WO2024254664A1 - Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée avec des cires ou avec une émulsion de polymères, et composite thermoplastique - Google Patents

Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée avec des cires ou avec une émulsion de polymères, et composite thermoplastique Download PDF

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Publication number
WO2024254664A1
WO2024254664A1 PCT/BR2024/050252 BR2024050252W WO2024254664A1 WO 2024254664 A1 WO2024254664 A1 WO 2024254664A1 BR 2024050252 W BR2024050252 W BR 2024050252W WO 2024254664 A1 WO2024254664 A1 WO 2024254664A1
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WIPO (PCT)
Prior art keywords
wax
cellulose
pulp
polymer
thermoplastic
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PCT/BR2024/050252
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English (en)
Portuguese (pt)
Inventor
Antonio José Felix De CARVALHO
Talita Rocha RIGOLIN
Bruna Papa SPADAFORA
Laura De Araujo HSIA
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Universidade de Sao Paulo USP
Suzano SA
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Universidade de Sao Paulo USP
Suzano SA
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Priority claimed from BR102023011656-6A external-priority patent/BR102023011656A2/pt
Application filed by Universidade de Sao Paulo USP, Suzano SA filed Critical Universidade de Sao Paulo USP
Publication of WO2024254664A1 publication Critical patent/WO2024254664A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • 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
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene

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 with waxes, or with polymer emulsions, and to a thermoplastic composite prepared from each of said processes.
  • Said thermoplastic composites present good dispersion characteristics of the cellulose fibers and better mechanical properties in relation to the synthetic thermoplastic polymer.
  • the modification of the cellulose pulp with waxes is carried out before obtaining the composite with the thermoplastic polymer and, thus, also provides benefits in relation to the processing of the thermoplastic composites.
  • 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.
  • WO 2000/076322 A1 discloses a cellulose composite composition including hydrophobic wax, anionic polymer and cellulose.
  • the composite composition is formed by coagulating, regenerating and drying a mixture consisting of hydrophobic wax emulsion, anionic polymer emulsion and viscose.
  • the composite thus formed has a hydrophobic surface with reduced adhesion to hydrophilic surfaces compared to regenerated cellulose alone, or compared to cellulose including only paraffin wax or cellulose including only anionic polymer.
  • Document US 2019/0023882 A1 relates to a thermoplastic resin composition containing a thermoplastic synthetic resin, cellulose in a content of 10 to 70 parts by mass relative to 100 parts by mass of the thermoplastic synthetic resin and an organic peroxide.
  • the document discloses that the process employing the organic peroxide as an additive is capable of dispersing the cellulose in a convenient and uniform manner in a resin with a high hydrophobic property and is also capable of improving the mechanical strength of the molded material that was formed by molding the resin composition obtained by the process.
  • document US 8,663,425 B2 refers to a method for manufacturing microfibrous cellulose composite sheets, which includes a process in which a polymer emulsion is mixed with an aqueous suspension including microfibrous cellulose, the mixed fluid is dehydrated in a porous base material through filtration and then dried. According to the document, it is possible to provide a manufacturing method in which a microfibrous cellulose composite sheet can be produced extremely efficiently, and the composite sheet obtained has excellent characteristics in terms of strength. [0012] Indeed, there are a number of challenges related to the processing of synthetic solid polymers, particularly with regard to compatibility with other components.
  • 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 does 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 that combines two materials with different characteristics
  • the present invention relates to a new and inventive process for modifying cellulose pulp with polyolefin waxes (polyethylene and polypropylene), petroleum waxes or synthetic waxes, or with polymeric emulsions for the preparation of thermoplastic composite materials that present good dispersion characteristics, as well as improved mechanical properties in relation to the thermoplastic polymer.
  • the present invention also relates to a thermoplastic composite prepared from each of the said processes.
  • the present invention discloses a process for preparing thermoplastic composites of cellulose pulp modified with polyolefin, petroleum or synthetic waxes, or with polymer emulsions, and the thermoplastic composite prepared from each of said processes, for coating cellulose fibers, with low polarity polymeric materials, so that it presents good dispersion of the fibers and without the presence of fiber agglomerates, in addition to good mechanical properties.
  • the invention relates to a process for treating cellulose fibers with solid waxes, or with an emulsion of polymers or waxes, 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.
  • One embodiment of the invention relates to a process for preparing a thermoplastic composite of cellulose pulp modified with polyolefin, petroleum or synthetic waxes comprising the following steps: a) dewatering the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) by pressing and filtering; b) adding a wax to the dewatered pulp in a mixer; c) extruding the mixture from step b) generating a wax-treated pulp; d) drying the wax-treated pulp; e) processing and composting the material obtained in step d) with a thermoplastic resin; and f) obtaining a composite material.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • thermoplastic composite of cellulose pulp modified with polyolefin, petroleum or synthetic waxes in which the cellulose pulp treated with wax has a better compaction characteristic in relation to an untreated pulp, and this allows greater ease in feeding and processing the treated pulp.
  • Another embodiment of the invention relates to a process for preparing a thermoplastic composite of cellulose pulp modified with polymer emulsion or polyolefin wax emulsion, petroleum or synthetic, comprising the following steps: a) dewatering the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) by pressing and filtration; b) adding a polymer or wax emulsion to the dewatered pulp in a mixer, generating an emulsion-treated pulp; c) drying the emulsion-treated pulp; d) crushing and extruding the material obtained in step c) with a thermoplastic polymer; and e) obtaining a composite material.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • thermoplastic composite of cellulose pulp modified with polymer or wax emulsion in which the cellulose pulp treated with polymer or wax emulsion has good mechanical properties and good fiber dispersion characteristics in the polymer matrix compared to an untreated pulp.
  • 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 thermoplastic composite presents an increase in the 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.
  • FIG. 1 is a flowchart illustrating the processes for preparing a thermoplastic composite material from cellulose pulp modified with waxes or polymer emulsion.
  • FIG. 2 is a flowchart illustrating the process of preparing a thermoplastic composite material from wax-modified cellulose pulp.
  • FIG. 3 is a representative image of the starting material, i.e., a never-dried bleached Kraft eucalyptus pulp having a solids content of 15%.
  • FIGS. 4A-4B represent images of injection molded specimens of high density polyethylene (HDPE) composites with bleached Kraft eucalyptus pulps treated with paraffin wax or polyolefin wax.
  • HDPE high density polyethylene
  • FIG. 4A is an image of a HDPE composite with 18% bleached Kraft eucalyptus pulp treated with 15% paraffin wax.
  • FIG. 4B is an image of a HDPE composite with 18% bleached Kraft eucalyptus pulp treated with 15% polyethylene (PE) wax.
  • FIG. 5 is an illustrative image of the composite in pellet form after extrusion.
  • FIG. 6 is an illustrative image of a thin film pressed with a thickness of 0.5 mm from the extruded noodle of composition containing 18% cellulose, 4.5% paraffin wax compatibilized with 4% Licocene, 1% CaCOs and 72.5% HDPE.
  • FIG. 8A is a representative image of a blend of bleached Kraft Eucalyptus wet pulp having a solids content of 15% and polycaprolactone (PCL) emulsion having a solids content of 17.6% prior to drying, with a ratio of 80% cellulose and 20% PCL.
  • PCL polycaprolactone
  • FIG. 8B is a representative image of a mixture of wet bleached Kraft eucalyptus pulp and polycaprolactone (PCL) emulsion after drying, with up to 80% solids.
  • PCL polycaprolactone
  • FIG. 8C is a representative image of materials mixed prior to the composite extrusion step, with the following composition: 50% bleached Kraft eucalyptus pulp treated with PCL emulsion, 1% CaCOs, high density polyethylene (HDPE) and 4% compatibilizer (Licocene 6452).
  • FIGS. 9A-9D are images of injection molded specimens of high-density polyethylene (HDPE) composites with bleached Kraft eucalyptus pulps treated with polymer emulsions.
  • HDPE high-density polyethylene
  • FIG. 9D is an image of a HDPE composite with 50% bleached Kraft Eucalyptus pulp treated with PCL emulsion.
  • 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.
  • 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 absence of visible agglomerates indicates good dispersion, and better processing, in addition to more desirable mechanical properties of specific polymers and ensuring a good mixing of the polymer with waxes or with polymer emulsions.
  • 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 process comprises the modification of cellulose in the form of chemical pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) via extrusion with waxes, or with polymer emulsions, and its subsequent use as reinforcement in composites with thermoplastic resin.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • 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 an extrusion process with polyolefin, petroleum or synthetic waxes, or with polymer emulsions, so as to allow a better dispersion of the cellulose fibers in the polymer matrix.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • thermoplastic composite from cellulose pulp modified with waxes, or polymer or wax emulsions, allows obtaining a product with good mechanical properties for later use as reinforcement in a thermoplastic matrix.
  • the treatment of cellulose pulp with waxes allows for greater ease in processing and feeding into the extruder to prepare the thermoplastic composite due to the greater compaction provided by the wax.
  • a process for preparing composites of cellulose fibers and thermoplastic polymers is disclosed, in which the cellulose fiber in the form of pulp, microfibrillated cellulose or nanofibrillated cellulose is initially treated directly with waxes or emulsions of polymers or waxes, followed by drying and extrusion with the thermoplastic polymer matrix, in which ease of processing and/or high dispersion of the fibers is achieved.
  • 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 cellulose pulp modified with polyolefin, petroleum and synthetic waxes comprises the following steps: a) dewatering the wet pulp or nanofibrillated cellulose (NFC) by pressing and filtering; b) adding a wax to the dewatered pulp in a mixer; c) extruding the mixture from step b) generating a wax-treated pulp; d) drying the wax-treated pulp; e) processing and composting the material obtained in step d) with a thermoplastic resin; and f) obtaining a composite material.
  • NFC nanofibrillated cellulose
  • a compatibilizer is used in step e).
  • the compatibilizer is from the class of polypropylene copolymers functionalized with maleic anhydride with an acidity of 37 - 45 mgKOH/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 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 as high as possible, preferably until the solid content is greater than about 25%.
  • these materials are obtained from bleached eucalyptus pulp wet Kraft pulp.
  • the wax added to the dewatered pulp from step b) is in the form of flakes, shavings, or powder, and may be a polyolefin wax such as polyethylene and polypropylene, oxidized or not, petroleum wax such as micro or macro paraffin wax or paraffin, or synthetic wax such as Fisher-Tropsch wax.
  • a polyolefin wax such as polyethylene and polypropylene, oxidized or not, petroleum wax such as micro or macro paraffin wax or paraffin, or synthetic wax such as Fisher-Tropsch wax.
  • Modification of fibers with waxes in the form of flakes, shavings or powder presents a difficulty in mixing due to the flow characteristics of the cellulose pulp.
  • modification of the pulp with waxes is carried out in the presence of water and at a temperature suitable for melting the wax and thus coating the cellulose fibers in mixing step b).
  • the wax added to the cellulose pulp is in the proportion of 5 to 15% wax relative to dry cellulose.
  • the mixer in step b) is a solids mixer, such as a ribom blender, or similar.
  • the extruder used in step c) is a twin-screw extruder with a degassing zone and the extrusion temperature is in the range of 80 ° C to 200 ° C.
  • the extrusion temperature is in the range of 90 ° C to 130 ° C.
  • drying step d) is performed in a hot air counterflow dryer and, optionally, a vacuum drying chamber may be used at the extruder outlet.
  • the fibers are dispersed.
  • the material obtained after drying step d) has a residual water content in the range of 15 to 25%.
  • the thermoplastic resin of step e) 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.
  • the material obtained in step e) is subjected to a processing step, in which the material can be mixed with the polyolefin or added directly into the addition hopper or by side feeding, for example, via a side-feeder.
  • the 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 extrusion with waxes 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 with waxes through an extrusion process.
  • the wax-treated cellulose pulp has better compaction characteristics than untreated pulp, and this allows for greater ease in feeding the treated pulp into the extruder and its processing.
  • thermoplastic composite of cellulose pulp modified with waxes of the present invention 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.
  • modification of the cellulose pulp with waxes also allows for improved processing of the thermoplastic composite due to the greater compaction provided by the wax.
  • thermoplastic composite of cellulose pulp modified with waxes presents improvements in mechanical properties in relation to synthetic polymers.
  • the wax-modified cellulose pulp thermoplastic composite exhibits improved elastic modulus, tensile strength, and elongation at break relative to a synthetic polymer.
  • the process for preparing a thermoplastic composite of polymer emulsion-modified cellulose pulp comprises the following steps: a) dewatering the wet pulp, microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC) by pressing and filtering; b) adding a polymer or wax emulsion to the wet pulp in a mixer generating an emulsion-treated pulp; c) drying the emulsion-treated pulp; d) grinding and extruding the material obtained in step c) with a thermoplastic polymer; and e) obtaining a composite material.
  • MFC microfibrillated cellulose
  • NFC nanofibrillated cellulose
  • a compatibilizer is used in step d).
  • the compatibilizer is from the class of propylene copolymers functionalized with maleic anhydride, such as Licocene 6452.
  • propylene copolymers functionalized with maleic anhydride 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, MFC or NFC is 13.7%.
  • the wet cellulose pulp is a chemical or semi-chemical pulp, bleached or unbleached, mechanical pulp, thermomechanical, chemical-thermomechanical, 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 as high as possible, preferably until the solid content is greater than about 25%.
  • the material is already dispersed and coats the cellulose fibers immediately in the mixing step b).
  • the emulsion is added to the pulp via a pump, being a synthetic polymer or paraffin wax emulsion.
  • the synthetic polymer or wax emulsion is added at a solids content of 15 to 60% directly to the wet pulp.
  • the solids content of the emulsion is in the range of 15 to 40%. More preferably, the solids content of the emulsion is in the range of 15 to 30%.
  • the polymer In the case of polymer emulsion, the polymer must be from the non-caking category, for example, polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyvinyl acetate (PVAC), among others.
  • PCL polycaprolactone
  • PHB polyhydroxybutyrate
  • PVAC polyvinyl acetate
  • the wax is a polyolefin wax (polyethylene or polypropylene), petroleum waxes such as paraffins, micro paraffinic waxes and macro paraffinic waxes and synthetic waxes such as Fisher-Tropsch.
  • the mixer in step b) is a solids mixer such as a ribom blender, or similar.
  • the drying step c) is carried out by passing a current of hot air, but at a temperature below the melting point of the polymer or wax that make up the emulsion.
  • the material obtained in step d) is subjected to a processing step, in which the dry material is crushed or dismembered, and then extruded in a twin-screw extruder with a degassing zone with a thermoplastic polymer to generate the composite material with excellent dispersion of the cellulosic fibers.
  • the thermoplastic polymer of step d) 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.
  • the process consists of modifying cellulose pulp (or microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC)), never dried, with low water content, via extrusion with polymer emulsions, 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 with synthetic polymer emulsions through an extrusion process.
  • Cellulose pulp treated with polymer or wax emulsion has a higher modulus of elasticity, in addition to good mechanical properties and good fiber dispersion characteristics in the polymer matrix compared to untreated pulp.
  • thermoplastic composite of cellulose pulp modified with polymer or wax emulsion of the present invention 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 of the present invention is a never-dried bleached Kraft eucalyptus pulp that 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.
  • thermoplastic composite of cellulose pulp modified with polymer emulsion presents improvements in mechanical properties in relation to synthetic polymers.
  • thermoplastic composite of the present invention 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 with waxes
  • thermoplastic composite of cellulose pulp modified with waxes The following is a process for preparing a thermoplastic composite of cellulose pulp modified with waxes. [01 10] The process consists of modifying never-dried Kraft eucalyptus cellulose pulp with low water content, via extrusion with polyolefin or paraffin waxes and its subsequent direct use as reinforcement in a thermoplastic matrix.
  • a solid wax in the form of flakes, shavings or powder is then added to this material (dewatered pulp) in a conventional mixer for solid materials, such as a ribbon blender or similar.
  • the wax may be a polyolefin wax (e.g. polyethylene or polypropylene), petroleum waxes (paraffin, and micro and macro paraffinic waxes) and synthetic waxes such as Fischer-Tropsch, and also ethylene and propylene copolymer waxes, stearic waxes, etc.).
  • Wax should be used in a proportion of 5 to 15% wax in relation to dry cellulose.
  • the material is then extruded in a twin-screw extruder with a degassing zone, generating material that must be dried in a dryer with a counterflow of hot air, and a vacuum drying chamber can optionally be used at the extruder outlet.
  • thermoplastic resin preferably a polyolefin
  • the material can be mixed with polyolefin or added via side-feeder. Processing should preferably be 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, as seen in FIG. 6, where it is possible to verify the absence of visible agglomerates in pressed film with a thickness of 0.5 mm.
  • Example 2 Composition of exemplary formulations of high-density polyethylene (HDPE) composites with wax-treated pulps
  • HDPE high-density polyethylene
  • HDPE with wax-treated pulps as identified in Table 1 above, tensile mechanical property tests were performed in accordance with ASTM D638 or equivalent to evaluate and compare the results obtained for thermoplastic composites of wax-modified cellulose pulp in relation to the results obtained for the synthetic thermoplastic polymer.
  • the test speed was 10 mm/min.
  • Table 2 illustrates the results of the mechanical properties of the tested samples of the synthetic polymer and of the exemplary formulations of thermoplastic composites with wax-treated pulps, specifically in relation to the elastic modulus (GPa), tensile strength (MPa) and elongation at break (%) of each of these samples.
  • Table 2 Mechanical properties in tension
  • Example 4 Process for preparing thermoplastic composite from cellulose pulp modified with polymer emulsion
  • thermoplastic composite of cellulose pulp modified with polymer emulsion The following is a process for preparing a thermoplastic composite of cellulose pulp modified with polymer emulsion.
  • the process consists of modifying the “total” or partial cellulose pulp that has never been dried with a low water content, via extrusion with an emulsion of a synthetic polymer and its subsequent direct use as reinforcement in a thermoplastic matrix.
  • PCL caprolactone polymer emulsion
  • a solid content of 25 to 60% is added directly to the wet pulp.
  • the emulsion is 20% PCL with a cellulose base (i.e., the mixture has 80% cellulose/20% PCL).
  • the material is dried by passing a current of hot air, but at a temperature below the melting point of PCL.
  • the dry material is then crushed or dismembered and then extruded in a twin screw extruder with a degassing zone with the thermoplastic polymer (preferably a polyolefin), to generate a composite material with excellent dispersion of the cellulosic fibers.
  • the thermoplastic polymer preferably a polyolefin
  • Example 5 Composition of exemplary formulations of high-density polyethylene (HDPE) composites with eucalyptus pulps treated with emulsions
  • HDPE high-density polyethylene
  • Table 3 indicates the components and their respective proportions in each of the exemplary formulations.
  • Table 4 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 with emulsions, specifically in relation to the elastic modulus (GPa), tensile strength (MPa) and elongation at break (%) of each of these samples.
  • GPa elastic modulus
  • MPa tensile strength
  • % elongation at break

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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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 avec des cires, ou avec des émulsions de polymères, ainsi qu'un composite thermoplastique préparé au moyen de chacun desdits procédés. Le procédé s'applique à la modification de la cellulose sous forme de pâte chimique, de cellulose microfibrillée (MFC) ou de cellulose nanofibrillée (NFC) par extrusion avec des cires, ou avec une émulsion de polymères, et à son utilisation postérieure comme renfort dans des composites avec de la résine thermoplastique.
PCT/BR2024/050252 2023-06-13 2024-06-13 Procédé de préparation de composite thermoplastique de pâte cellulosique modifiée avec des cires ou avec une émulsion de polymères, et composite thermoplastique Pending WO2024254664A1 (fr)

Applications Claiming Priority (2)

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BR102023011656-6A BR102023011656A2 (pt) 2023-06-13 Processo de preparação de compósito termoplástico de polpa celulósica modificada com ceras ou com emulsão de polímeros, e compósito termoplástico
BR1020230116566 2023-06-13

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WO2024254664A1 true WO2024254664A1 (fr) 2024-12-19

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