others.
  • the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) of step a) has a solids content of at least 10%, originating from hardwood such as eucalyptus or softwood such as pine.
  • the solids content of the wet pulp, MFC or NFC is in the range of 10 to 15%. More preferably, the solids content of the wet pulp or NFC is 15%.
  • the wet cellulose pulp is a chemical or semi-chemical pulp, bleached or unbleached, mechanical pulp, thermomechanical pulp, chemical-thermomechanical pulp, enzymatic pulp, among others.
  • the wet cellulose pulp is a bleached Kraft eucalyptus pulp.
  • the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) is dewatered by pressing and filtering until the solid content is between 10% and 50%.
  • these materials are obtained from bleached eucalyptus pulp wet Kraft pulp.
  • isopropanol or another water-miscible and easily removable solvent is added to the dewatered pulp, wherein the other solvent may be selected from the group consisting of ethanol, methanol, n-butanol, acetone, etc.
  • the mixture is then pressed and filtered to eliminate excess liquid, until it preferably reaches a solids content of at least 25% and so that the resulting mixture has a liquid phase with a water content of around 40% or less.
  • the process should be repeated several times, preferably two more times, so that several cycles of isopropanol addition and pressing/filtration are performed.
  • the final pulp with a solids content of 25% should have a water content in its liquid phase of less than 10%.
  • An aprotic solvent is then added to the resulting material as a swelling agent in step e) until the cellulose/aprotic solvent ratio is 1:1 by mass or greater.
  • the aprotic solvent is N-methyl-2-pyrrolidone (NMP).
  • the material from step e) is then subjected to evaporation of the isopropanol in a vessel with agitation such as a blender or similar under a flow of nitrogen and application of vacuum to eliminate the isopropanol and drag away the residual water, so that in the end it results in a composition with 50% pulp in NMP and a residual water in relation to the cellulose of less than 5% (step g)).
  • a vessel with agitation such as a blender or similar under a flow of nitrogen and application of vacuum to eliminate the isopropanol and drag away the residual water, so that in the end it results in a composition with 50% pulp in NMP and a residual water in relation to the cellulose of less than 5% (step g)).
  • step g) to the material from step g) is then added alkynyl succinic anhydride (ASA) and potassium carbonate (K2CO3) in a molar ratio of ASA/K2CO3 of 1:1 (mol/mol).
  • ASA alkynyl succinic anhydride
  • K2CO3 potassium carbonate
  • step h) The material from step h) is then extruded in an extruder, such as a twin screw, CP Farrel, etc., at room temperature or at temperatures in the range of 50 to 120 °C.
  • an extruder such as a twin screw, CP Farrel, etc.
  • step j) The product resulting from step j) is dispersed in ethanol, in a material/ethanol ratio of 1:5, being pressed and filtered. Then, the same process is carried out in step k) with a diluted solution of 1% acetic acid, water and isopropanol in a cellulose/isopropanol ratio of 1:2.
  • the product resulting from step k) is drained and dried in a dryer with counterflow of hot air at temperatures below 90 °C.
  • step I The material resulting from step I) appears as a flocculate that can be easily broken down into smaller particles.
  • the fibers After drying the treated pulp, the fibers are dispersed.
  • the material obtained after the drying step I) is subjected to a processing step, in which the material is added in step m) via the main funnel together with a thermoplastic polymer or by means of a side-feeder type doser in a twin-screw extruder for incorporating the thermoplastic polymer to produce a composite with excellent fiber dispersion.
  • the thermoplastic polymer of step m) is a polyolefin.
  • the polyolefin is selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and copolymers of propylene and ethylene.
  • processing is carried out in a twin-screw extruder with a granulation system in the head to generate the composite material with excellent dispersion of the cellulosic fibers.
  • the process consists of modifying cellulose pulp (or microfibrillated cellulose (MFC), or nanofibrillated cellulose (NFC)), never dried, with low water content, via reactive extrusion (REX) with anhydrides and its subsequent direct use as reinforcement in a thermoplastic matrix.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • thermoplastic composite obtained from the modification of cellulose pulp through a reactive extrusion process with alkenyl succinic anhydride (ASA).
  • ASA alkenyl succinic anhydride
  • thermoplastic composite of cellulose pulp modified via REX with ASA is a composite of cellulose fiber in a polymer matrix, in which the cellulose fiber is a cellulose pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) that acts as a reinforcing agent, that is, it is related to the mechanical properties of thermoplastic polymers.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • the starting material for obtaining the thermoplastic composite is a eucalyptus pulp obtained by the Kraft process, bleached but never dried, which has a solids content of at least 10%.
  • Coating cellulose fibers with low polarity materials such as polymers allows for improved dispersion of the fibers in the polymer matrix.
  • the modification of the cellulose pulp via the reactive extrusion process with ASA also allows a decrease in the amount of swelling solvent and aprotic solvent used, with a consequent optimization of the washing process through the decrease in the amount of steps or solvents in all phases of the process.
  • the process proposed by the present application represents a reduction in the use of anhydrides (ASA) of 5.3 times in relation to state-of-the-art processes, indicated by the increase in the initial cellulose mass/ASA mass ratio from 1.4 to 7.4, in addition to a reduction in the amount of swelling agent (NMP) of 50%.
  • ASA anhydrides
  • thermoplastic composite of cellulose pulp modified via reactive extrusion presents improvements in mechanical properties in relation to synthetic polymers.
  • the REX-modified cellulose pulp thermoplastic composite with anhydride exhibits improved elastic modulus, tensile strength, and elongation at break relative to a synthetic polymer.
  • Example 1 Process for preparing thermoplastic composite from cellulose pulp modified via REX with anhydrides
  • the process consists of modifying never-dried Kraft eucalyptus cellulose pulp with low water content, via reactive extrusion (REX) with alkenyl succinic anhydride (ASA) and its subsequent direct use as reinforcement in a thermoplastic matrix.
  • REX reactive extrusion
  • ASA alkenyl succinic anhydride
  • the wet bleached eucalyptus Kraft pulp, microfibrillated cellulose or eucalyptus nanofibrillated cellulose (with a solids content (TS) of 10 - 15%) is dewatered by pressing and vacuum-assisted filtration until it reaches a solids content of between 25% and 30%.
  • TS solids content
  • This mixture was fed into a twin-screw extruder with a free outlet at the head.
  • the reaction occurred with the extruder at room temperature (resistances turned off) and with a screw rotation of 200 rpm.
  • the modified pulp may undergo thorough washing with ethanol, aqueous acetic acid solution (1% v/v) and distilled water, or it may be washed with ethanol alone.
  • ASA-modified pulp dried in an oven at 60°C (48.5 g of dry modified pulp) was mixed with 207.5 g of high-density polyethylene (HDPE) (HC 7260/Braskem) and 10.8 g of maleic anhydride-grafted polypropylene (PP-g-MA) (LICOCENE® PP MA 6452/Clariant) and 2.7 g of calcium carbonate (CaCOs), generating a formulation with 18% modified pulp, 4% PP-g-MA, 1% CaCO 3 and 77% HDPE.
  • HDPE high-density polyethylene
  • PP-g-MA maleic anhydride-grafted polypropylene
  • CaCOs calcium carbonate
  • the mixture was processed in a twin screw extruder with a temperature profile from the feed zone to the die of: 130, 130, 130, 135, 140 and 140 °C with a screw rotation of 200 rpm and with the material being fed through the dosing funnel.
  • the material obtained in the form of noodles was granulated.
  • the granulated composite obtained was dried in an oven at 70 °C for injection of type 1 tensile test specimens (ASTM format) in a Battenfeld injection machine, type Plus 35/75 Unilog B2, under the following conditions: temperature of 160 °C, injection pressure of 90 bar and mold temperature of 40 °C.
  • ASTM format type 1 tensile test specimens
  • Example 2 Mechanical Properties Test Results in Tensile
  • Table 1 illustrates the results of the mechanical properties of the tested samples of the synthetic polymer and of the exemplary formulations of thermoplastic composites with pulps treated via REX with ASA, specifically in relation to the elastic modulus (GPa), tensile strength (MPa) and elongation at break (%) of each of these samples.

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Abstract

La présente invention vise à fournir un procédé de préparation de composite thermoplastique à partir de pâte de cellulose modifiée par extrusion réactive avec des anhydrides, ainsi qu'un composite thermoplastique préparé au moyen dudit procédé. Le procédé s'applique à la modification de la cellulose sous forme de pâte chimique, de cellullose microfibrillée (MFC) ou de cellulose nanofibrillée (NFC) par extrusion réactive (REX) en présence d'un solvant aprotique à capacité d'intumescence de la cellulose, et à son utilisation postérieure comme renfort dans des composites avec de la résine thermoplastique.
PCT/BR2024/050251 2023-06-13 2024-06-13 Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée par extrusion réactive avec des anhydrides, et composite thermoplastique WO2024254663A1 (fr)

Applications Claiming Priority (2)

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