WO2011103193A2 - Copolyesters comprenant des motifs répétés issus de ω-hydroxy(acides gras) - Google Patents

Copolyesters comprenant des motifs répétés issus de ω-hydroxy(acides gras) Download PDF

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WO2011103193A2
WO2011103193A2 PCT/US2011/025086 US2011025086W WO2011103193A2 WO 2011103193 A2 WO2011103193 A2 WO 2011103193A2 US 2011025086 W US2011025086 W US 2011025086W WO 2011103193 A2 WO2011103193 A2 WO 2011103193A2
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acid
dimethyl
copolyester
hydroxyfatty
cooh
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WO2011103193A3 (fr
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Richard A. Gross
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SyntheZyme LLC
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SyntheZyme LLC
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Priority to EP11745179.9A priority Critical patent/EP2536776A4/fr
Priority to CA2790192A priority patent/CA2790192A1/fr
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Publication of WO2011103193A3 publication Critical patent/WO2011103193A3/fr
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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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to aliphatic or aliphatic-aromatic polyesters and copolyesters comprised of biobased ⁇ -hydroxyfatty acids or derivatives of such materials, processes for the preparation of such polyesters and copolyesters, and compositions thereof having improved properties.
  • Aliphatic polyesters are generally considered to be rapidly biodegradable.
  • U.S. Pat. No. 3,932,319 which is incorporated herein by reference in its entirety, broadly discloses blends of aliphatic polyesters and naturally occurring biodegradable materials.
  • Aliphatic polyesters and copolyesters are a group of biodegradable polymers that may be synthesized from readily renewable building blocks such as lactic acid and fatty acid-derived materials. Such polyesters are synthesized via polycondensation reactions between aliphatic dicarboxylic acids with diols, transesterification of diesters with diols, polymerization of hydroxy acids, and ring-opening polymerization of lactones. Resulting products can be used in industrial and biomedical applications such as for controlled release drug carriers, implants and surgical sutures. Moreover, polyesters with functional groups along chains or in pendant groups are attracting increased interest since these groups can be used to regulate polymeric material properties.
  • ⁇ , ⁇ -dicarboxylic acids were almost exclusively produced by chemical conversion processes.
  • the chemical processes for production of ⁇ , ⁇ -dicarboxylic acids from non-renewable petrochemical feedstocks usually produces numerous unwanted byproducts, requires extensive purification and gives low yields (See, for example, Picataggio et al.,1992, Bio/Tech ology 10, 894-898).
  • ⁇ , ⁇ -dicarboxylic acids with carbon chain lengths greater than 13 atoms are not readily available by chemical synthesis. While several chemical routes to synthesize long-chain ⁇ , ⁇ -dicarboxylic acids are available, their synthesis is difficult, costly and requires toxic reagents.
  • ⁇ , ⁇ -unsaturated diacids e.g. maleic acid and fumaric acid
  • longer chain unsaturated ⁇ , ⁇ -dicarboxylic acids or those with other functional groups are difficult to obtain on a large commercial scale because the chemical oxidation often used to obtain them cleaves the unsaturated bonds or modifies them resulting in cis-trans isomerization (and other) by-products.
  • ⁇ , ⁇ -dicarboxylic acids when cultured in n-alkanes and fatty acids, including Candida tropicalis, Candida cloacae, Cryptococcus neoforman and Corynebacterium sp. (Shiio et al., 1971, Agr. Biol. Chem. 35,2033-2042; Hill et al., 1986, Appl. Microbiol. Biotech. 24: 168-174; and Broadway et al., 1993, J. Gen. Microbiol. 139, 1337-1344).
  • Candida tropicalis and similar yeasts are known to produce ⁇ , ⁇ -dicarboxylic acids with carbon lengths from C12 to C22 via an co-oxidation pathway.
  • the terminal methyl group of n-alkanes or fatty acids is first hydroxylated by a membrane-bound enzyme complex consisting of cytochrome P450 monooxygenase and associated NADPH cytochrome reductase, which is the rate-limiting step in the co-oxidation pathway.
  • cytochrome P450 monooxygenase and associated NADPH cytochrome reductase Two additional enzymes, the fatty alcohol oxidase and fatty aldehyde dehydrogenase, further oxidize the alcohol to create co- aldehyde acid and then the corresponding ⁇ , ⁇ -dicarboxylic acid (Eschenfeldt et al., 2003, App!. Environ. Microbiol. 69, 5992-5999).
  • Mutants of C. tropicalis in which the co-oxidation of fatty acids is impaired may be used to improve the production of ⁇ , ⁇ -dicarboxylic acids (Uemura et al., 1988, J. Am. Oil. Chern. Soc. 64,1254-1257; and Yi et al.,1989, Appl. Microbiol. Biotech. 30, 327-331).
  • Genetically modified strains of the yeast Candida tropicalis have been developed to increase the production of ⁇ , ⁇ -dicarboxylic acids.
  • An engineered Candida tropicalis (Strain H5343, ATCC No.
  • the copolyesters of the present invention comprise co-hydroxyfatty acids and, therefore, have primary instead of secondary hydroxyl groups. As a consequence, they have increased reactivity over corresponding hydroxyfatty acids with internal or secondary hydroxyl groups, such as ricinoleic acid (12-Hydroxy-9-cis-octadecenoic acid) and 12-hydroxystearic acid, for esterification and urethane synthesis. Furthermore, polyesters from ricinoleic acid and 12- hydroxystearic acid have alkyl pendant groups that decrease material crystallinity and melting points. As such, co-hydroxyfatty acids can replace ricinoleic acid and 12-hydroxystearic acid in certain copolymer applications requiring higher performance. Owing to their unique attributes, functional ⁇ -hydroxy fatty acids of the present invention can be used in a wide variety of applications including as monomers to prepare next generation polyethylene-like
  • poly(hydroxyalkanoates), surfactants, emulsifiers, cosmetic ingredients and lubricants, co- Hydroxyfatty acids can also serve as precursors for vinyl monomers used in a wide-variety of carbon back bone polymers.
  • Direct polymerization of ⁇ -hydroxy fatty acids via condensation polymerization gives next generation polyethylene-like polyhyroxyalkanoates that can be used for a variety of commodity plastic applications.
  • the copolyesters of the present invention can be designed for use as novel bioresorbable medical materials. Functional groups along polymers provide sites to bind or chemically link bioactive moieties to regulate the biological properties of these materials. Another use of functional polyesters is in industrial coating formulations, components in drug delivery vehicles and scaffolds that support cell growth during tissue engineering and other regenerative medicine strategies.
  • Microbial PHAs are formed within cells to produce specific polymer compositions with corresponding physical properties. Beyond what can be achieved by changing the physiological conditions of fermentations, further manipulation of the polymer product structure requires a re-engineering of intracellular enzymes involved in polymer synthesis, which is costly and time consuming. As a result, this limitation restricts the range of polymer structures and corresponding material properties that can be derived from microbial PHA manufacturing processes.
  • the process of the present invention provides for the synthesis of monomer ⁇ - hydroxyfatty acids by fermentation and then carrying out subsequent chemical polymerizations (for example the synthesis of PHAs) using ⁇ -hydroxyfatty acid monomers obtained by fermentation.
  • Significant advantages are realized by this approach relative to the above described combination microbial synthesis of both monomer and polymer.
  • Key advantages of the present invention are as follows: i) ⁇ -hydroxyfatty acids are excreted outside of cells, thus simplifying their isolation from other cellular material, ii) since only monomer products are produced, these monomers can be copolymerized with a wide range of bioderived or petrochemical derived monomers to manufacture a diverse range of polymer products.
  • the strategy of bioproduction of monomers that are subsequently polymerized by chemical methods has been successfully implemented to produce commercial products such as
  • poly(propyleneterephtalate), poly(lactic) acid and others See, for example, Robert W. Lenz and Robert H. Marchessault, "Bacterial Polyesters: Biosynthesis, Biodegradable Plastics and
  • Yang, et al. "Two-Step Biocatalytic Route to Biobased Functional Polyesters from o-Carboxy Fatty Acids and Diols," Biomacromolecules, 1 l(l),259-68, described the formation of biobased polyesters catalyzed using immobilized Candida antarctica Lipase B (N435) as catalyst.
  • the polycondensations with diols were performed in bulk as well as in diphenyl ether.
  • the biobased co-carboxy fatty acid monomers 1 , 18-cis-9-octadecenedioic, 1 ,22-cis-9-docosenedioic, and 1 ,18- cis-9,10-epoxy-octadecanedioic acids were synthesized in high conversion yields from oleic, erucic and epoxy stearic acids by whole-cell biotransformations catalyzed by C. tropicalis ATCC20962.
  • the present invention relates to aliphatic or aliphatic-aromatic polyesters and
  • copolyesters comprised of biobased ⁇ -hydroxyfatty acids or derivatives of such materials, processes for the preparation of such polyesters and copolyesters, and compositions thereof having improved properties.
  • the copolyesters of the present invention may also contain additional components that can be selected from aliphatic or aromatic diacids, diols and hydroxyacids obtained from synthetic and natural sources.
  • the biobased ⁇ -hydroxyfatty acids that comprise the polyesters and copolyesters of the present invention are made using a fermentation process from pure fatty acids, fatty acid mixtures, pure fatty acid ester, mixtures of fatty acid esters, and triglycerides from various sources.
  • the polyesters of the present invention may contain various amounts and types of ⁇ -carboxyfatty acids depending on the engineered yeast strain used for the bioconversion as well as the feedstock(s) used.
  • One embodiment of the present invention is a process for preparing an aliphatic or aliphatic/aromatic copolyester comprising the steps of: (i) admixing one or more co-hydroxyfatty acids or an ester thereof, produced by fermentation of a feedstock using an engineered yeast strain, with one or more diacids or an ester thereof, one or more diols in a molar amount equal to the one or more diacids, one or more hydroxyacids and optionally an additive that is a member selected from the group consisting of a branching agent, an ion-containing monomer, and a filler; (ii) heating the mixture in the presence of one or more catalysts to between about 180 DC to about 300 DC; and (iii) recovering the copolyester material.
  • Another embodiment of the present invention is a process for preparing an aliphatic or aliphatic/aromatic copolyester which comprises the steps of: (i) preparing one or more ⁇ - hydroxyfatty acids by fermentation of a feedstock using an engineered yeast strain; (ii) optionally preparing one or more co-hydroxyfatty acid esters from the one or more ⁇ - hydroxyfatty acids; (iii) admixing the one or more ⁇ -hydroxyfatty acids or an ester thereof with one or more diacids or an ester thereof, one or more diols in a molar amount equal to the one or more diacids, and optionally an additive that is a member selected from the group consisting of a branching agent, an ion-containing monomer, and a filler; (iv) heating the mixture in the presence of one or more catalysts to between about 180 DC to about 300 DC; and (v) recovering the copolyester material.
  • Yet another embodiment of the present invention is a process for preparing an aliphatic or aliphatic/aromatic copolyester which comprises the steps of: (i) preparing one or more ⁇ - hydroxyfatty acids by fermentation of a feedstock using an engineered yeast strain; (ii) preparing one or more co-hydroxyfatty acid lactones or co-hydroxyfatty acid lactone multimers from the one or more co-hydroxyfatty acids; (iii) admixing the one or more co-hydroxyfatty acid lactones or co- hydroxyfatty acid lactone multimers with one or more diacids or an ester thereof, one or more diols in a molar amount equal to the one or more diacids, and optionally an additive that is a member selected from the group consisting of a branching agent, an ion-containing monomer, and a filler; (iv) heating the mixture in the presence of one or more catalysts; and (v) recovering the copolyester material.
  • a preferred embodiment of the present invention is a process wherein the one or more diacids or an ester thereof is an co-carboxyfatty acid or an ester thereof obtained by fermentation of a feedstock using an engineered yeast strain.
  • Another preferred embodiment of the present invention is a process which comprises heating the mixture for a second time to between about 180°C to about 260 °C under reduced pressure after the heating step, and a further process wherein the reduced pressure is between about 0.05 to about 2 mmHg.
  • Yet another preferred embodiment of the present invention is a process wherein the one or more co-hydroxyfatty acids or an ester thereof is a lactone or macrolactone multimer of the ⁇ - hydroxyfatty acid.
  • a preferred embodiment of the present invention is a process which comprises selecting the feedstock from a pure fatty acid, a mixture of fatty acids, a pure fatty acid ester, a mixture of fatty acid esters and triglycerides, or a combination thereof.
  • Another preferred embodiment of the present invention is a process wherein the engineered strain of yeast is an engineered strain of Candida tropicalis, and even more preferred is a process wherein the engineered strain of Candida tropicalis is selected from Candida tropicalis strains DP!, DP390, DP415, DP417, DP421 , DP423, DP434 and DP436.
  • One embodiment of the present invention is a process wherein the catalyst is selected from a salt or oxide of Li, Ca, Mg, Mn, Zn, Pb, Sb, Sn, Ge, and Ti, a further process wherein the salt is an acetate salt, an oxide selected from an alkoxide or glycol adduct and a process of where the catalyst is titanium tetraisopropoxide, titanium tetraethoxide, titanium tetrabutoxide, titanium tetrachloride or stannous octanoate.
  • a preferred embodiment of the present invention is a process wherein the ⁇ -hydroxyfatty acids is a member selected from the group consisting of ⁇ -hydroxylauric acid ( ⁇ - ⁇ -LA), co- hydroxymyristic acid ( ⁇ - ⁇ - ⁇ ), ⁇ -hydroxypalmitic acid ( ⁇ - ⁇ - ⁇ ), ⁇ -hydroxy palmitoleic acid (co-OH-POA), co-hydroxystearic acid ( ⁇ - ⁇ -SA), ⁇ -hydroxyoleic acid ( ⁇ - ⁇ - ⁇ ), ⁇ - hydroxyricinoleic acid ( ⁇ - ⁇ -RA), ⁇ -hydroxylinoleic acid ( ⁇ - ⁇ -LA), co-hydroxy-a-linolenic acid, (co-OH-ALA), ohydroxy-y-linolenic acid ( ⁇ - ⁇ -GLA), ⁇ -hydroxybehenic acid ( ⁇ - OHBA) and ⁇ -hydroxyerucic acid ( ⁇ - ⁇ - ⁇ ).
  • ⁇ -hydroxylauric acid ⁇ - ⁇ -LA
  • co- ⁇ - ⁇ - ⁇
  • Another preferred embodiment of the present invention is a process which comprises partially or completely hydrogenating the feedstock prior to fermentation.
  • product ⁇ -hydroxyfatty acids or their esters e.g. methyl esters
  • ⁇ -carboxyfatty acids or their esters are partially or completely hydrogenated prior to their use as monomers to prepare polyesters.
  • a preferred embodiment of the present invention is a process which comprises selecting the one or more diacids or an ester thereof from ⁇ -carboxyllauric acid ( ⁇ -COOH-LA), ⁇ - carboxymyristic acid (co-COOH-MA), ⁇ -carboxypalmitic acid ( ⁇ -COOH-PA), co- carboxypalmitoleic acid ( ⁇ -COOH-POA), co-carboxystearic acid (co-COOH-SA), ⁇ - carboxyoleic acid ( ⁇ -COOH-OA), ⁇ -carboxyricinoleic acid ( ⁇ -COOH-RA), ⁇ -carboxyllinoleic acid ( ⁇ -COOH-LA), ⁇ -carboxy-a-linolenic acid (co-COOH-ALA), co-carboxy-y-linolenic acid ( ⁇ -COOH-GLA), ⁇ -carboxybehenic acid (co-COOH-BA), ⁇ -carboxyerucic acid ( ⁇ -COOH-E
  • Another preferred embodiment of the present invention is a process which comprises selecting one or more diols that are prepared by reduction of diacids or an ester thereof from co- carboxyllauric acid ( ⁇ -COOH-LA), ⁇ -carboxymyristic acid ( ⁇ -COOH-MA), ⁇ -carboxypalmitic acid ( ⁇ -COOH-PA), ⁇ -carboxypalmitoleic acid (co-COOH-POA), ⁇ -carboxystearic acid (co- COOH-SA), ⁇ -carboxyoleic acid ( ⁇ -COOH-OA), ⁇ -carboxyricinoleic acid ( ⁇ -COOH-RA), ⁇ - carboxyllinoleic acid ( ⁇ -COOH-LA), ⁇ -carboxy-a-linolenic acid ( ⁇ -COOH-ALA), co-carboxyy- linolenic acid ( ⁇ -COOH-GLA), ⁇ -carboxybehenic acid ( ⁇ -COOH-BA), ⁇ -carbox
  • Another preferred embodiment of the present invention is a process which comprises selecting one or more diols from ethylene glycol, 1,3-propanediol, 1 ,4-butanediol, 1 ,6- hexanediol, 1 ,8-octanediol, 1,1 O-decanediol, 1, 12-dodecanediol, 1 , 14-tetradecanediol, 1 ,16- hexadecanediol, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, 4,8-bis(hydroxymethyl)tricyclo[ S.2.1.0/2.6]decane, 1 ,4-cyclohexanedimethanol, die ethylene glycol), tri( ethylene glycol), a poly(ethylene oxide)glycol, a poly(butylene ether) glycol, and isosorbide, or a mixture thereof.
  • Yet another preferred embodiment of the present invention is a process which comprises selecting the one or more diacids or an ester thereof and including it as a component of the monomer mixture to be polymerized.
  • Diacids or an ester thereof can be selected from the group consisting of oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, methyl succinic acid, itaconic, dimethly itaconic acid, maleic acid, dimethyl maleic acid, fumaric acid, dimethly fumaric acid, glutaric acid, dimethyl glutarate, 2- methyl glutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, 1, 1 1 -undecanedicarboxylic
  • tetracosanedioic acid dimer acid, 1,4-cyclohexanedicarboxylicacid, dimethyl-1,4- cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic acid, dimethyl-1,3- cyclohexanedicarboxylate, 1 , 1-cyclohexanediacetic acid, 2,S-norbomanedicarboxylic, and mixtures of two or more thereof.
  • Still another preferred embodiment of the present invention is a process which comprises selecting the one or more diacids or an ester thereof and including it as a component of the monomer mixture to be polymerized.
  • Diacids or an ester thereof can be selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethylisophthalate, 2,6-napthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7 -naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4' -diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether dicarboxylate, 4,4' -diphenyl ether dicarboxylic acid, dimethyl-4,4' -diphenyl ether dicarboxylate, 3,4' -diphenyl sulfide dicarboxylic acid, dimethyl-3,4' -diphenyl s
  • Another embodiment of the present invention is a process which comprises selecting one or more a-hydroxyfatty acids or an ester thereof and including it as a component of the monomer mixture to be polymerized.
  • a more preferred embodiment of the present invention is a process wherein the a-hydroxyfatty acid is selected from a-hydroxylauric acid (a-OH-LA), a- hydroxymyristic acid (a-OH-MA), a-hydroxypalmitic acid (a-OH-PA), a-hydroxy palmitoleic acid (a-OH-POA), a-hydroxy stearic acid (a-OH-SA), a-hydroxyoleic acid (a-OH-OA), a- hydroxyricinoleic acid (a-OH-RA), a-hydroxylinoleic acid (a-OH-LA), a-hydroxy-a-linolenic acid, (a-OH-ALA), a-hydroxy-y-linolenic acid (a-OH-GLA), a-hydroxybehenic acid (a-
  • One embodiment of the present invention is a copolyester formed by a process of the present invention comprising an aliphatic or aliphatic/aromatic copolyester comprising one or more ⁇ -hydroxyfatty acids produced by fermentation of a feedstock using an engineered yeast strain, one or more diacids, one or more diols in a molar amount equal to the one or more diacids, and optionally an additive that is a member selected from the group consisting of a branching agent, an ion-containing monomer, and a filler.
  • additional ⁇ - hydroxyacids other than those derived from fermentation of yeast are used in the process of copolyester formation of the present invention.
  • the branching agent is selected from glycerol, pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric acid, 1 ,2,4- benzenetricarboxylic acid, (trimellitic acid), trimethyl-l,2,4-benzenetricarboxylate, 1,2,4- benzenetricarboxylic anhydride, (trimellitic anhydride), 1,3,5-benzenetricarboxylic acid, 1 ,2,4,5- benzenetetracarboxylic acid, (pyromellitic acid), 1,2,4,5-benzenetetracarboxylic dianhydride, (pyromellitic anhydride), 3,3' ,4,4' -benzophenonetetracarboxylic dianhydride, 1 ,4,5,8- naphthalenetetracarboxylic dianhydride, citric acid, tetrahydrofuran-2,3,4,5-
  • the filler is selected from calcium carbonate, non-swellable clays, silica, alumina, barium sulfate, sodium carbonate,
  • magnesium sulfate titanium dioxide
  • zeolites aluminum sulfate, diatomaceous earth
  • magnesium sulfate magnesium carbonate
  • barium carbonate kaolin
  • mica carbon, calcium oxide, magnesium oxide, aluminum hydroxide and polymer particles.
  • Yet another embodiment of the present invention is a reactive extrusion process for preparing a polymer blend which comprises combining one or more copolyesters comprising ⁇ - hydroxyfatty acid repeat units, one or more additional polymers and optionally a catalyst in a reaction vessel, and providing sufficient energy to the combination of the one or more copolyesters comprising ⁇ -hydroxyfatty acid repeat units, the one or more additional polymers and the optional catalyst in order to form a blend wherein the one or more additional polymers are grafted from the one or more copolyesters.
  • a more preferred embodiment of the present invention is a reactive extrusion process wherein the weight ratio the ⁇ -hydroxyfatty acid copolyester and the second polymer has from 1 to 99% by wt. of the ⁇ -hydroxyfatty acid copolyester.
  • An even more preferred embodiment of the present invention is a reactive extrusion process wherein the polyester blend involves a process of reactive extrusion that compatibilizes the blend.
  • Another embodiment of the present invention is a copolyester wherein the copolyester has inherent viscosity suitable for processing by injection molding, film blowing and formation of an article.
  • Yet another embodiment of the present invention is a film comprising a copolyester of the present invention, a fiber comprising a copolyester of the present invention, a coating comprising a copolyester of the present invention, a molded article comprising a copolyester of the present invention, a foam comprising a copolyester of the present invention.
  • the biobased ⁇ -hydroxyfatty acids that comprise the polyesters and copolyesters of the present invention are obtained from pure fatty acids, fatty acid mixtures, pure fatty acid ester, mixtures of fatty acid esters, and triglycerides from various sources, using a fermentation process comprising an engineered yeast strain, such as Candida tropicalis.
  • These copolyesters may contain various amounts and types of ⁇ -carboxyfatty acids depending on the engineered yeast strain used for the bioconversion as well as the feedstock(s) used. Mixtures of ⁇ -hydroxy and a- hydroxyfatty acids are also suitable for use in copolyesters prepared as part of this invention.
  • biobased ⁇ -hydroxyfatty acids and co-carboxyfatty acids of the present invention belong to the larger family of ⁇ -oxidized fatty acids and are synthesized by microbial fermentation using an engineered yeast strain, such as the Candida tropicalis strain described in U.S. Appl. Ser. No. 12/436, 729, which is incorporated herein by reference in its entirety.
  • Biobased ⁇ -hydroxyfatty acids, ⁇ , ⁇ -dicarboxylic acids, and mixtures thereof may be obtained by oxidative conversion of fatty acids to their corresponding ⁇ -hydroxyfatty acids, ⁇ , ⁇ -dicarboxylic acids, or a mixture of these products. Conversion is accomplished by culturing fatty acid substrates with a yeast, preferably a strain of Candida and more preferably a strain of Candida tropicalis.
  • Preferred strains include the engineered strain of Candida tropicalis selected from Candida tropicalis strains DPI, DP390, DP415, DP417, DP421 , DP423, DP434 and DP436.
  • the yeast converts fatty acids to ⁇ -hydroxy fatty acids, co-carboxyfatty acids ( ⁇ , ⁇ - dicarboxylic acids also known as ⁇ , ⁇ -carboxyfatty acids) and mixtures thereof. Fermentations are conducted in liquid media containing pure fatty acids, fatty acid mixtures, pure fatty acid ester, mixtures of fatty acid esters, and triglycerides from various sources. Biological conversion methods for these compounds use readily renewable resources such as fatty acids as starting materials rather than non-renewable petrochemicals, and give the target ⁇ -hydroxyfatty acids and mixtures of ⁇ -hydroxyfatty acids and ⁇ -carboxyfatty acids ( ⁇ , ⁇ -dicarboxylic acids).
  • co-hydroxy fatty acids and ⁇ , ⁇ -dicarboxylic acids can be produced from inexpensive long-chain fatty acids, which are readily available from renewable agricultural and forest products such as soybean oil, palm oil and com oil.
  • a wide range of ⁇ -hydroxyfatty acids and ⁇ , ⁇ -dicarboxylic acids having different carbon length and degree of unsaturation can be prepared because the yeast biocatalyst accepts a wide range of fatty acid substrates.
  • a number of fatty acids are found in natural biobased materials such as natural oils. These natural oils and other sources may be used as feedstocks for fermentation.
  • the common name, scientific name and sources for these fatty acids are shown in Table 1.
  • the fatty acids in table 1 are provided as examples of natural fatty acids and the present invention is not limited to the fatty acids disclosed in table 1.
  • any fatty acid, even a fatty acid having additional functional groups such as double bonds, epoxides or hydroxyl groups, and in particular any fatty acid from either a natural or non-natural source (for example a synthetic fatty acid) can be used as a source of ⁇ -hydroxyfatty acid for the copolyesters of the present invention.
  • Triglycerides and fatty acid esters derived from triglycerides may be used as feedstocks for the fermentation.
  • the ⁇ -hydroxyfatty acids produced by fermentation will consist of a mixture of co- hydroxylated fatty acids that correspond to structures found from the sourced triglyceride.
  • the fatty acids comprising fatty acid feedstocks of the present invention may comprise one or more double bonds.
  • the feedstock is partially or completely hydrogenated prior to fermentation.
  • product ⁇ -hydroxyfatty acids or their esters e.g. methyl esters
  • ⁇ -carboxyfatty acids or their esters are partially or completely hydrogenated prior to their use as monomers to prepare polyesters.
  • the ⁇ -hydroxyfatty acids produced by fermentation may contain up to 75% of co- carboxyfatty acid, up to 50% of co-carboxyfatty acid, less than 5% of ⁇ -carboxyfatty acid, less than 3% of ⁇ -carboxyfatty acid, less than 1 % of ⁇ -carboxyfatty acid, or no ⁇ -carboxyfatty acid.
  • These combinations of co-hydroxyfatty acids and co-carboxyfatty acids produced by fermentation may be used to prepare the copolyesters of the present invention.
  • the co-hydroxyfatty acid monomer obtained by microbial fermentation comprises less than 15% co-carboxyfatty acid, preferably less than 10% co-carboxyfatty acid, more preferably less than 5% co-carboxyfatty acid, even more preferably less than 1% co-carboxyfatty acid, much more preferably less than 0.5% co- carboxyfatty acid and most preferably less than 0.1 % ⁇ -carboxyfatty acid.
  • the co-hydroxyfatty acid monomer contains no ⁇ -carboxyfatty acid, or an undetectable quantity of co-carboxyfatty acid.
  • the co-hydroxyfatty acid monomer obtained by microbial fermentation also comprises co-carboxyfatty acid.
  • the ⁇ -hydroxyfatty acid monomer comprises preferably at least 15% ⁇ -carboxyfatty acid, more preferably at least 20% ⁇ -carboxyfatty acid, even more preferably at least 30% co-carboxyfatty acid, much more preferably at least 50% ⁇ -carboxyfatty acid and most preferably at least 75% co-carboxyfatty acid.
  • the ⁇ -hydroxyfatty acid monomer contains more ⁇ -carboxyfatty acid than ⁇ -hydroxyfatty acid.
  • copolyesters of the present invention can have a repeat unit sequence described by being block-like, random or degrees between these extremes. They are aliphatic or
  • aliphatic/aromatic copolyesters formed by copolymerization of an co-hydroxyfatty acid with a diol, a diacid and optionally one or more additives known in the art or described herein.
  • co-hydroxyfatty acids A-B
  • diols B-B
  • diacids A-A
  • the diacid component of the copolyester may be co-carboxyfatty acids obtained by microbial fermentation, any other diacid obtained from either a natural or synthetic source, or a combination thereof.
  • the co-hydroxyfatty acid (A-B) component of the copolyester will consist of from 10 to 100% of the copolymer.
  • the remaining 0 to 90% of the monomers will be comprised of a diol (B-B), a diacid (A-A), and optionally any other additive known in the art or described herein.
  • the percent composition of the polymers and monomers described herein refer to weight percent.
  • the copolyesters of the present invention comprise one or more hydroxyacids (also denoted A-B), or an ester thereof, obtained from either a natural or synthetic source.
  • the hydroxyacid can be shorter in chain length than a-OH-lactic acid or co-OH-lactic acid, mayor may not be derived from a bioprocess, and can have the hydroxyl group at various positions relative to the carboxylic acid functionality.
  • a more preferred embodiment of the present invention is a process wherein the hydroxyacid is selected from the group consisting of lactic acid, glycolic acid (hydroxyacetic acid), 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid and 6-hydroxyhexanoic acid. Any of the hydroxyacids may be used in the present invention as a hydroxyacid ester, lactone or lactone multimer. Methods for the formation of hydroxyacid esters, lactones and lactone multimers are well known in the art.
  • low molecular weight copolyesters for example in order to obtain a low molecular weight diol pre-polymer for use in the production of thermoplastic polyurethanes, a person skilled in the art would know to employ a molar excess of diol (B-B) monomer in relation to the diacid (A-A) monomer.
  • low molecular weight copolyesters having reactive terminal functional groups represented by X may be obtained by adding molecules having both an acid and a reactive group (A-X), an alcohol and a reactive group (B-X), and preferably both A-X and B-X molecules.
  • a person skilled in the art would know how by controlling the concentration of A-X and B-X molecules relative to the concentration of A-B, AA and B-B monomers one can control the chain length of resulting low molecular weight prepolymers with terminal reactive functional groups X.
  • reactive groups include, but are not limited to an epoxide, an acrylate, an azide, a terminal alkyne, maleimide, 5- norbomene, a double bond, and a thiol.
  • the copolyesters of the present invention may comprise a non-fatty acid derived hydroxyfatty acid (A-B) in addition to the co-hydroxyfatty acid (A-B).
  • the diacids (A-A) of the present invention may be co-diacids derived from the fermentation of a fatty acid feedstock, a non-fatty acid derived diacid, or a mixture thereof.
  • the diol can be prepared by reduction of co-carboxyfatty acid dimethyl esters. The conversion of carboxylic esters to their corresponding hydroxyl group is well known to those skilled in the art. Also, ⁇ - .
  • carboxyfatty acids can be prepared, for example, by feeding fatty acids, pure fatty acids, fatty acid mixtures, pure fatty acid ester, mixtures of fatty acid esters, and triglycerides from various sources, using a fermentation process comprising an engineered yeast strain, such as Candida tropicalis Strain H5343 (ATCC No. 20962).
  • an engineered yeast strain such as Candida tropicalis Strain H5343 (ATCC No. 20962).
  • One embodiment of the present invention is a copolyester comprising 50-100% co- hydroxyfatty acid (A-B), a 0-50% equimolar mixture of a diol (B-B) and a diacid (A-A), and optionally one or more additives known in the art or described herein.
  • A-B co- hydroxyfatty acid
  • B-B a 0-50% equimolar mixture of a diol
  • A-A diacid
  • additives known in the art or described herein.
  • a second embodiment of the present invention is a copolyester comprising 5-50% co- hydroxyfatty acid (A-B), a 50-95% equimolar mixture of a diol (B-B) and a diacid (A-A), and optionally one or more additives known in the art or described herein.
  • A-B co- hydroxyfatty acid
  • B-B diol
  • A-A diacid
  • additives known in the art or described herein.
  • Another embodiment of the present invention is a copolyester comprising an a- hydroxyfatty acid in addition an co-hydroxyfatty acid.
  • Methods to prepare a-hydroxyfatty acids and representative ⁇ -hydroxyfatty acid structures are described in International PCT Publication WO 2009/127009 AI, which is incorporated herein by reference in its entirety.
  • a still further embodiment of the present invention is a copolyester comprising 50-100% of a mixture of co-hydroxyfatty acid (A-B) and ⁇ -hydroxyfatty acid (A-B), a 0-50% equimolar mixture of a diol (B-B) and a diacid (A-A), and optionally one or more additives known in the art or described herein.
  • the copolyester may comprise 75% or more ⁇ -hydroxyfatty acid, 50% ⁇ -hydroxyfatty acid or less than 25% ⁇ -hydroxyfatty acid. Preferably comprising at least 25% ⁇ -hydroxyfatty acid, more preferably at least 10% ⁇ -hydroxyfatty acid, even more preferably at least 7.5% ⁇ -hydroxyfatty acid and most preferably at least 5% ⁇ -hydroxyfatty acid.
  • a second embodiment of the present invention is a copolyester comprising 5-50% of a mixture of co-hydroxyfatty acid (A-B) and ⁇ -hydroxyfatty acid (A-B), a 50-95% of a mixture consisting of a diol (B-B), a diacid (A-A) and optionally one or more additives known in the art or described herein.
  • the copolyester may comprise 45% or more ⁇ -hydroxyfatty acid, 30% a- hydroxyfatty acid or less than 15% ⁇ -hydroxyfatty acid. Preferably comprising at least 15% a- hydroxyfatty acid, more preferably at least 10% a-hydroxyfatty acid, even more preferably at least 7.5% a-hydroxyfatty acid and most preferably at least 5% a-hydroxyfatty acid.
  • the ⁇ -hydroxyfatty acid copolyesters of the present invention will generally have an inherent viscosity in the range of about 0.24 and about 2.0 dL/g as measured at 25° C in a 60/40 parts by weight solution of phenol/tetrachloroethane.
  • the co-hydroxyfatty acid copolyesters of the present invention will generally have an inherent viscosity of about 0.7 to about 2.0 dL/g, more preferably an inherent viscosity of between about 1.0 and about 2.0 dL/g, and even more preferably an inherent viscosity of about 1.10 and about 1.90 dL/g.
  • the co- hydroxyfatty acid copolyesters of the present invention preferably have an inherent viscosity of greater than 1.0 dL/g, more preferably greater than 1.2 dL/g, even more preferably greater than 1.5 dL/g and most preferably greater than 1.8 dL/g.
  • the co-hydroxyfatty acids of the present invention include but are not limited to co- hydroxyl auric acid ( ⁇ - ⁇ -LA), ⁇ -hydroxymyristic acid (co-OH-MA), ⁇ -hydroxypalmitic acid ( ⁇ - ⁇ - ⁇ ), ⁇ -hydroxy palmitoleic acid ( ⁇ - ⁇ - ⁇ ), ⁇ -hydroxystearic acid ( ⁇ - ⁇ -SA), co- hydroxyoleic acid (co-OH-OA), ⁇ -hydroxyricinoleic acid ( ⁇ - ⁇ -RA), ⁇ -hydroxylinoleic Acid ( ⁇ - ⁇ -LA), ⁇ -hydroxy-a-linolenic acid, (co-OH-ALA), co-hydroxy-y-linolenic acid (co- OHGLA), co-hydroxybehenic acid ( ⁇ - ⁇ - ⁇ ) and ⁇ -hydroxyerucic acid ( ⁇ - ⁇ - ⁇ ).
  • the ⁇ -carboxyfatty acids of the present invention include but are not limited to co- carboxyllauric acid (co-COOH-LA), co-carboxymyristic acid ( ⁇ -COOH-MA), ⁇ -carboxypalmitic acid ( ⁇ -COOH-PA), ⁇ -carboxypalmitoleic acid ( ⁇ -COOH-POA), ⁇ -carboxystearic acid (co- COOH-SA), ⁇ -carboxyoleic acid (co-COOH-OA), ⁇ -carboxyricinoleic acid ( ⁇ -COOH-RA), co- carboxyllinoleic acid ( ⁇ -COOH-LA), ⁇ -carboxy-a.-linolenic acid ( ⁇ -COOH-ALA), co-carboxyy- linolenic acid ( ⁇ -COOH-GLA), ⁇ -carboxybehenic acid ( ⁇ -COOH-BA) and ⁇ -carboxyerucic acid ( ⁇ -COOH-EA).
  • the co-carboxyfatty acids are prepared using pure fatty acids, fatty acid mixtures, pure fatty acid ester, mixtures of fatty acid esters, and triglycerides from various sources as feedstocks in a fermentation process comprising an engineered yeast strain, such as Candida tropicalis Strain H5343 (ATCC No. 20962).
  • the co-hydroxyfatty acids produced by the fermentation will consist of a mixture of co- hydroxylated fatty acids, or a mixture of co-hydroxylated and co-carboxylated fatty acids, that correspond to the fatty acids comprising the sourced triglyceride.
  • the feedstock may be subjected to chemical manipulation prior to fermentation.
  • a fatty acid feedstock can be subjected to hydrogenolysis, thereby saturating all or some of the double bond containing fatty acids.
  • co-hydroxyfatty acids or their esters e.g.
  • methyl esters and co- carboxyfatty acids or their esters produced by fermentations may be subjected to chemical manipulation. For example, they can be subjected to hydrogenolysis, thereby saturating all or some of their double bonds.
  • the resulting ⁇ -hydroxyfatty acids or their esters (e.g. methyl esters) and co-carboxyfatty acids or their esters will be greatly simplified and comprise a mixture of products that differ only in chain length.
  • the dicarboxylic acids (A-A) of the present invention may be selected from any dicarboxylic acid.
  • Non-limiting examples include unsubstituted or substituted; straight chain, branched, cyclic aliphatic, aliphatic-aromatic, or aromatic diacids having, for example, from 2 to 36 carbon atoms or poly(alkylene ether) diacids with molecular weights preferably between about 250 to about 4,000.
  • Diacids used can be in free acid form or can be used as corresponding esters such as dimethyl ester derivatives. Methods for the formation of carboxylic acid esters are well known in the art.
  • useful aliphatic diacid components include oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, methyl succinic acid, itaconic, dimethly itaconic acid, maleic acid, dimethyl maleic acid, fumaric acid, dimethly fumaric acid, glutaric acid, dimethyl glutarate, 2-methylglutaric acid, 3 -methyl glutaric acid, adipic acid, dimethyl adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, 1, 1 1 -undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, undecanedioic acid, 1, 12-dodecanedicarboxylic acid,
  • hexadecanedioic acid docosanedioic acid, tetracosanedioic acid, dimer acid, 1 ,4- cyclohexanedicarboxylic acid, dimethyl-I,4-cyclohexanedicarboxylate, 1,3- cyclohexanedicarboxylic acid, dimethyl-I,3-cyclohexanedicarboxylate, 1, 1-cyclohexanediacetic acid, 2,5-norbomanedicarboxylic, and mixtures of two or more thereof.
  • aromatic diacid components include aromatic dicarboxylic acids or esters, and include terephthalic acid, dimethyl terephthal ate , isophthalic acid, dimethylisophthalate, 2,6-napthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7- naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4' -diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether dicarboxylate, 4,4'-diphenyl ether dicarboxylic acid.dimethyl- 4,4'diphenyl ether dicarboxylate, 3,4' -diphenyl sulfide dicarboxylic acid, dimethyl-3,4' -diphenyl sulfide dicarboxylate, 4,4' -diphenyl sulfide dicarboxylic acid, dimethyl-4,4' -diphenyl
  • the diol (B-B) of the present invention may be selected from any dihydric alcohol, glycol, or diol.
  • Non-limiting examples include unsubstituted or substituted; straight chain, branched, cyclic aliphatic, aliphatic-aromatic, or aromatic diols having, for example, from 2 to 36 carbon atoms or poly(alkylene ether) diols with molecular weights between about 250 to about 4,000.
  • diols include ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,8-octanediol, 1 ,1 O-decanediol, 1 , 12-dodecanediol, 1 , 14-tetradecanediol, 1 ,16-hexadecanediol, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, 4,8-bis(hydroxymethyl)tricyclo[ 5.2.1.0/2.6]decane,l,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene glycol), poly(ethylene oxide)glycols, poly(butylene ether) glycols, and isosorbide, or a mixture thereof.
  • Diols of the present invention may also be prepared by the reduction of a diacid, including ⁇ -carboxyfatty acid dimethyl esters.
  • Methods for the reduction of carboxylic acids and carboxylic acid esters are well known in the art. Common methods include the use of hydride reducing agents such as lithium aluminum hydride (LAH) and diisobutyl aluminum hydride (DIBAL), among others.
  • LAH lithium aluminum hydride
  • DIBAL diisobutyl aluminum hydride
  • alkylene refers to either straight or branched chain alkyl groups, such as -CH2-CH2-CH2- or -CH2-CH(CH3)-CH2-, and the term “cycloalkylene” refers to cyclic alkylene groups which may or may not be substituted.
  • cycloalkylene refers to cyclic alkylene groups which may or may not be substituted.
  • oxyalkylene refers to an alkylene group which contains one or more oxygen atoms, such as -CH2-CH2-0-CH2-CH2-, which also may be linear or branched.
  • glass transition temperature means that temperature below which a polymer becomes hard and brittle, like glass.
  • the term "precursor film” is meant to include films that have not been stretched or otherwise physically manipulated prior to use and/or evaluation and analysis. This includes films that contain a filler material, such as calcium carbonate, that have not been stretched to create the pores around the calcium carbonate to allow water vapor to pass through the film.
  • a filler material such as calcium carbonate
  • the term “stretched film” is meant to include films that have been stretched to create pores around a filler material. These stretched films are ready for use in an absorbent article as they will allow water vapor to pass through.
  • Methods of preparing aliphatic and aromatic-aliphatic copolyesters are known in the art. Most commonly, a mixture of monomers that includes a dicarboxylic acid (designated A- A), and a diol (designated B-B) are reacted in the presence of a catalyst. Water is driven off, and under proper conditions, a copolyester results that can have a repeat unit sequence described by being block-like, random or degrees between these extremes.
  • Alternative synthetic methods include using methyl esters in place of the carboxylic acids. In these methods methanol is volatilized rather than water during the reaction. Other synthesis methods are also known to those skilled in the art.
  • reactions are carried out using diols and diacids (or diesters or anhydrides) at temperatures from about 150°C to about 300 °c in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof.
  • polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof.
  • One embodiment of the present invention is a process for the preparation of an aliphatic or aliphatic/aromatic copolyester comprising one or more co-hydroxyfatty acids, or an ester thereof, and one or more ⁇ -carboxyfatty acids, or an ester thereof, obtained by fermentation of a feedstock using an engineered strain of yeast.
  • the process involves adding a diol in a molar amount equal to the molar amount of the co-carboxyfatty acid components and heating the mixture in the presence of a catalyst or catalyst mixture to between about 180°C to about 300 DC.
  • the catalyst can either be included initially in the reactant mixture, or can be added one or more times while the mixture is heated. Desirably the polymerization is performed in two stages.
  • reaction mixture In a first stage, said reaction mixture is heated between 180°C and 220 °c at or slightly above atmospheric pressure, and in a second stage, heating said reaction mixture between 180°C and 260 °C under a reduced pressure of 0.05 to 2.00 mm of Hg.
  • the conditions and the catalysts depend in part upon whether the diacids are polymerized as true acids or as dimethyl esters. The heating and stirring are continued for a sufficient time and to a sufficient temperature, generally with removal of excess reactants under vacuum, to yield a molten polymer having a high enough molecular weight to be suitable for making fabricated products.
  • a suitable catalyst is selected from salts of Li, Ca, Mg, Mn, Zn, Pb, Sb, Sn, Ge, and Ti, such as acetate salts and oxides, including glycol adducts, and Ti alkoxides.
  • Such catalysts are known, and a catalyst or combination or sequence of catalysts used can be selected by a skilled practitioner.
  • the preferred catalyst and preferred conditions can vary depending upon, for example, whether the diacid monomer is polymerized as the free diacid or as a dimethyl ester, and/or on the chemical composition of the diol, hydroxyfatty acid and diacid components.
  • the catalyst used can be modified as the reaction proceeds. Any catalyst system known for use in such polymerizations can be used.
  • Titanium-based catalyst systems e.g. titanium tetraisopropoxide, titanium tetraethoxide, titanium tetrabutoxide, titanium tetrachloride
  • Catalyst concentrations generally range from 10 to 1000 ppm.
  • reactions are best carried out in two stages as described herein. The final stages of the reaction are generally conducted under high vacuum «10 mm of Hg) in order to produce a high molecular weight polyester.
  • a solvent may be necessary when synthesizing polymers of high viscosity or when using monomers, and forming polymers, with melting points above 100°C.
  • preferred organic solvents are those not containing a hydroxyl group, including but not limited to tetrahydrofuran, toluene, diethyl ether, diphenyl ether, diisopropyl ether, dioxane, isooctane, do de cane, methylene chloride and chloroform.
  • the range of solvent used is from 0.0% to 90% by weight relative to the monomer.
  • Condensation polymerizations of diacids and diols may also be performed using enzyme catalysis with enzymes such as lipase.
  • Mahapatro et al., 2004, Macromolecules 37, 35-40 describes.catalysis of condensation polymerizations between adipic acid and 1 ,8-octanediol using immobilized Lipase B from Candida antarctica (CALB) as the catalyst. Effects of substrates and solvents on lipase-catalyzed condensation polymerizations of diacids and diols have been also described. See Olsson, et al., Biomacromolecules, 2003, 4: 544-551.
  • U.S. Patent No. 6,486,295 which is incorporated by reference herein in its entirety, describes the formation of copolymers using lipase catalyzed transesterification reactions of preformed polymers and monomers.
  • the ⁇ , ⁇ -dicarboxylic acid methyl esters were synthesized by metathetical dimerization of 9-decenoic, 10-undecenioc and 13- tetradecenioc acid methyl esters, and polycondensation with 1,4-butanediol in diphenyl ether yielded the polyesters with molecular weight (Mw) of 7800-9900 g/mol.
  • Mw molecular weight
  • Uyama et al. report polymerization of epoxidized fatty acids (in side-chain) with divinyl sebacate and glycerol to prepare epoxide-containing polyesters in good yields. See Uyama, et al., 2003,
  • Biomacromolecules 4, 21 1-215 which is hereby incorporated by reference in its entirety.
  • cis-9,10-epoxy-18-hydroxyoctadecanoic acid isolated from suberin in the outer bark of birch, was used as a monomer in the synthesis an
  • the preferred lipases of the present invention include Candida antartica Lipase B, PS-30, immobilized form of Candida antartica lipase B such as Novozym 435, immobilized lipase PS from Pseudomonas fluorescens, immobilized lipase PC from Pseudomonas cepacia, lipase PA from Pseudomonas aeruginosa, lipase from Porcine Pancreas (PPL), Candida cylindreacea (CCL), Candida rugosa (CR), Penicillium roquelorti (PR) , Aspergillus niger (AK), and
  • Lypozyme 1M from Mucor miehei can be used as catalysts.
  • the cutinase from Humicola insolens immobilized on a macroporous resin is useful for catalysis of polyester synthesis.
  • a solvent may be necessary when synthesizing polymers of high viscosity or when using monomers, and forming polymers, with melting points above 100°C.
  • preferred organic solvents are those not containing a hydroxyl group, including but not limited to tetrahydrofuran, toluene, diethyl ether, diphenyl ether,
  • diisopropylether and isooctane The range of solvent used is from 0.0% to 90% by weight relative to the monomer. Although a solvent is not necessary, using an amount of solvent approximately twice the volume of the monomer has been found to provide satisfactory results.
  • the copolyesters of the present invention may also be formed by ring-opening polymerization of the corresponding lactone or a macro lactone multimer of the ⁇ -hydroxyfatty acids.
  • the macrolactone multimer may comprise two or more ⁇ -hydroxyfatty acids.
  • Ring opening polymerization is a polymerization process in which polymerization proceeds as a result of ring-opening of a cyclic compound as a monomer to synthetically yield a polymer.
  • polyethyleneimines, polysiloxanes and polyesters are produced through ring-opening polymerization.
  • Ring-opening polymerization has been applied to synthesize a number of polyesters, such as polylactides and polycaprolactones. For example, ring-opening
  • polymerization of ⁇ -caprolactone using heat and a catalyst such as stannous octanoate provides the polyester polycaprolactone.
  • Polylactic acid is obtained first through bacterial fermentation to produce lactic acid, then lactic acid is catalytically converted to lactide, a cyclic dimer, which is used as a monomer for polymerization.
  • Polylactic acid of high molecular weight is produced by ring-opening polymerization using a stannous octanoate catalyst in most industrial applications, however tin(II) chloride has also employed.
  • the copolyesters of the present invention may be formed by ring-opening polymerization by first cyclizing the ⁇ -hydroxyfatty acids to their corresponding lactones or macro lactone multimers. Methods for the formation of lactones and macro lactone multimers are well known in the art.
  • Ring-opening polymerization of lactones and the ⁇ -hydroxyfatty acid lactones of the present invention may be catalyzed by any number of catalysts, including antimony compounds, such as antimony trioxide or antimony trihalides, zinc compounds (zinc lactate) and tin compounds like stannous octanoate (tin(II) 2-ethylhexanoate), tin(II) chloride or tin alkoxides.
  • antimony compounds such as antimony trioxide or antimony trihalides
  • zinc compounds zinc lactate
  • tin compounds like stannous octanoate (tin(II) 2-ethylhexanoate), tin(II) chloride or tin alkoxides.
  • Stannous octanoate is the most commonly used initiator, since it is approved by the U.S. Food and Drug Administration (FDA) as a food stabilizer.
  • FDA U.S. Food and
  • the ⁇ -hydroxyfatty acid lactones of the present invention may be copolymerized using ring-opening polymerization in the presence of one or more additional lactones.
  • Additional lactones useful in the present invention include a-hydroxyfatty acid lactones or macro lactone multimers, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprylolactone, ⁇ -valerolactone, P-methyl-8-valerolactone, ⁇ -stearolactone, ⁇ -caprolactone, 2- methyl-E-caprolactone, 4-methyl-e-caprolactone, ⁇ -caprylolactone, and ⁇ -palmitolactone.
  • cyclic dimers such as glycolides and lactides can also be used as monomers in ring opening polymerization, as with lactones.
  • cyclic carbonate compounds such as ethylene carbonate, 1,3-propylene carbonate, neopentyl carbonate, 2-methyl-l,3-propylene carbonate, and 1 ,4-butanediol carbonate can be used herein.
  • copolyesters of the present invention have variable biobased content and
  • the biodegradable aliphatic-aromatic copolyester comprises from about 15 mole % to about 25 mole % of aromatic dicarboxylic acid or an ester thereof, from about 25 mole % to about 35 % mole % of aliphatic dicarboxylic acid or an ester thereof, and from about 40 mole % to about 60 mole % dihydric alcohol and wherein the weight average molecular weight of the copolyester is from about 100,000 to about 130,000 Daltons, and wherein the number average molecular weight of the copolyester is from about 40,000 to about 60,000 Daltons.
  • the co-hydroxyfatty acid copolyesters of the present invention have a melting temperature from about 90°C to about 150 0c.
  • the ⁇ -hydroxyfatty acid copolyesters of the present invention preferably have a melting temperature greater than 100°C, more preferably greater than 140°C, even more preferably greater than 1 10 °c and most preferably greater than 120°C.
  • the monomer composition of the polymer can be selected for specific uses and for specific sets of properties. For example, one skilled in the art knows that thermal properties of a copolyester are determined by the chemical identity and level of each component utilized in the copolyester composition. Inherent viscosity is another property of the copolyester known to one of skill in the art to vary based on copolyester composition. Inherent viscosity is a viscometric method for measuring molecular size. Inherent viscosity is based on the flow time of a polymer solution through a narrow capillary relative to the flow time of the pure solvent through the capillary. The units of inherent viscosity are typically reported in deciliters per gram (dL/g). Copolyesters having adequate inherent viscosity for many applications can be made by the processes disclosed herein and by those methods known to one skilled in the art.
  • melt condensation can be used to obtain copolymers of adequate inherent viscosity.
  • Solid state polymerization can be used to obtain even higher inherent viscosities (molecular weights).
  • Copolyesters made by melt polymerization, after extruding, cooling and pelletizing may be semi crystalline or essentially noncrystalline.
  • Noncrystalline material can be made semicrystalline by heating it to a temperature above the glass transition temperature for an extended period of time. This induces crystallization so that the product can then be heated to a higher temperature to raise the molecular weight.
  • the polymer can be crystallized prior to solid-state polymerization by treatment with a relatively poor solvent for polyesters, which induces crystallization by reducing the T g.
  • Solvent induced crystallization is known for polyesters and is disclosed, for example, in U.S. Pat. Nos. 5,164,478 and 3,684,766, which are incorporated herein by reference in their entireties.
  • the semicrystalline polymer can then be subjected to solid state polymerization by placing the pelletized or pulverized polymer into a stream of an inert gas, usually nitrogen, or under a vacuum of 1 Torr, at an elevated temperature, but below the melting temperature of the polymer for an extended period of time until the desired molecular weight is achieved.
  • copolyesters of this invention are essentially linear. However, these copolyesters can be modified with low levels of one or more branching agents.
  • a branching agent is a molecule that has at least three functional groups that can participate in a polyester-forming reaction, such as hydroxyl, carboxylic acid, carboxylic ester, phosphorous based ester (potentially trifunctional) and anhydride (difunctional).
  • Typical branching agents useful in the present invention include glycerol, pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric acid (and derivatives thereof), 1 ,2,4-benzenetricarboxylic acid, (trimellitic acid), trimethyl-l,2,4-benzenetricarboxylate, 1,2,4-benzenetricarboxylic anhydride, (trimellitic anhydride), 1,3,5-benzenetricarboxylic acid, 1 , 2,4,5 -benzenetetracarboxylic acid, (pyromellitic acid), 1,2,4,5-benzenetetracarboxylic dianhydride, (pyromellitic anhydride), 3,3' ,4,4' -benzophenonetetracarboxylic dianhydride, 1 ,4,5 ,8-naphthalenetetracarboxylic dianhydride, citric acid, tetrahydrofuran-2,3,4,5
  • the total amount of branching agent may be less than about 10% by weight of the total polymer. Alternatively, the branching agent may be less than about 5%, or less than about 3%.
  • a preferred range for branching agents in the present invention is from about 0.1 to about 2.0 weight %, more preferably about 0.2 to about 1.0 weight %, based on the total weight of the polyester. Addition of branching agents at low levels does not have a significant detrimental effect on the physical properties and provides additional melt strength which can be very useful in film extruding operations. High levels of branching agents incorporated in the copolyesters can result in copolyesters with poor physical properties (e.g., low elongation and low
  • phosphites such as those described in U.S. Patent No. 4,097,431 entitled “Aromatic Copolyester Composition,” which is incorporated by reference herein in its entirety.
  • phosphites include, but are not limited to, tris-(2,4-di-t-butylphenyl)phosphite;
  • diphosphite 2,2-methylenebis-(4,6-di-t-butylphenyl)octylphosphite; 4,4-butylidenebis-(3- methyl-6-t-butylphenyl-di-tridecyl)phosphite; l,l ,3-tris-(2-methyl-4-tridecylphosphite-5-t- butylphenyl)butane; tris-(mixed mono- and nonylphenyl)phosphite; tris-(nonylphenyl)phosphite; and 4,4' -isopropylidene bis-(phenyl-dialkylphosphite).
  • Preferred compounds are tris-(2,4-di- tbutylphenyl) phosphite; 2,2-methylenebis-(4,6-bi-t-butylphenyl)octylphosphite; bis-(2,6-di- tbutyl-4-methylphenyl)pentaerythritol diphosphite, and tetrakis-(2,4-di-t-butylphenyl)- 4,4'biphenylenephosphonite.
  • the total level for the presence of each or both of the phosphite and phosphonite is in the range of about 0.05-2.0 weight %, preferably 0.1-1.0 weight %, and more preferably 0.1-0.5 weight %.
  • Particularly preferred phosphites include Weston stabilizers such as Weston 619, a product of General Electric Specialty Chemicals Company, distearyl pentaerythritol diphosphite, Ultranox stabilizers such as Ultranox 626, an aromatic phosphite produced by General Electric Specialty Chemicals Company, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, and Irgafos 168, an aromatic phosphite produced by Ciba-Geigy Corp.
  • Another example of an aromatic phosphite compound useful within the context of this invention is Ultranox 633, a General Electric Specialty Chemical Company developmental compound.
  • the copolyesters of the present invention may be prepared by including one or more ion- containing monomers in the monomer mixture to be polymerized.
  • the ion-containing monomer may be, for example, an alkaline earth metal salt of a sulfonate group.
  • Copolyesters containing sulfonate groups are sulfonated copolyesters.
  • the sulfonated copolyesters contain from 0.1 to 5 mole percent of sulfonate groups. While it is not intended that the present invention be bound by any particular theory, it is believed that the presence of the sulfonate groups enhances the biodegradation rates of the copolyesters.
  • the sulfonate groups can be introduced in aliphatic or aromatic monomers or can be introduced as end groups.
  • Exemplary aliphatic sulfonate components include metal salts of sulfosuccinic acid.
  • Exemplary aromatic sulfonate components useful as end-groups include metal salts of 3-sulfobenzoic acid, 4-sulfobenzoic acid, and 5- sulfosalicylic acid.
  • Sulfonate components may contain a sulfonate salt group attached to an aromatic dicarboxylic acid.
  • Aromatic nuclei that can be present in the aromatic dicaraboxylic acid include benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl, methylenediphenyl.
  • the sulfonate component can be the residue of a sulfonate-substituted phthalic acid, terephthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid.
  • the sulfonate component can be the metal salt of 5-sulfoisophthalic acid or a lower alkyl ester of 5-sulfoisophthalate.
  • the metal salt can be selected from monovalent or polyvalent alkali metal ions, alkaline earth metal ions, or other metal ions.
  • Preferred alkali metal ions include sodium, potassium and lithium.
  • alkaline earth metals such as magnesium are also useful.
  • Other useful metal ions include the transition metal ions, such as zinc, cobalt or iron.
  • the multivalent metal ions are useful, for example, when an increased viscosity of the sulfonated copolyesters are desired. End use examples where such melt viscosity enhancements may prove useful include melt extrusion coatings, melt blown containers or film, and foam.
  • the amount of sulfonate group-containing component in the sulfonated aliphatic-aromatic copolyester is 0.1 to 4.0 mole percent.
  • copolyesters of the present invention may be blended with other polymeric materials, which may be biodegradable or non-biodegradable, and may be naturally derived, modified naturally derived or synthetic.
  • blendable biodegradable materials include poly(vinyl alcohol), polyethylene glycols, sulfonated aliphatic-aromatic copolyesters, such as those sold under the Biomax® trade name by the DuPont Company, aliphatic-aromatic copolyesters, such as are sold under the Eastar Bio® trade name by the Eastman Chemical Company, those sold under the Ecoflex® trade name by the BASF corporation, and those sold under the EnPol® trade name by the Ire Chemical Company; aliphatic polyesters, such as the poly( alkylene succinates), poly(l ,4-butylene succinate) (Bionolle ® 1001 , from Showa High Polymer Company), poly(ethylene succinate), poly(I,4-butylene adipate-co-succinate) (Bion
  • blendable nonbiodegradable polymeric materials include polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, polyolefins, poly(ethylene-co-glycidylmethacrylate), poly(ethylene-co- methyl methacrylate-co-glycidyl acrylate), poly(ethylene-co-n-butyl acrylate-co-glycidyl acrylate), poly(ethylene-co-methyl acrylate), poly(ethylene-co-ethyl acrylate), poly(ethylene-co- butyl acrylate), poly(ethylene-co-methacrylie acid), metal salts of poly(ethylene-co-methacrylic acid), poly(methacrylates), such as poly(methyl methacrylate), poly(ethyl methacrylate), poly(ethylene-co-carbon monoxide), poly(vinyl acetate), poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl alcohol), polypropylene,
  • blendable natural or modified natural polymeric materials include starch, starch derivatives, modified starch, thermoplastic starch, cationic starch, anionic starch, starch esters (e.g. starch acetate), starch hydroxyethyl ether, alkyl starches, dextrins, amine starches, phosphate starches, dialdehyde starches, cellulose, cellulose derivatives, modified cellulose, cellulose acetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose valerate, cellulose triacetate, cellulose tripropionate, cellulose tributyrate, and cellulose mixed esters such as cellulose acetate propionate and cellulose acetate butyrate, cellulose ethers, such as methylhydroxyethylcellulose, hydroxymethylethylcellulose, carboxymethylcellulose, methyl cellulose, ethylcellulose, hydroxyethycellulose, and hydroxyethylpropylcellulose,
  • starch esters e
  • polysaccharides alginic acid, alginates, phycocolloids, agar, gum arabic, guar gum, acacia gum, carrageenan gum, furcellaran gum, ghafti gum, psyllium gum, quince gum, tamarind gum, locust bean gum, gum karaya, xanthan gum, gum tragacanth, proteins, Zein® prolamine derived from com, collagen, derivatives thereof such as gelatin and glue, casein, sunflower protein, egg protein, soybean protein, vegetable gelatins, gluten, and mixtures derived therefrom.
  • Thermoplastic starch can be produced, for example, as in U.S. Pat. No. 5,362,777, which discloses the mixing and heating of native or modified starch with high boiling plasticizers, such as glycerin or sorbitol, in such a way that the starch has little or no crystallinity, a low glass transition temperature and a low water content.
  • high boiling plasticizers such as glycerin or sorbitol
  • the polymeric material to be blended with the copolyester of the present invention can be added to the copolyester at any stage during the polymerization or after the polymerization is completed.
  • the polymeric materials may be added with the copolyester monomers at the start of the polymerization process.
  • the polymeric material can be added at an intermediate stage of the polymerization, for example, as the precondensate passes into the polymerization vessel.
  • the polymeric material can be added after the copolyester exits the polymerization reactor.
  • the copolyester and the polymeric material can be melt fed to any intensive mixing operation, such as a static mixer or a single- or twin-screw extruder and thereby compounded with the copolyester.
  • the copolyester can be combined with the polymeric material in a subsequent postpolymerization process.
  • a subsequent postpolymerization process includes intensive mixing of the molten copolyester with the polymeric material, which may be provided through static mixers, Brabender mixers, single screw extruders, twin screw extruders as described hereinabove with regard to the incorporation of fillers.
  • the copolyesters of the present invention may be blended with other polymers, including biodegradable polymers, using the process of reactive extrusion.
  • Reactive extrusion is an attractive route for polymer processing in order to carry out melt-blending, and various reactions including polymerization, grafting, branching and functionalization as well (See, for example, Mani, R., et al., J. Polymer Sci.: Part A: Polymer Chem., 1999, 37, 1693-1702; Michaeli, W., et al., J. Appl. Polymer Sci., 1993,48, 871-886; Kye, H., et al., J. of Appl. Polymer Sci., 1994, 52, 1249-1262; U.S. Patent No.
  • Copolymerization by reactive extrusion is an important process in the production of new copolymers, in part because the properties, namely the phase behavior, optical and mechanical properties of the newly formed copolymer can be altered based on the degree of
  • Resulting copolyesters from transesterification are composed of repeat units from both the ⁇ -hydroxyfatty acid copolyester and the second polyester.
  • the sequence distribution of resulting copolyesters can vary from random to block copolymers and any intermediate degree of block character (e.g. multiblocks where sequences have varying average sequence lengths).
  • Methods for performing reactive trans esterification are well known to those skilled in the art.
  • a number of catalysts may be employed to compatibilize or modify the blend structure by transesterification. These catalysts include but are not limited to inorganic oxycompounds such as alkoxides, phenoxides, enolates or carboxylates of calcium, aluminum, titanium, zirconium, tin, antimony or zinc.
  • a typical family of catalysts known in the art to promote transesterification are aluminum trialkoxides.
  • Reactive Extrusion and U.S. Patent No. 7,053,151 entitled “Grafted Biodegradable Polymer Blend Compositions,” which are incorporated herein by reference in their entirety, describe the formation of grafted polymer blends of biodegradable polymers using reactive extrusion.
  • a radical initiator is added in order to promote grafting between the polymer chains of the different polymers in order to produce a new polymer with different properties.
  • Methods to make polyester blends are described by a melt phase reaction in which a molten polyester is reacted with a free radical initiator and a polar monomer or mixture of two or more polar monomers, particularly polar vinyl monomers. The melt phase
  • modification is termed "reactive extrusion" in that a new polymer species is created upon the modification reaction.
  • the ingredients including a polyester containing some content of co- hydroxyfatty acid repeat units, a free radical initiator, a polar monomer or a mixture of polar monomers in a predetermined ratio are added simultaneously to a melt mixing device or an extruder.
  • the polyester with OJ-hydroxyfatty acid repeat units may be fed to a feeding section of a twin screw extruder and subsequently melted, and a mixture of a free radical initiator and polar monomer or mixture of polar monomers, is injected into the biodegradable polymer melt under pressure, the resulting melt mixture is then allowed to react.
  • the polyester with ⁇ -hydroxyfatty acid repeat units is fed to the feeding section of a twin screw extruder, then the free radical initiator and polar monomer, or mixture of monomers, are fed separately into the twin screw extruder at different points along the length of the extruder.
  • the heated extruder extrusion is performed under high shear and intensive dispersive and distributive mixing resulting in a grafted blend of polyesters of high uniformity.
  • Blends of the present invention may be substantially free of surfactants, plasticizers, compatibilizers, catalysts and inorganic fillers.
  • inorganic fillers and/or plasticizers may be added to the blends.
  • the copolyester ' s of the present invention or blends comprising copolyesters of the present invention can be filled with inorganic, organic and/or clay fillers such as, for example, wood flour, gypsum, talc, mica, carbon black, wollastonite, montmorillonite minerals, chalk, diatomaceous earth, sand, gravel, crushed rock, bauxite, limestone, sandstone, aerogels, xerogels, micro spheres, porous ceramic spheres, gypsum dihydrate, calcium aluminate, magnesium carbonate, ceramic materials, pozzolamic materials, zirconium compounds, xonotlite (a crystalline calcium silicate gel), perlite, vermiculite, hydrated or unhydrated hydraulic cement particles, pumice, zeolites, kaolin, clay fillers, including both natural and synthetic clays and treated and untreated clays, such as organoclays and clays which have been surface treated with silanes and stea
  • Fillers can increase the Young's modulus, improve the dead-fold properties, improve the rigidity of the film, coating or laminate, decrease the cost, and reduce the tendency of the film, coating, or laminate to block or self-adhere during processing or use.
  • the use of fillers has been found to produce plastic articles which have many of the qualities of paper, such as texture and feel, as disclosed by, for example, Miyazaki, et. al., in U.S. Pat. No. 4,578,296, which is incorporated by reference herein in its entirety.
  • plasticizers which may be added to improve processing and/or final mechanical properties, or to reduce rattle or rustle of the films, coatings, or laminates made from the copolyesters, include soybean oil, epoxidized soybean oil, com oil, castor oil, linseed oil, epoxidized linseed oil, mineral oil, alkyl phosphate esters, plasticizers sold under the trademark "Tween” including Tween® 20 plasticizer, Tween® 40 plasticizer, Tween® 60 plasticizer, Tween® 80 plasticizer, Tween® 85 plasticizer, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, citrate esters, such as trimethyl citrate, triethyl citrate (Citroflex® 2, produced by Morflex, Inc.
  • the additives, fillers or blend materials can be added before the polymerization process, at any stage during the polymerization process and/or in a post polymerization process. Any known filler material can be used.
  • Exemplary suitable clay fillers include kaolin, smectite clays, magnesium aluminum silicate, b.entonite clays, montmorillonite clays, hectorite clays, and mixtures derived therefrom.
  • the clays can be treated with organic materials, such as surfactants, to make them organophilic.
  • Suitable commercially available clay fillers include Gelwhite MAS 100, a commercial product of the Southern Clay Company, which is defined as a white smectite clay, (magnesium aluminum silicate); Claytone 2000, a commercial product of the Southern Clay Company, which is defined as an organophilic smectite clay; Gelwhite L, a commercial product of the Southern Clay Company, which is defined as a montmorillonite clay from a white bentonite clay; Cloisite 30 B, a commercial product of the Southern Clay Company, which is defined as an organophilic natural montmorillonite clay with bis(2-hydroxyethyl)methyl tallow quarternary ammonium chloride salt; Cloisite Na, a commercial product of the Southern Clay Company, which is defined as a natural montmorillonite clay; Garamite 1958, a commercial product of the Southern Clay Company, which is defined as a mixture of minerals; Laponite RDS, a commercial product of the Southern Clay Company, which is defined as a synthetic layered silicate with
  • PG Polymer Grade (PG) Montmorillonite PGN, a commercial product of the Nanocor Company, which is defined as a high purity aluminosilicate mineral, sometimes referred to as a
  • clay filler Any clay filler known can be used. Some clay fillers can exfoliate, providing nanocomposites. This is especially true for the layered silicate clays, such as smectite clays, magnesium aluminum silicate, bentonite clays, montmorillonite clays, hectorite . clays, As discussed above, such clays can be natural or synthetic, treated or not.
  • the particle size of the filler can be within a wide range. As one skilled within the art will appreciate, the filler particle size can be tailored to the desired use of the filled copolyester composition. It is generally preferred that the average diameter of the filler be less than about 40 microns, more preferably less than about 20 microns. However, other filler particle sizes can be used.
  • the filler can include particle sizes ranging up to 40 mesh (US Standard) or larger.
  • filler particle sizes can also be advantageously used.
  • mixtures of calcium carbonate fillers having average particle sizes of about 5 microns and of about 0.7 microns may provide better space filling of the filler within the copolyester matrix.
  • the use of two or more filler particle sizes can allow improved particle packing. Two or more ranges of filler particle sizes can be selected such that the space between a group of large particles is substantially occupied by a selected group of smaller filler particles.
  • the particle packing will be increased whenever any given set of particles is mixed with another set of particles having a particle size that is at least about 2 times larger or smaller than the first group of particles.
  • the particle packing density for a two-particle system will be maximized whenever the size of a given set of particles is from about 3 to about 10 times the size of another set of particles.
  • three or more different sets of particles can be used to further increase the particle packing density.
  • the optimal degree of packing density depends on a number of factors such as, for example, the types and concentrations of the various components within both the thermoplastic phase and the solid filler phase; the film-forming, coating or lamination process used; and the desired mechanical, thermal and other performance properties of the final products to be manufactured. Andersen, et. al., in U.S. Pat. No. 5,527,387, discloses particle packing techniques, and is incorporated by reference herein in its entirety. Filler concentrates which incorporate a mixture of filler particle sizes are commercially available by the Shulman
  • The-filler can be added to the copolyester at any stage during the polymerization or after the polymerization is completed.
  • the fillers can be added with the copolyester monomers at the start of the polymerization process. This is preferable for, for example, the silica and titanium dioxide fillers, to provide adequate dispersion of the fillers within the polyester matrix.
  • the filler can be added at an intermediate stage of the
  • the filler can be added after the copolyester exits the polymerizer.
  • the copolyester can be melt fed to any intensive mixing operation, such as a static mixer or a single- or twin-screw extruder and compounded with the filler.
  • Blends of the present invention may further include various non-polymeric components including among others nucleating agents, anti-block agents, antistatic agents, slip agents, antioxidants, pigments or other inert fillers and the like. These additions may be employed in conventional amounts, although typically such additives are not required in the composition in order to obtain the toughness, ductility and other attributes of these materials. One or more of these non-polymeric components may be employed in the compositions in conventional amounts known to one skilled in the art.
  • Coupling, compatibilizing or mixing agents may be added to the reactive extrusion process in order to promote the interfacial adhesion thereof between the polymers and/or with optional fillers.
  • the copolyesters are modified by free radical grafting of unsaturated compounds including polar monomers such as maleic anhydride or esters, acrylic or methacrylic acid or esters, vinylacetate, acrylonitrile, and styrene.
  • polar monomers such as maleic anhydride or esters, acrylic or methacrylic acid or esters, vinylacetate, acrylonitrile, and styrene.
  • Virtually any olefinically reactive residue that can provide a reactive functional group on modified biodegradable thermoplastic polyesters can be useful in the invention.
  • copolyesters of the present invention or blends comprising copolyesters of the present invention may be used with, or contain, one or more additives. It is preferred that the additives are nontoxic, biodegradable and bio-benign.
  • additives include thermal stabilizers such as, for example, phenolic antioxidants; secondary thermal stabilizers such as, for example, thioethers and phosphates; UV absorbers such as, for example, benzophenone- and
  • UV stabilizers such as, for example, hindered amine light stabilizers (HALS).
  • HALS hindered amine light stabilizers
  • Other additives include plasticizers, processing aids, flow enhancing additives, lubricants, pigments, flame retardants, impact modifiers, nucleating agents to increase crystallinity, antiblocking agents such as silica, and base buffers such as sodium acetate, potassium acetate, and tetramethyl ammonium hydroxide, (for example, as disclosed in U.S. Pat. Nos. 3,779,993, 4,340,519, 5,171,308, 5,171 ,309, and 5,219,646 and references cited therein, which are incorporated by reference herein in their entireties).
  • copolyesters and copolyester blends of the present invention can be converted to dimensionally stable objects selected from the group consisting of films, fibers, foamed objects and molded objects. Furthermore, they can be converted to thin films by a number of methods known to those skilled in the art. For example, thin films can be formed by dipcoating as described in U.S. Pat. Nos. 4,372,311 , by compression molding as described in 4,427,614, by melt extrusion as described in 4,880,592, and by melt blowing (extrusion through a circular die). All three patents are incorporated by reference herein in their entireties. Films can be also prepared by solvent casting.
  • Solvents that may dissolve these copolyesters and, if so, would be suitable for casting include methylene chloride, chloroform, other chlorocarbons, and tetrahydrofuran.
  • Copolyesters of this invention are preferably processed in a temperature range of 10°C to 30 °c above their melting temperatures. Orientation of films is best conducted in the range of -10°C below to 100°C above the copolyester melting temperature.
  • Films prepared from the copolyesters of the present invention will have relatively low water vapor transmission rates (WVTR), are ductile (flexible), have good elongations (will stretch before breaking) and good tear strengths relative to other biodegradable films.
  • WVTR water vapor transmission rates
  • the copolyester component of the films of the present invention have a weight average molecular weight and a number average molecular weight such that the copolyester has a suitable tensile strength. If the molecular weight numbers are too small, the copolyester will be too tacky and have too low tensile strength and elongation at break values. If the molecular weight numbers are too high, various processing issues, such as a need for increased temperature to deal with increased viscosity, are encountered. Suitable weight average molecular weights for the copolyesters are from about 90,000 to about 160,000 Daltons, preferably from about 100,000 to about 130,000 Daltons, and more preferably from about 105,000 to about 120,000 Daltons. Suitable number average molecular weights for the copolyesters are from about 35,000 to about 90,000 Daltons, preferably from about 40,000 to about 70,000 Daltons, and more preferably from about 45,000 to about 65,000 Daltons.
  • copolyesters described herein for use in the films of the present invention will generally have a glass transition temperature such that the copolyester has suitable flexibility characteristics for use in a film.
  • the copolyesters of the present invention will have a glass transition temperature of less than about 0 °C, and optionally less than about - 10°C.
  • the hydroxyfatty acid copolyesters can also be injection molded.
  • the copolyesters of the present invention can be molded into numerous types of flexible objects, such as bottles, pen barrels, toothbrush handles, cotton swab applicators and razor blade handles. They can also be used to prepare foamed food service items. Examples of such items include cups, plates, and food trays.
  • biodegradable or “biodegradable polymer” generally refers to a polymer that can be readily decomposed by biological means, such as a microbial action, environmental exposure, heat and/or moisture.
  • a biodegradable polymer When tested according to ASTM D6340-98, a biodegradable polymer is one that is at least about 80% dissolved and/or decomposed after 180 days in a controlled compost environment as set forth in the procedure.
  • Copolyesters with greater than 50 wt% co-hydroxyfatty acid content are expected to be biodegradable, but the actual rate and extent of biodegradation will vary with copolymer composition. In general, copolyesters with monomers whose homopolymers degrade rapidly are expected to provide copolyesters with increased degradation rates, and copolyesters with monomers whose homo- or copolyesters are non-degradable, or slowly biodegrade, are expected to provide copolyesters with decreased degradation rates.
  • Biodegradable materials such as many of the copolyester compositions of the present invention, are initially reduced in molecular weight in the environment by the action of heat, water, air, microbes and other factors. This reduction in molecular weight results in a loss of physical properties (film strength) and often in film breakage.
  • the monomers and oligomers are then assimilated by the microbes. In an aerobic environment, these monomers or oligomers are ultimately oxidized to C02, H20, and new cell biomass. In an anaerobic environment the monomers or oligomers are ultimately oxidized to C02, H2, acetate, methane, and cell biomass.
  • Successful biodegradation requires that direct physical contact must be established between the biodegradable material and the active microbial population or the enzymes produced by the active microbial population.
  • An active microbial population useful for degrading the films and blends of the invention can generally be obtained from any municipal or industrial wastewater treatment facility or compo sting facility.
  • successful biodegradation requires that certain minimal physical and chemical requirements be met such as suitable pH, temperature, oxygen concentration, proper nutrients, and moisture level.
  • the poly(hydroxyfatty acid-co-diacid/diol) copolyesters of the present invention are expected to be biodegradable in compo sting environments and, hence, would be particularly useful in the preparation of barrier films in disposable articles.
  • Composting can be defined as the microbial degradation and conversion of solid organic waste into soil.
  • One of the key characteristics of compost piles is that they are self-heating; heat is a natural by-product of the metabolic break down of organic matter. Depending upon the size of the pile, or its ability to insulate, the heat can be trapped and cause the internal temperature to rise. Efficient degradation within compost piles relies upon a natural progression or succession of microbial populations to occur. Initially, the microbial population of the compost is dominated by mesophilic species (optimal growth temperatures between 20-45 °C).
  • the process begins with the proliferation of the indigenous mesophilic microflora and metabolism of the organic matter. This results in the production of large amounts of metabolic heat which raise the internal pile temperatures to approximately 55-65°C.
  • the higher temperature acts as a selective pressure which favors growth of thermophilic species on one hand (optimal growth range between 45-60 °C), while inhibiting the mesophiles on the other.
  • Municipal compost units are also typically aerobic processes, which supply sufficient oxygen for the metabolic needs of the microorganisms permitting accelerated biodegradation rates.
  • Tensile strength, elongation at break, and tangent modulus of the films can be measured by ASTM method D882; the tear force is measured by ASTM method D1938; the oxygen and water vapor transmission rates are measured by ASTM methods D3985 and F372, respectively.
  • Inherent viscosities can be measured at a temperature of 25°C for a 0.500 gram sample in 100 mL of a 60/40 by weight solution of phenol tetrachloroethane. DSC measurements are usually made at a scan rate of 20°C/min.
  • Molecular weights can be measured by gel permeation chromatography and are most commonly based on polystyrene equivalent molecular weights.
  • copolyesters The composition of the copolyesters is given in brackets following the name.
  • poly(co-hydroxyfatty acid-a>-diacidldiol) [83/12/5] refers to a copolyester which was prepared from 83% ⁇ -hydroxyfatty acid, 12% diacid and 5% diol.
  • the percent composition refers to percent by weight.
  • the mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 1.0 hour, at 210° C for 1.0 hour, and at 220° C for 1.0 hour.
  • the reaction temperature is then increased to 250° C.
  • the internal pressure is reduced to 0.3 mm Hg, and the reaction is allowed to progress for 2.0 hrs.
  • the resulting copolyester may be semicrystalline and can be isolated using standard techniques.
  • the copolyester may be analyzed using standard methods well known to those of ordinary skill in the art. For example, IV (dL/g), T g (° C) and T m
  • a 500 mL single-neck round bottom flask is charged with 14-hydroxytetradecanoic acid methyl ester (129 g, 0.5 mole), trimethylol propane (0.27 g, 0.002 mole), tetradecanedioic acid (0.8 g, 0.003 mole) and 1.5 ml of a solution containing titanium isopropoxide (1.25 wt/vol% Ti).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and is then immersed in a Belmont metal bath.
  • the mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 1.0 hour, at 210° C for 1.0 hour, and at 220° C for 1.0 hour.
  • the reaction temperature is then increased to 250° C. After stabilizing at 250° C, the internal pressure is reduced to 0.3 mm Hg, and the reaction is allowed to progress for 2.0 hrs.
  • the resulting copolyester may be
  • copolyester may be analyzed using standard methods well known to those of ordinary skill in the art. For example, IV (dL/g), T g (° C) and T m (° C) analysis can be performed using DSC, mole % DEG can be determined by NMR, and M n and M w values may be obtained using GPC.
  • a 500 mL single-neck round bottom flask is charged with a mixture of ⁇ -hydroxyfatty acids produced by fermenting palm oil with an engineered yeast strain (125 g), butane diol (43 g, 0.48 mole), terephthalic acid (80 g, 0.48 mole) and 1.4 ml of a chloroform solution containing titanium isopropoxide (1.25 wt vol% Ti).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200 0 C for 1.0 hour, at 210 0 C for 1.0 hour, and at 220 ° C for 1.0 hour.
  • the reaction temperature is then increased to 250° C.
  • the internal pressure is reduced to 0.3 mm Hg, and the reaction is allowed to progress for 2.0 hrs.
  • the resulting copolyester may be semicrystalline and can be isolated using standard techniques.
  • the copolyester may be analyzed using standard methods well known to those of ordinary skill in the art. For example, IV (dL/g), T g (° C) and T m (° C) analysis can be performed using DSC, mole % DEG can be determined by NMR, and M n and M w values may be obtained using GPC.
  • a 500 mL single-neck round bottom flask is charged with 14-hydroxytetradecanoic acid (48.8 g, 0.2 mole), and 2.27 mL of a 1-butanol solution containing titanium isopropoxide (lOmg/mL).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the reaction mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the internal pressure is reduced to 0.1 mm Hg, and the reaction is allowed to continue for 4.0 hours.
  • the isolated product provides a T g of -31°C (by DMT A), a T m of 91°C (by DSC), and a M w of 170,000 (by GPC).
  • results from tensile testing of compression molded bars provide a Young's Modulus of 426 ⁇ 46MPa, an elongation at break of 728 ⁇ 80%, and a stress at break value of 15. l ⁇ 28MPa.
  • a 500 mL single-neck round bottom flask is charged with 16-hydroxyhexadecanoic acid (54.4 g, 0.2 mole) and 2.27 mL 1-butanol solution containing titanium isopropoxide (10 mg/mL).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the reaction mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the internal pressure is reduced to 0.1 mm Hg, and the reaction is continued for 4.0 hours.
  • the isolated product has a T m value of 98° C (by DSC) and a M w of 180,000 (by GPC).
  • results from tensile testing of compression molded bars provide a Young's Modulus of 377120 MPa, an elongation at break value of 370+130%, and a stress at break value of 15.8 ⁇ 1.0 MPa.
  • a 500 mL single-neck round bottom flask is charged with 18-hydroxyoctadecanoic acid (60 g, 0.2 mole), and 2.27 mL of a 1-butanol solution containing titanium isopropoxide (10 mg/mL).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the reaction mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the internal pressure is reduced to 0.1 mm Hg, and the reaction is allowed to progress for 4.0 hours.
  • the isolated product has a T m of 102°C (by DSC) and a M w of 230,000 (by GPC).
  • tensile testing of compression molded bars provide a Young's Modulus of 447140 MPa, an elongation at break of 522180%, and a stress at break of 17.913.9 MPa by tensile test.
  • a 500 mL single-neck round bottom flask is charged with 16-hydroxyoctadecanoic acid (27.2 g, 0.1 mole), 18-hydroxyoctadecanoic acid (30.0 g, 0.1 mole) and 2.27 mL of a 1-butanol solution containing titanium isopropoxide (lOmg/mL).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the internal pressure is reduced to 0.1 mm Hg, and the reaction is allowed to progress for 4.0 hours.
  • Analysis of the isolated product provides a T m of 99.3° C using DSC.
  • a 500 mL single-neck round bottom flask is charged with 14-hydroxytetradecanoic acid (48.8 g, 0.2 mole), and 2.27 mL of a 1-butanol solution containing titanium isopropoxide (10 mg/mL).
  • the flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the reaction mixture is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the internal pressure is reduced to 0.1 mm Hg, and the reaction is allowed to progress for 2.0 hours.
  • lactide 48.8 g, 0.34 mole
  • stannous octoate 0.244 g, 0.6 mmole
  • the reaction flask is then immersed in a silicone oil bath at 140° C, an inert atmosphere is maintained, such as nitrogen, and the reaction is continued for 6.0 hours.
  • the isolated product has a T g . of 54.7° C, a T m of 140.7° C (by DSC) and a M w of 53,000 using GPC.
  • a 500 mL single-neck round bottom flask is charged with 14-hydroxytetradecanoic acid (48.8 g, 0.2 mole), 1,4-butanediol (61.0 g 0.67 mole), dimethyl cyclohexanedicarboxylate (134.2 g, 0:67 mole) and titanium butoxide (0.0427 g 0.05 mmole).
  • the reaction flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the flask is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • the isolated product has a T g of -27° C, a T m of 131-138° C (by DSC) and a M w of 121,000 using GPC.
  • a 500 mL single-neck round bottom flask is charged with 14-hydroxytetradecanoic acid (48.8 g, 0.2 mole), 1,4-butanediol (62.0 g 0.69 mole), dimethyl cyclohexanedicarboxylate (133.2 g, 0.69 mole) and titanium butoxide (0.0427 g 0.05 mmole).
  • the reaction flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the reaction is heated with stirring under an inert atmosphere, such as nitrogen, at 200° C for 2.0 hours.
  • the reaction temperature is then increased to 220° C.
  • a 500 mL three-neck round bottom flask is charged with poly(a>-hydroxytetradecanoic acid) (100 g, 0.132 mol monomer unit) and an 4.0 mL aliquot from a titanium n-butoxide (20 mg/mL) solution.
  • the reaction flask is fitted with a metal stirrer and a nitrogen inlet and then immersed in a Belmont metal bath.
  • the flask is heated with stirring under an inert atmosphere, such as nitrogen, at 220° C for 5 min in order to uniformly disperse the titanium n-butoxide throughout the poly(co-hydroxytetradecanoic acid) matrix.
  • the procedure provides poly(co-hydroxytetradecanoic acid) with 600 ppm titanium n-butoxide dispersed within the matrix.
  • Poly(co-hydroxytetradecanoic acid) (5 g) and poly(lactic acid) (5 g) containing titanium n-butoxide are transferred to a 100 mL reactor flask fitted with an overhead metal stirrer and an inlet tube for inert gas. Under inert atmosphere with overhead stirring, the reaction is heated at 220°C and continued for 2.0 hrs.
  • the resulting reactive blending product has a T g of 64.0° C (by DMTA) and a T m of 152.2° C using DSC.
  • tensile testing of compression molded bars provides a Young's modulus of 598 ⁇ 20 MPa, elongation at break of 120 ⁇ 30 % and tensile strength of 17.7 ⁇ 0.7MPa.
  • Blown film from a copolyester of the present invention is produced using a laboratory scale blown film line which consists of a Killion 1.25 inch extruder with a 15 : 1 gear reducer.
  • the copolyester is dried overnight between 50 and 60° C in dehumidified air dryers prior to processing.
  • the screw is a Maddock mixing type with an L/D of 24 to 1 , although a general purpose screw can also be used. Compression ratio for the mixing screw is 3.5: 1 and a 1.21 inch diameter die with a 5 mil die gap is used.
  • the air ring is a Killion single-lip, No.2 type.
  • Temperature set points for the extruders can vary depending on the level of inert additives, if any, but are generally in the range of 10°-30° C above the melting point of the copolyester.
  • blow up ratio BUR
  • DDR draw-down ratio
  • Films can also be solvent cast from the copolyesters of the present invention.
  • the copolyesters are dried either under vacuum or by desiccant drying and dissolved in either chloroform or methylene chloride at a concentration of 10-20 wt %.
  • the films are cast on stainless steel plates and are drawn down to approximately 15 mil with a "doctor" blade. The solvent is evaporated slowly to leave films of approximately 1.5 mil in thickness.
  • Physical properties of the solvent cast films including IV (dL/g), elongation at break (%), tangent modulus (psi) and tensile strength (psi) can be measured.
  • small-scale compost units are employed to simulate the active treatment processes found in a municipal solid waste composter. These bench-scale units display the same key features that distinguish the large-scale municipal compost plants.
  • the starting organic waste is formulated to be representative of that found in municipal solid waste streams: a carbon to nitrogen of 25: 1 ratio, a 55% moisture content, a neutral H, a source of readily degradable organic carbon (e.g. cellulose, protein, simple carbohydrates, and lipids), and a particle size to allow air flow through the mass.
  • a carbon to nitrogen of 25: 1 ratio a carbon to nitrogen of 25: 1 ratio
  • a 55% moisture content e.g. cellulose, protein, simple carbohydrates, and lipids
  • a source of readily degradable organic carbon e.g. cellulose, protein, simple carbohydrates, and lipids
  • a particle size e.g. cellulose, protein, simple carbohydrates, and lipids
  • the efficiency of the bench scale compost units are determined by monitoring the temperature profiles and dry weight disappearance of the compost. Films are harvested after 15 days of incubation and washed, dried, and weighed to determine weight loss. Biodegradation can be measured by film weight loss, and or loss of molecular weight, after composting.
  • the ⁇ -hydroxyfatty acid copolyesters of the present invention can also be injection molded, for example, on a Toyo 90-1.
  • the copolyester is dried in a desiccant dryer at about 60° C for approximately 16 hours prior to injection molding.
  • Exemplary molding conditions are Open Cycle Time (4 sec), Inject + Hold Time (20 sec), Cooling Time (50 sec), Inject Time (4 sec), Total Cycle Time (78 sec), Nozzle Temp. (120° C), Zone 1 Temp. (120° C), Zone 2 Temp. (120° C), Zone 3 Temp. (120° C), Zone 4 Temp. (110° C), Injection Pressure (600 psi), Hold Pressure (600 psi), Mold Temp.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention porte sur des polyesters et copolyesters aliphatiques ou aliphatiques-aromatiques constitués de ω-hydroxy(acides gras) d'origine biologique ou de dérivés de ceux-ci, sur des procédés pour leur préparation et sur des compositions de ceux-ci présentant des propriétés améliorées. Les copolyesters de la présente invention peuvent également contenir des composants supplémentaires qui peuvent être choisis parmi des diacides, diols et hydroxyacides aliphatiques ou aromatiques obtenus à partir de sources synthétiques et naturelles. Les ω-hydroxy(acides gras) d'origine biologique qui constituent les polyesters et copolyesters de la présente invention sont fabriqués à l'aide d'un procédé de fermentation à partir d'acide gras purs, de mélanges d'acides gras, d'un ester d'acide gras pur, de mélanges d'esters d'acides gras et de triglycérides provenant de diverses sources. Les polyesters de la présente invention peuvent contenir diverses quantités et divers types de ω-hydroxy(acides gras) selon la souche de levure manipulée utilisée pour la bioconversion ainsi que la ou les charges d'alimentation utilisées.
PCT/US2011/025086 2010-02-16 2011-02-16 Copolyesters comprenant des motifs répétés issus de ω-hydroxy(acides gras) Ceased WO2011103193A2 (fr)

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CA2790192A CA2790192A1 (fr) 2010-02-16 2011-02-16 Copolyesters comprenant des motifs repetes issus de .omega.-hydroxy(acides gras)

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CN104231234A (zh) * 2014-09-26 2014-12-24 山西大学 氨基吡咯锌锂双金属催化剂及其制备方法和应用
JP2016515150A (ja) * 2013-03-06 2016-05-26 ディーエスエム アイピー アセッツ ビー．ブイ． 熱可塑性コポリエーテルエステルエラストマーを含む難燃性組成物
EP3039051A4 (fr) * 2013-08-30 2017-05-17 Trent University Polyesters et copolyesters aliphatiques issus d'huiles naturelles et leurs propriétés physiques correspondantes
CN107815473A (zh) * 2017-11-03 2018-03-20 云南民族大学 一种二苯醚类化合物及其制备方法和应用
CN111995846A (zh) * 2020-09-16 2020-11-27 贺州学院 一种ptt/人造岗石废渣复合材料及其制备方法
CN113502042A (zh) * 2021-09-10 2021-10-15 苏州瀚海新材料有限公司 一种纳米增强改性聚酯及其制备方法
CN114316543A (zh) * 2021-12-31 2022-04-12 珠海麦得发生物科技股份有限公司 一种聚羟基脂肪酸酯颗粒及其制备方法
WO2022125916A1 (fr) * 2020-12-11 2022-06-16 Celanese International Corporation Mousse formée à partir d'une composition d'ester de cellulose
CN118580477A (zh) * 2024-06-21 2024-09-03 浙江康隆达特种防护科技股份有限公司 一种生物基聚合物、生物基组合物及其制备方法和应用
CN119684577A (zh) * 2024-12-10 2025-03-25 青岛科技大学 一种新型生物基可闭环回收热塑性弹性体及其制备方法

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JP2016515150A (ja) * 2013-03-06 2016-05-26 ディーエスエム アイピー アセッツ ビー．ブイ． 熱可塑性コポリエーテルエステルエラストマーを含む難燃性組成物
EP3039051A4 (fr) * 2013-08-30 2017-05-17 Trent University Polyesters et copolyesters aliphatiques issus d'huiles naturelles et leurs propriétés physiques correspondantes
CN104231234A (zh) * 2014-09-26 2014-12-24 山西大学 氨基吡咯锌锂双金属催化剂及其制备方法和应用
CN107815473A (zh) * 2017-11-03 2018-03-20 云南民族大学 一种二苯醚类化合物及其制备方法和应用
CN107815473B (zh) * 2017-11-03 2021-05-18 云南民族大学 一种二苯醚类化合物及其制备方法和应用
CN111995846A (zh) * 2020-09-16 2020-11-27 贺州学院 一种ptt/人造岗石废渣复合材料及其制备方法
WO2022125916A1 (fr) * 2020-12-11 2022-06-16 Celanese International Corporation Mousse formée à partir d'une composition d'ester de cellulose
CN113502042A (zh) * 2021-09-10 2021-10-15 苏州瀚海新材料有限公司 一种纳米增强改性聚酯及其制备方法
CN114316543A (zh) * 2021-12-31 2022-04-12 珠海麦得发生物科技股份有限公司 一种聚羟基脂肪酸酯颗粒及其制备方法
CN118580477A (zh) * 2024-06-21 2024-09-03 浙江康隆达特种防护科技股份有限公司 一种生物基聚合物、生物基组合物及其制备方法和应用
CN119684577A (zh) * 2024-12-10 2025-03-25 青岛科技大学 一种新型生物基可闭环回收热塑性弹性体及其制备方法

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