WO2023038519A1 - Modification de biopolymères à l'aide de polyols et de polyacides - Google Patents

Modification de biopolymères à l'aide de polyols et de polyacides Download PDF

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WO2023038519A1
WO2023038519A1 PCT/NL2022/050494 NL2022050494W WO2023038519A1 WO 2023038519 A1 WO2023038519 A1 WO 2023038519A1 NL 2022050494 W NL2022050494 W NL 2022050494W WO 2023038519 A1 WO2023038519 A1 WO 2023038519A1
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forming
acid
biopolymer
modified
ester
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PCT/NL2022/050494
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WO2023038519A9 (fr
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Stephen James Picken
Jure ZLOPASA
Robbert Aad George BINNEVELD
Willem Otto Julius Böttger
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Technische Universiteit Delft
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • 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
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal 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
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention is in the field of a method of modifying polymers produced by biological species, in particular microorganisms, by reacting un-modified biopolymer, a modified biopolymer obtained by said method, an adhesive comprising said modified biopolymer, a fibre reinforced composite comprising said modified biopolymer, and a fibre reinforce panel comprising said fibre reinforced composite.
  • a fibre-reinforced composite is a building material that consists of three components, namely fibres (for strength and stiffness) as a discontinuous or dispersed phase, a matrix (binder) as a continuous phase, and the fine interphase region, also known as the interface.
  • fibres for strength and stiffness
  • matrix binder
  • fine interphase region also known as the interface.
  • Fibres may need to be refined, blended, and compounded, such as in case of natural fibres from cellulosic waste streams.
  • a high-strength fibre composite material in a polymer matrix can be formed thereby.
  • the designated waste or base raw materials used in this instance are those of waste thermoplastics and various categories of cellulosic waste including straw, rice husk and saw dust.
  • plant-based polymeric material such as cellulose-based material thereof
  • a polyester may be formed directly from chemical products, such as by reacting an aliphatic polyalcohol and an aliphatic Poly carboxylic acid, such as is shown on W02020/152082 Al, WO 2020/212427 Al, and WO 2021/023495 Al, which material may be used for manufacturing a laminate and the like.
  • Naturally occurring materials such as cotton, starch, and rubber were familiar materials for years before synthetic polymers such as polyethene and Perspex appeared on the market.
  • Many commercially important polymers are synthesized by chemical modification of naturally occurring polymers. Prominent examples include the reaction of nitric acid and cellulose to form nitrocellulose and the formation of vulcanized rubber by heating natural rubber in the presence of sulphur. Ways in which polymers can be modified include oxidation, cross-linking, and end-capping. Such polymers may find application as fibre reinforced composite materials.
  • microorganisms are capable of producing biochemical compounds, such as lactic acid.
  • a microbial culture is used.
  • microbial organisms reproduce in predetermined culture medium under controlled laboratory conditions. It is often essential to isolate a pure culture of microorganisms.
  • a pure (or axenic) culture is a population of cells or multicellular organisms growing in the absence of other species or types. Remarkably also non-pure cultures are capable of producing chemical substances.
  • Bacteria are capable of producing a wide variety of chemical substances, such as lactic acid, but also methane, and are therefore used in food industry, in waste treatment, and so on.
  • microbiological conversion a microbiological conversion
  • biobased polymeric substances such as extracellular polymeric substances (EPS), in particular polysaccharide comprising materials, obtainable from granular sludge can be produced in large quantities.
  • EPS extracellular polymeric substances
  • biobased carboxylic acid-like chemicals which may be present in an ionic form (e.g. cationic or anionic). Examples of such production methods can be found in W02015/057067 Al, and WO20 15/050449 Al, whereas examples of extraction methods for obtaining said biobased polymers can be found in Dutch Patent application NL2016441 and in WO2015/190927 Al.
  • G G
  • PG polyglycerols
  • GTA glycerol triacetate
  • GTB glycerol tributyrate
  • the water-based fracturing fluid composition contains a thickening agent, a cross-linking agent, a fracturing auxiliary agent and water, and the water-based fracturing fluid composition is characterized in that the thickening agent is citric acid-modified welan gum.
  • granules of granular sludge can be readily removed from a reactor by e.g. physical separation, settling, centrifugation, cyclonic separation, decantation, filtration, or sieving to provide extracellular polymeric substances in a small volume.
  • physical separation, settling, centrifugation, cyclonic separation, decantation, filtration, or sieving to provide extracellular polymeric substances in a small volume.
  • Extracellular polymeric substances obtainable from granular sludge do not require further purification or treatment to be used for some applications, hence can be applied directly.
  • the extracellular polymeric substances are preferably isolated from bacteria (cells) and/or other non-extracellular polymeric substances.
  • the granular sludge can be suitably produced by bacteria belonging to the order Pseudomonadaceae, such as pseudomonas and/or Acetobacter bacteria (aerobic granular sludge); or, by bacteria belonging to the order Planctomycetales (anammox granular sludge), such as Brocadia anammoxidans.
  • Na2COs is found to provide biopolymers with an number average molecular weight of 50-75 kDa
  • NaOH at a pH of 11-12 provides biopolymers with an number average molecular weight of 20-45 kDa
  • NaOCl provides biopolymers with an number average molecular weight of about 120 kDa(100-150 kDa)[as determined with GPC/SEC, Shimadzu Nexpera GPC],
  • algae alginate e.g. from seaweed
  • Calcium alginate wound dressings are used worldwide in view of creating a moist wound environment that encourages more effective healing.
  • the alginate referred to here does not relate to a biopolymer of microbial origin.
  • biopolymers such as alginate
  • a problem with biopolymers is that upon further treatment water may need to be removed, which is difficult.
  • the present invention relates to a product comprising a modified biopolymer, such as the above modified extracellular polymeric substance, a method of producing said modified biopolymer, and further aspects thereof, which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages.
  • the present invention relates in a first aspect to a method of obtaining a modified biopolymer comprising providing an amount of at least one un-modified biopolymer or providing at least one un-modified bio-polyester produced by at least one microbial species, such as an extra-polymeric substance, and (i) modifying the at least one un-modified biopolymer by reacting the unmodified biopolymer with at least one biodegradable and non-toxic es- ter-forming or ether-forming or anhydride-forming compound, wherein the ester-forming or ether-forming or anhydride-forming compound is capable of forming at least two of esters and/or ethers, wherein the ester-forming or ether-forming or anhydride-forming compound is selected from polyols, polyacids, such as poly carboxylic acids, poly alcohols, poly aldehydes, molecules comprising at least one OH-group and one COOH group, and combinations thereof, at an elevated temperature, during a reaction
  • the reaction may be inter-biopolymer molecule, intra- biopolymer molecule, or both. Surprisingly the water, being produced by the reaction, and/or being present, can be removed and therefore does not substantially hinder the present modification.
  • the reactive compound is preferably a polyol, or a polyacid. In this respect the prefix “poly” can also relate to “oligo”, that is 2-6, such as 3-4. It is important that in the reactive compound at least two ester-forming and/or ether-forming and/or anhydride-forming moieties are present, in order to modify the un-modified biopolymer.
  • the extracellular polymeric substances comprise a major portion consisting of exopolysaccharides, and a minor portion, such as less than 30 % w/w, typically less than 10 %w/w, consisting of lipids and/or other components more hydro- phobic than the exopolysaccharides, such as proteins.
  • the phrase “at least two” implies two or more, in particular three or more, more in particular 4-6, such as the ester-forming and/or ether-forming and/or anhydride-forming moieties.
  • polyols like glycerol, sorbitol and analogous, and/or polyacids, for instance citric acid
  • CA citric acid
  • citric acid and e.g. glycerol (GLY) can be included into the biopolymer to modify the plasticity or flow of the resin obtained.
  • GLY glycerol
  • This ratio may be about 3/1 in weight, based on the effective available acid groups (+2 in CA) and +3 OH in GLY.
  • the level of acidity will influence the number of effectively available carboxylic groups in the polymer (COOH in acid ALE, for Na-ALE the carboxylic groups in the polymer do not participate).
  • the Kaumera resin formulation of this generic type e.g.
  • Kaumera/25 CA + x%(3 CA/1 GLY) are suitable as a binder for e.g. fibre reinforced panel manufacturing.
  • the aliphatic PHBV polyesters obtained from e.g. vegetable waste composting can be modified using CA/GLY and similar additions, to cleave the polymer chains, and decorate the ends with branched acid or OH functional end- groups of the PHBV chains. This may be useful to control the degree of crystallization, the melting point of the formulation, and the 'tackiness' of the final mixture, after some esterifica- tion/cleavage at elevated temperature, again typically above 140C.
  • PHBV based formulations are considered useful for optimizing the polymer performance as a matrix resin, or in adhesives (solvent based, hot melt, and pressure sensitive adhesives). It is worth noting that glycerol can be replaced by analogous polyols like sorbitol (6 OH groups) in case of evaporation of the GLY at elevated temperatures, etc.
  • the present invention relates to a modified, plasticized, or functionalized biopolymer obtainable by a method according to the invention. It is considered an important advantage of the present method of modifying, and the modified biopolymers obtained thereby, that characteristics of the un-modified biopolymers can be adapted largely as desired.
  • the biopolymers can be plasticized, or functionalized, or modified in general, with a specific application thereof in mind, such as the use as an adhesive compound, or the use in a fibre reinforced composite.
  • Said modified biopolymer may have a melting point of >150 °C, and/or a tackiness of > 200 J/m2, and/or a glass transition temperature of ⁇ 50 °C (high temperature compostable), preferably ⁇ 40 °C, such as ⁇ 20 °C.
  • PHBV high temperature compostable
  • PHBV ⁇ 0 C.
  • a biopolymer PHBV based formulation that has a good hot melt and short-term tackiness properties is obtained.
  • the present invention relates to an adhesive comprising a biopolymer according to the invention, such as a solvent based adhesive, and a hot melt adhesive.
  • the present invention relates to a fibre reinforced composite
  • a fibre reinforced composite comprising 1-70 wt.% of an adhesive according to the invention, and 30-99 wt.% fibres, in particular cellulosic fibres, hemp fibres, flax fibres, and viscose fibres, preferably wherein the composite is 50-90% cured.
  • the invention relates, in a further aspect, to a fibre reinforced panel comprising a fibre reinforced composite according to the invention.
  • the present invention relates in a first aspect to a method according to claim 1.
  • the present method comprises (i) modifying the at least one un-modified biopolymer or providing at least one un-modified bio-polyester, (ii) plasticizing the at least one modified biopolymer or un-modified bio-polyester by reacting with an 0.1-35% stoichiometric amount of at least one biodegradable and non-toxic ester-forming or ether-forming or anhydride-form- ing compound, in particular 1-30 % stoichiometric amount, such as 5-25% stoichiometric amount, wherein the ester-forming or ether-forming or anhydride-forming compound is capable of forming at least two of esters and/or ethers, wherein the ester-forming or ether-forming or anhydride-forming compound is selected from polyols, polyacids, such as poly carboxylic acids, poly alcohols, molecules comprising at least one OH-group and one COOH group
  • an un-modified biopolymer in particular a bio-polyester.
  • the bio-polyester is considered to be less reactive than an unmodified biopolymer having OH-groups available for reacting and optionally further groups for reacting.
  • the bio-polyester can still be modified, such as plasticized, and/or functionalized, with at least one biodegradable and non-toxic ester-forming or ether-forming or anhydride- forming compound, typically under similar reaction conditions.
  • step of plasticizing a small fraction of the available reactive moi eties (or groups) is reacted, typically with an 0.1-25% stoichiometric amount of such reactive groups being available, preferably with an 1-8% stoichiometric amount, such as with an 2-5% stoichiometric amount thereof.
  • the modified biopolymer or bio-polyester can be functionalized in a similar manner, by reacting a small fraction of the available reactive moieties (or groups), typically with an 0.1-25% stoichiometric amount of such reactive groups being available, preferably with an 1-8% stoichiometric amount, such as with an 2-5% stoichiometric amount thereof.
  • plasticity and/or function of the biopolymer or bio-polyester can be modified.
  • the un-modified biopolymer has various moieties or groups available for reacting, such as comprises OH-groups available for reacting and optionally at least one of NH X groups for reacting, carboxylic groups for reacting, RSC Hx groups for reacting, RPC Hx groups for reacting, ester-groups for reacting, ether-groups for reacting, O-acetyl groups for reacting, which typically are ketone group, sulfone groups for reacting, sulfonate groups for reacting, sulphonamide groups for reacting, and combinations thereof.
  • biopolymers produced by at least one microbial species may vary in terms of molecular weight, in terms of functional groups and amounts thereof being present in the biopolymer, in terms of sequence of monomers, dimers, etc.
  • the un-modified biopolymer and the ester-forming or ether-forming or anhydride-form- ing compound are preferably provided in a stoichiometric ratio of biopolymer: compound of 0.7:1 to 2:1, more preferably 1 : 1 to 1.5: 1.
  • the characteristics of the present unmodified microbial polymer can be modified as desired.
  • the polyacid is selected from organic polyacids, such as dicarboxylic acids and tricarboxylic acids, such as citric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and malonic acid.
  • organic polyacids such as dicarboxylic acids and tricarboxylic acids, such as citric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and malonic acid.
  • the ester-forming or ether-forming or anhydride-forming compound in the step of (i) modifying by reacting the unmodified biopolymer is provided in a weight ratio compound:biopolymer of 1 : 10 to 1 : 1, preferably 1 :6 to 1 :2, such as 1 :5 to 1 :4.
  • the modified biopolymer is obtained at a temperature of > 100 °C, preferably > 140 °C, such as > 160 °C, and preferably ⁇ 185 °C. Typically the temperature is increased significantly, in order to speed up the reaction.
  • the modified biopolymer is reacted during 5-180 minutes, such as 10-60 minutes, such as 20-30 minutes, which is considered to be relatively quickly.
  • the pressure is ⁇ 1000 kPa, such as ⁇ 100 kPa, in particular ⁇ 50 kPa, more in particular ⁇ 10 kPa, that is, under a reduced pres- sure, in particular under a reduced water pressure. As such water being formed during the reaction is removed rather easily.
  • the un-modified biopolymer is selected from polysaccharides, wherein the saccharide is preferably selected from trioses, tetroses, pentoses, hexoses, heptoses, octoses, dodecyloses, from amino sugars, such as galactosamine, glucosamine, sialic acid, N-acetylglucosamine, from sulfosugars, such as sulfoqui- novose, and carrageenan, from ascorbic acid, and mannitol, from polyuronic acids, such as comprising glucuronic acid, d-Galacturonic acid, and mannuronic acid, poly sugar acids, such as comprising aldonic acid, ulosonic acid, uronic acid, aldaric acid, Glyceric acid (3C), Xy- lonic acid (5C), Gluconic acid (6C), Ascorbic acid (6C), Neuraminic acid
  • the un-modified biopolymer is anionic or cationic. In view of solubility in water such may be an advantage.
  • the un-modified biopolymer is a non-linear biopolymer.
  • the un-modified biopolymer has an average molecular weight of >5kDa (size exclusion chromatography), preferably > 10 kDa, more preferably >20 kDa, such as > 100 kDa.
  • Size exclusion chromatography such as by using a Shimadzu SEC, can be done using a suitable protocol, which are readily available. Such applies to other molecular weights as well.
  • the un-modified biopolymer has an average molecular weight of ⁇ 1500kDa (size exclusion chromatography), preferably ⁇ 1000 kDa, more preferably ⁇ 500 kDa.
  • the un-modified biopolymer has a multifunctionality, that is has different reactive groups, such as exemplified above.
  • the multifunctionality introduces some complexity at the one end, but also offers versatility at the other end.
  • the modified biopolymer-com- pound ester has an average molecular weight of >10 kDa.
  • the polyol and polyacid are provided in a molar ratio of available OH-groups in polyol: avail able acid groups in polyacid of 1 : 10 to 1:2, preferably 1 :5 to 1 :3.
  • a partial reaction is performed, such as forming an anhydride, thereby removing a H2O molecule, and still remaining reactive functionality of the COOH, which may be used later.
  • a partial reaction is performed, such as forming an anhydride, thereby removing a H2O molecule, and still remaining reactive functionality of the COOH, which may be used later.
  • the modified biopolymer-com- pound ester is post-cured at a temperature of > 150 °C, preferably > 160 °C, such as > 170 °C.
  • the modified biopolymer-com- pound ester is post-cured during 5-120 minutes, such as 10-60 minutes, such as 20-30 minutes.
  • the un-modified biopolymer comprises 30-200 % free OH-groups, in particular 50-150%, and/or comprises 5-30% free COOH groups, in particular 10-25%, and/or comprises 1-10% free NH2 groups, in particular 5-8%.
  • the unmodified biopolymers have an number average molecular weight of 50-75 kDa, such as after extraction with Na2CCf have an number average molecular weight of 20-45 kDa, such as after extraction with NaOH at a pH of 11-12, or have an number average molecular weight of 100-150 kDa, e.g. about 120 kDa , such as after extraction with NaOCl [as determined with GPC/SEC],
  • the modified biopolymer is nonsoluble in water.
  • fibres are added to the modified or un-modified biopolymer, in particular cellulosic fibres, such as fibres of 0.2-7 mm length, in particular 1-5 mm in length such as 2-4 mm.
  • a water content of the modified or un-modified biopolymer is reduced, such as by hot-pressing at a temperature of 140-170 °C, in particular 145-160 °C, and/or under a pressure of 1-100 kN, in particular 10-30 kN, such as 15-20 kN, and/or during a time of 10-60 minutes, in particular 15-45 minutes, such as 38-42 minutes.
  • a water content of the modified or un-modified biopolymer is reduced by pre-drying of the modified or un-modi- fied biopolymer during a time of 10-240 minutes, in particular 60-180 minutes, at a temperature of 50-100 °C, in particular 70-80 °C.
  • the present fibre reinforce composite has a flexural modulus of 1-7 GPa (ASTM D790-17), and/or has a flexural strength of 5-30 MPa (ASTM D790-17).
  • a T g of -6 to -10 °C was obtained, depending on an amount on HV in the PHBV.
  • the melting temperature was > 150 °C for PHBV with small amounts of HV..
  • Kaumera extracellular substances obtainable from granular sludge
  • Thin Kaumera/CA films were made at Chaincraft, by drying a solution of the two components.
  • a film thickness of 100 to 200 pm was desired. Therefore, before a first iteration at creating the films, the thickness that would result from the drying process was calculated by using the geometry of the cupcake trays the films were to be made in and estimating the eventual density of the film. The assumptions in this calculation, however, were plenty, which resulted in insufficiently coherent films. Several batches were made, of which the last one is described here.
  • the films were once again dried at 40 °C, this time in a vacuum oven, to remove any moisture. Afterwards, they were placed in a desiccator. Before testing, the films were cut into 3mm wide strips to be able to fit in the DMTA machine.
  • DMTA testing the strips were manually cut to a length of approximately 2 cm to fit in the machine. Temperature sweep measurements were done for different temperature ranges in between -50 °C and 300 °C with a heating rate of 2 °C/min. The load was amplitude controlled, where the amplitude was set manually to be sure that the samples were in the linear regime. The load was always applied at 1 Hz. The machine used was a Perkin Elmer DMTA e7.
  • the glass transition temperature is obtained by reading the temperature at the point where the storage modulus becomes 1.25 GPa, which is around 20 °C.
  • the glass transition point was determined derived to be about 40 °C.
  • For TGA an initial 2 °C/min sweep for the pure Kaumera and 25% CA samples are taken. This showed water released per CA reaction.
  • the amount of water released per citric acid molecule, on average, can be calculated from this data. The higher this number is, the higher the degree of cross-linking, because a molecule reacting with a Kaumera chain releases 1 water molecule, whereas a citric acid molecule reacting with another releases only 0.5 water molecules per CA molecule.
  • the upper limit will be 2, which is when each CA molecule reacts with a Kaumera chain on both sides.
  • the numbers were around 0.5 for 24w% samples, and 0.3 for 50w% samples. This indicates that the samples with a lower CA content, were more efficiently cross-linked than those with a higher content.
  • a set of 20 samples consisting of 64 g of citric acid, 160 g of ALE and 56 g of shredded toilet paper.
  • a set of 10 samples consisting of 46 g of citric acid, 160 g of ALE and 56 g of shredded toilet paper.
  • a set of 18 samples consisting of 64 g of citric acid, 160 g of ALE and 56 g of ReCell R cellulose.
  • the 3 -point-bending test were performed at the mechanical lab in the faculty for maritime, mechanical and materials engineering at TU Delft. They were performed according to the standard ASTM D790-17, which was the most up to-date version of the ASTM standard for testing "Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials" (ASTM International, 2017), the strain rate, which was given as 0:01mm/mm/min by ASTM International (2017).. The tests were performed on a Zwick Z010 tensile tester, using a 10 kN load cell.
  • the machine was operated using the Zwick/Roell TestXpert 2.0 software. Furthermore, a Mituyoto micrometer was used to measure the dimensions of the samples, and a pair of digital calipers was used to measure the support span.
  • ReCell is a recycled cellulose fibre form sewage water.
  • Fibre reinforced composites formed by the present method typically had a flexural modulus Efl ex of 1-7 GPa, such as 2-5 GPa, and a flexural strength Gf of 5-30 MPa using the 3-point bending test, typically 10-20 MPa.
  • Figs, la-b, 2-3, and 4a-b show exemplary reactions.
  • Fig. la shows a schematic reaction between two biopolymers, left and right, having reactive groups for reacting. Shown are OH-reactive groups, COOH-groups, NH2-reactive groups, whereas other groups, such as RSO4Hx groups, RPO4Hx groups, ester-groups, ethergroups, O-acetyl groups, sulfone groups, sulfonate groups, and sulphonamide groups, are not shown, but may be present.
  • Citric acid is added, and reacts under forming of two esters in the example. Likewise, the citric acid may react with one or more of the other reactive groups. In fig. lb a similar reaction as with the citric acid above is shown with glycerol.
  • Fig. 2 shows a schematic reaction between a modified biopolymer and a glycerol.
  • the modified biopolymer is thereby functionalized.
  • the modified biopolymer is plasticized.
  • the terms “functionalize” and “plasticize” may at least partly overlap, depending e.g. on the type of biopolymer, reactant, reaction conditions, etc.
  • Fig. 3 shows a schematic “reaction” between a modified biopolymer and a glycerol.
  • the glycerol is incorporated into the modified biopolymer.
  • the modified biopolymer is thereby plasticized.
  • Fig. 4a shows a schematic reaction between an un-modified biopolymer, in this case polylactic acid, and citric acid.
  • the citric acid reacts with an end-group of the polylactic acid. Therewith the polylactic acid is thereby functionalized. Likewise the modified biopolymer is plasticized.
  • Fig. 4b shows a schematic reaction between an un-modified biopolymer, in this case polylactic acid, and citric acid.
  • the citric acid reacts with an intermediate group of the polylactic acid, effectively dividing the polylactic acid in two polymer chain parts, one with p monomers, and the other with q monomers, and the citric acid moiety in between. Therewith the polylactic acid is thereby functionalized.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de modification de polymères produits par des espèces biologiques, en particulier des microorganismes, par réaction d'un biopolymère non modifié, un biopolymère modifié obtenu par ledit procédé, un adhésif comprenant ledit biopolymère modifié, un composite renforcé par des fibres et comprenant ledit biopolymère modifié et un panneau renforcé par des fibres, comprenant ledit composite renforcé par des fibres.
PCT/NL2022/050494 2021-09-09 2022-08-30 Modification de biopolymères à l'aide de polyols et de polyacides WO2023038519A1 (fr)

Applications Claiming Priority (2)

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NL2029164A NL2029164B1 (en) 2021-09-09 2021-09-09 Modification of biopolymers using polyols and polyacids
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