 HARDENED POLYDROXIALCANOATE COMPOSITIONS
专利摘要:
hardened polyhydroxyalkanoate compositions the hardened polyhydroxyalkanoate resin compositions are presented, which comprise thermoplastic polyhydroxyalkanoate compositions and a hardener comprising a vinyl acetate copolymer or homopolymer and, optionally, polyvinyl alcohol. 公开号:BR112012004108B1 申请号:R112012004108-8 申请日:2010-08-27 公开日:2020-02-18 发明作者:Robert S. Whitehouse 申请人:Cj Cheiljedang Corporation； IPC主号:
专利说明:
HARDENED POLYDROXIALCANOATE COMPOSITIONS RELATED APPLICATION This application claims the benefit of Provisional Application No. 61 / 237,368, filed on August 27, 2009. The entirety of the teachings in the above application is hereby incorporated by reference. CONTEXT OF THE INVENTION Biodegradable plastics are of increasing industrial interest as replacements or supplements for non-biodegradable plastics in a wide variety of applications and in particular for packaging applications. A class of biodegradable polymers is that of polyhydroxyalkanoates (PHAs). These polymers are synthesized by soil microbes for use as intracellular storage material. Articles made from polymers are generally recognized by soil microbes as a food source. Thus, there has been a great interest in the commercial development of these polymers, particularly for disposable consumer items. To date, however, PHAs have had limited commercial availability, with only the poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer (PHBV) being available in remarkable quantities. Although several PHAs are capable of being processed on conventional processing equipment, many problems have been encountered with polymers. These include the lack of processability in some situations, which can limit the commercial applications available for use of the polymer; the molecular weight can be difficult to 2/78 keep. Furthermore, the crystallization kinetics of the polymer is poorly understood, and longer cycle times are often necessary during the processing of these polymers, which further limits their commercial acceptance. PHA compositions that contain high levels of 3-hydroxybutyrate monomer may have physical limitations, such as problems of fragility and thermal stability at melt processing temperatures (for example, those temperatures used in injection molding, sheet extrusion and conversion of blown film), and the resulting products may not have an acceptable degree of hardness for many applications. Therefore, there is a need for hardened PHA compositions. SUMMARY OF THE INVENTION Presented in this document are hardened polyhydroxyalkanoate resin compositions comprising (A) copolymers, polyhydroxyalkanoate homopolymers and mixtures thereof, and (B) a hardener comprising a vinyl acetate copolymer or homopolymer and a monomer, as presented herein document, and optionally polyvinyl alcohol. Specifically, the hardener comprises a vinyl acetate homopolymer or vinyl acetate copolymer produced from vinyl acetate and at least one monomer selected from: (a) ethylene; (b) (meth) acrylic esters (for example, one or more esters of branched or unbranched alcohols that 3/78 have 1 to 15 carbon atoms, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate , 2-ethylhexyl acrylate, norbornyl acrylate); (c) vinyl esters having 1 to 12 carbon atoms in the carboxylic acid radical (for example, vinyl propionate, vinyl laurate, alpha branched carboxylic acid vinyl esters having 9 to 13 carbon atoms); (d) monomer containing carboxyl group selected from the group of acrylic acid, methacrylic acid, crontonic acid, itaconic acid, fumaric acid, maleic acid and salts thereof; (e) glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide and vinyl pyrrolidone; and (f) vinyl alcohol. The hardener can optionally comprise polyvinyl alcohol which has about 60% to about 99.8% hydrolysis degree. A composition is provided that includes: (a) 50 weight percent to 99.8 weight percent biologically produced polyhydroxyalkanoate polymer, and (b) 0.2 weight percent to 50 weight percent of a hardening component (a hardener). The hardening component includes a vinyl acetate polymer comprising 60 to 100 weight percent vinyl acetate monomer, with the remainder being composed of at least one of the following: (i) up to about 4/78 weight percent ethylene; (ii) (meth) acrylic esters; (iii) vinyl esters that have 1 to 12 carbon atoms in the carboxylic acid radical; (iv) a monomer containing a carboxyl group selected from the group consisting of acrylic acid, methacrylic acid, crontonic acid, itaconic acid, fumaric acid, maleic acid and salts thereof; and (v) glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide or vinyl pyrrolidone; and (vi) vinyl alcohol. Also provided in this document is a method of forming a biodegradable polymeric composition. The method includes the combination of: a biologically produced polyhydroxyalkanoate polymer, a hardening component, and a nucleating agent, under conditions sufficient to form a largely homogeneous composition; thereby forming a biodegradable polymeric composition. The hardening component includes a vinyl acetate polymer comprising 60 to 100 weight percent vinyl acetate monomer, with the remainder being composed of at least one of the following: (i) up to about 14 percent weight percent ethylene; (ii) (meth) acrylic esters; (iii) vinyl esters that have 1 to 12 carbon atoms in the carboxylic acid radical; (iv) a monomer containing a carboxyl group selected from the group consisting of acrylic acid, methacrylic acid, crontonic acid, itaconic acid, fumaric acid, maleic acid and salts thereof; and (v) glycidyl methacrylate, methacrylate of 5/78 hydroxyethyl, acrylamide or vinyl pyrrolidone; and (vi) vinyl alcohol. In certain embodiments, the polyhydroxyalkanoate polymer component is in the form of a fine particle size powder and the vinyl polyacetate component is in the form of an emulsion, the components are combined in an aqueous process before the water is thermally removed. In addition, a method for forming a polymer resin pellet is provided herein, wherein the method includes combining: a biologically produced polyhydroxyalkanoate polymer, a curing component, a branching agent and a nucleating agent, wherein the composition it is melted and formed under suitable conditions to form a polymer resin pellet. The hardening component includes a vinyl acetate polymer comprising 60 to 100 weight percent vinyl acetate monomer, with the remainder being composed of at least one of the following: (i) up to about 14 percent weight percent ethylene; (ii) (meth) acrylic esters; (iii) vinyl esters that have 1 to 12 carbon atoms in the carboxylic acid radical; (iv) a monomer containing a carboxyl group selected from the group consisting of acrylic acid, methacrylic acid, crontonic acid, itaconic acid, fumaric acid, maleic acid and salts thereof; and (v) glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide or vinyl pyrrolidone; and (vi) vinyl alcohol. Also produced in this document are articles produced from any of the compositions 6/78 of the invention. The article is a film, sheet (including multilayer sheets), molding, fiber, filament, rod, tube, bottle or foam. The article is formed by molding, extruding or blowing the composition. In addition, a process for forming an article from the compositions is provided, as described in this document, and articles produced from the process. In any of the compositions, methods, processes or articles described in this document, (meth) acrylic esters are esters of branched or unbranched alcohols that have 1 to 15 carbon atoms, for example, methyl acrylate, methyl methacrylate , ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate. Vinyl esters are those that have 1 to 12 carbon atoms in the carboxylic acid radical (for example, vinyl propionate, vinyl laurate, alpha-branched carboxylic acid vinyl esters that have 9 to 13 carbon atoms); In certain embodiments, the vinyl acetate polymer is a vinyl acetate homopolymer. The vinyl acetate copolymer can include a vinyl polyacetate copolymer that has about 99 to 84 weight percent vinyl acetate and about 1 to 16 weight percent ethylene and acrylate comonomers. In other embodiments, the vinyl polyacetate polymer is produced by emulsion polymerization. 7/78 The hardener can further include up to about weight percent of a polyvinyl alcohol which is about 60 to 99.8 weight percent hydrolysis. The polyvinyl alcohol can include from 1 to 99 weight percent of a vinyl polyacetate homopolymer and from 99 to 1 weight percent of a vinyl acetate copolymer or copolymer mixture. Polyvinyl alcohol can have a molecular weight of about 10,000 Daltons up to about 1,000,000 Daltons. The polyvinyl alcohol component can be soluble in ice water or soluble in hot water. In any of the compositions, methods, processes or articles described herein, the polyhydroxyalkanoate polymer component can be in the form of a fine particle size powder and the vinyl polyacetate component can be in the form of an emulsion, being that the components are combined in an aqueous process before the water is thermally removed. In any of the compositions, methods, processes or articles described herein, from about 5 to about 95 weight percent of the composition is a biologically produced polyhydroxyalkanoate polymer. In certain embodiments, the biologically produced polyhydroxyalkanoate polymer is branched. In certain embodiments, the biologically produced polyhydroxyalkanoate polymer is a homopolymer of poly (3-hydroxybutyrate), a poly (3-hydroxybutyrate-co-4-hydroxybutyrate), a poly (3-hydroxybutyrate-co-3-hydroxyvalerate), a poly (38 / 78 hydroxybutyrate-co-5-hydroxyvalerate), or a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate). The biologically produced polyhydroxyalkanoate polymer can be a homopolymer of poly (3-hydroxybutyrate), a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate, a poly (3-hydroxybutyrate- co-3hydroxyvalerate) with a content of 5% to 22% of 3hydroxyvalerate, a poly (3-hydroxybutyrate-co-5hydroxyvalerate) with a content of 5% to 15% of 5hydroxyvalerate, or a poly (3-hydroxybutyrate-co-3hydroxyhexanoate ) with a content of 3% to 15% of 3 hydroxyhexanoate. The biologically produced polyhydroxyalkanoate can be a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate); a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate); a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate). The biologically produced polyhydroxyalkanoate can be a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate; a) a homopolymer of 9/78 poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with a content of 5% to 22% of 3-hydroxyvalerate; a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate; a) a poly (3-hydroxybutyrate-co4-hydroxybutyrate) with a content of 5% to 15% of 4hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-3-hydroxyvalerate) with a content of 5% to 22% of 3hydroxyvalerate ; a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with a content of 5% to 22% of 3-hydroxyvalerate mixed with b) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) with a content of 3% to 15% 3 hydroxyhexanoate. In other embodiments, the biologically produced polyhydroxyalkanoate is a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) and the weight of the polymer from a) is 5% to 95% of the combined weight polymer a) and polymer b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of the polymer of a) can be from 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3 10/78 hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a ) and polymer of b); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a ) and polymer of b); or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b). In still other embodiments, the weight of the polymer of a) is 20% to 60% of the combined weight of the polymer of a) and polymer of b) and the weight of the polymer of b) is 40% to 80% of the combined weight of the polymer of a) and polymer of b). For example, the weight of the polymer of a) is 25% to 55%, 30 to 60%, 35 to 55% or 40 to 55% of the combined weight of the polymer of a) or 21%, 22%, 23%, 24 %, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57% , 58%, 59%, or 60% of the combined weight of the polymer of a). The biologically produced polyhydroxyalkanoate can be a) homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% of 4-hydroxybutyrate; a) a homopolymer of 11/78 poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with a content of 20% to 50% of 5-hydroxyvalerate; a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that has a content of 5% to 50% of 3-hydroxyhexanoate; a) poly (3-hydroxybutyrate-4-hydroxybutyrate) with a content of 5% to 15% of 4hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-4-hydroxybutyrate) with a content of 20 to 50% of 4hydroxybutyrate; a) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-5-hydroxyvalerate) with a content of 20% to 50% of 5hydroxyvalerate; a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) that has a content of 5% to 50% 3 hydroxyhexanoate; a) a poly (3-hydroxybutyrate-co-3hydroxyvalerate) with a content of 5% to 22% of 3hydroxyvalerate mixed with b) poly (3-hydroxybutyrate-co4-hydroxybutyrate) with a content of 20 to 50% of 4hydroxybutyrate; a) a poly (3-hydroxybutyrate-co-3hydroxyvalerate) with a content of 5% to 22% of 3hydroxyvalerate mixed with b) a poly (3-hydroxybutyrate-5-hydroxyvalerate) with a content of 20% to 50% of 5hydroxyvalerate ; a) a poly (3-hydroxybutyrate-co-3hydroxyvalerate) with a content of 5% to 22% of 3hydroxyvalerate mixed with b) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) that has a content of 5% to 50% 3 12/78 hydroxyhexanoate; a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% of 4- hydroxybutyrate; a) a poly (3-hydroxybutyrate-co3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with a content of 20% to 50% of 5 -hydroxyvalerate; or a) a poly (3-hydroxybutyratoco-3-hydroxyhexanoate) with a content of 3% to 15% of 3hydroxyhexanoate mixed with b) a poly (3hydroxybutyrate-co-3-hydroxyhexanoate) having a content of 5% to 50% of 3-hydroxyhexanoate. In another embodiment, the biologically produced polyhydroxyalkanoate is a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% of 4-hydroxybutyrate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3hydroxyvalerate) with a content of 20% to 50% of 5hydroxyvalerate and the weight of the polymer of a) can be 5% to 95% of the combined weight of polymer a) and polymer b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) which has a content of 5% to 50% of 3-hydroxyhexanoate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3- 13/78 hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% of 4-hydroxybutyrate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% of 5-hydroxyvalerate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of B) ; a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 5% to 15% of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) having a content of 5% to 50% of 3-hydroxyhexanoate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and the polymer of b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with a content of 5% to 22% of 3-hydroxyvalerate mixed with b) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% of 4-hydroxybutyrate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with a content of 5% to 22% of 3-hydroxyvalerate mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% % of 5-hydroxyvalerate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with a content of 5% to 22% of 3-hydroxyvalerate mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that has 14/78 a content of 5% to 50% of 3-hydroxyhexanoate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and the polymer of b); a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20 to 50% 4-hydroxybutyrate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% of 5-hydroxyvalerate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b); or a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 3% to 15% of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) which has a content of 5% to 50% of 3-hydroxyhexanoate and the weight of the polymer of a) can be 5% to 95% of the combined weight of the polymer of a) and polymer of b). In still other embodiments, the weight of the polymer of a) is 20% to 60% of the combined weight of the polymer of a) and polymer of b) and the weight of the polymer of b) is 40% to 80% of the combined weight of the polymer of a) and polymer of b). In another modality, the biologically produced polyhydroxyalkanoate is further mixed with polymer c) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with a content of 20% to 50% of 4-hydroxybutyrate. The biologically produced polyhydroxyalkanoate can be 15/78 additionally mixed with c) a poly (3-hydroxybutyrate-5-hydroxyvalerate) with a content of 20% to 50% of 5 hydroxyvalerate. The biologically produced polyhydroxyalkanoate can be further mixed with c) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a content of 5% to 50% of 3-hydroxyhexanoate. In other embodiments, the weight of the polymer of c) is 5% to 95% of the combined polymer weight of a) polymer, b) polymer and ç). The weight of the c polymer is 5% to 40% of the combined polymer weight of a) polymer, b) polymer and c) polymer. In certain embodiments, a nucleating agent is included in the compositions, methods, processes or articles described in this document. The nucleating agent is selected from cyanuric acid, carbon black, mica, talc, silica, boron nitride, clay, calcium carbonate, synthesized silicic acid or a salt thereof, a metal salt of organophosphates. The nucleating agent may include aluminum hydroxidiphosphate or a compound comprising a heteroaromatic nucleus that contains nitrogen. The heteroaromatic nucleus containing nitrogen can be pyridine, pyrimidine, pyrazine, pyridazine, triazine, or imidazole. The nucleating agent may have a chemical formula selected from the group consisting of: 16/78 R R Formula 1 and Formulas Formula 3 Formula 4 Laugh Formula 5 their combinations in which each RI is independently H, NR 2 R 2 , OR 2 , SR 2 , SOR 2 , SO2R 2 , CN, COR 2 , CO2R 2 , CONR 2 R 2 , NO2, F, Cl, Br or I; and each R 2 is independently H or C 1 -C 6 alkyl. The nucleating agent is cyanuric acid. In any of the embodiments presented, the polymer is a polyhydroxyalkanoate. In particular embodiments, the polymer is a branched polyhydroxyalkanoate polymer. Other features and advantages of the invention will be clear from the following detailed description and from the claims. DETAILED DESCRIPTION OF THE INVENTION The present invention describes hardened thermoplastic compositions that comprise a polyhydroxyalkanoate component comprising one or more polyhydroxyalkanoate homopolymers, polyhydroxyalkanoate copolymers or mixtures thereof and a hardening component (for example, an impact hardener) that comprises an acetate homopolymer. vinyl one 17/78 vinyl acetate copolymer or mixtures thereof and, optionally, a polyvinyl alcohol component. For example, hardened polyhydroxyalkanoate resin compositions are presented herein that comprise (A) copolymers, polyhydroxyalkanoate homopolymers and mixtures thereof and (B) a hardening component (a hardener) comprising a vinyl acetate copolymer or homopolymer and at least one of the following monomers: ethylene, (meth) acrylic esters (branched or unbranched alcohol esters having 1 to 15 carbon atoms, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylate ethyl, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate), vinyl esters that have 1 to 12 carbon atoms in the carboxylic acid radical ( for example, vinyl propionate, vinyl laurate, alpha-branched carboxylic acid vinyl esters that have 9 to 13 carbon atoms), monomers that and contain carboxyl group (for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and salts thereof), glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide and vinyl pyrrolidone and (vi) alcohol vinyl. The hardener can optionally comprise polyvinyl alcohol which has about 60% to about 99.8% hydrolysis degree. 18/78 Methods for producing such compositions are also provided herein. For example, in certain embodiments, the hardened polyhydroxyalkanoate composition includes (i) about 50 to about 99.8 weight percent copolymer, polyhydroxyalkanoate homopolymer or mixtures thereof and (ii) about 0.2 to about from 50 percent by weight of an impact modifier comprising a vinyl acetate polymer comprising from about 60 percent by weight to about 100 percent by weight of vinyl acetate monomer and the remainder of acrylate, acids of vinyl methacrylate and vinyl esters that have from 2 to about 15 carbon atoms in the side chain. The hardened polyhydroxyalkanoate composition can further include about 0 to 15 weight percent polyvinyl alcohol which has about 60 weight percent to about 99.8% hydrolysis degree. In another aspect of the invention, the hardened polyhydroxyalkanoate composition includes about 55 to about 95 weight percent copolymer, polyhydroxyalkanoate homopolymer or mixtures thereof, about 60 to about 90 weight percent copolymer, homopolymer of polyhydroxyalkanoates or mixtures thereof, about 70 to about 99 weight percent copolymer, polyhydroxyalkanoate homopolymer or mixtures thereof, or about 75 to about 85 weight percent copolymer, polyhydroxyalkanoate homopolymer or mixtures thereof . 19/78 In certain embodiments, the composition is produced from the mixture by melting individual components to produce a homogeneous mixture. The mixture can then be used for conversion to parts manufactured through injection molding, sheet and profile extrusion, fiber extrusion, molded film extrusion, blown film extrusion, thermoforming, vacuum forming, blow molding, and rotational molding operations. For film applications, the composition of the invention can be the complete film or one or more layers in a multi-layer coextruder composite structure. Alternatively, the cured compositions can form different layers in a coextruded laminate, each layer having a slightly different composition. In certain aspects, the laminate may have 1 to 15 layers, for example, 2 layers, 3 layers, 4 layers or 5 layers, 6 layers, 7 layers, 8 layers, 10 layers, 11 layers, 12 layers, 13 layers, 14 layers or 15 layers. The overall size of the laminate is about 10 microns to about 100 microns, for example, 10 to 50 microns, 20 to 60 microns, 25 to 75 microns. Each individual layer can be 1 to 2 microns, 1 to 5 microns, 2 to 4 microns, 2 to 5 microns. For each laminate, at least one layer is a composition of the invention. In certain embodiments, the compositions of the invention comprise more than one layer. Alternatively, the hardened polyhydroxyalkanoate compositions are formed by combining the powdered or finely molded polyhydroxyalkanoate component in the vinyl acetate component. O 20/78 vinyl acetate polymer system is present as an emulsion or dispersion in water or solvent. The resulting emulsion or dispersion is then molded into a film or plate, dried to remove water or solvent, and then thermally melted to melt the individual components. In other embodiments, the hardened polyhydroxyalkanoate compositions further include additives. For example, in certain embodiments, one or more additives, such as plasticizers, process lubricants and thermal stabilizers, fillers, reinforcing agents, and flame retardants are included. In certain compositions of the invention, from about 1 to about 10 weight percent of monomeric or polymeric plasticizer (for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 , 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 weight percent); from about 0.1 to about 5 weight percent of process lubricants and thermal stabilizers (for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0 , 7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 , 0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9; 3.0, 3.1, 3.2 , 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4 , 5, 4.6, 4.7, 4.8, 4.9, or 5 weight percent) of about 3 to about 40 weight percent of cargo (for example, about 4 to about 35 weight percent, about 5 to about 30 weight percent, about 6 to about 25 weight percent, about 7 to about 20 weight percent, about 8 to about 15 percent weight percent, 10 to about 40 weight percent); from about 5 weight percent to about 40 weight percent of 21/78 reinforcing agents (for example, about 10 to about 35 weight percent, about 15 to about 30 weight percent, or about 18 to about 25 weight percent; about 0 , 5 weight percent to about 10 weight percent of nanocomposite reinforcing agents (e.g., about 0.75 to about 9 weight percent, about 1 to about 8 weight percent, about 2 to about 7 weight percent, about 3 to about 6 weight percent, about 4 to about 8.5 weight percent, about 5 to about 7.5 percent weight and / or about 1 to about 40 weight percent flame retardants (e.g., about 2 to about 37 weight percent, about 3 to about 35 weight percent, about about 4 to about 33 weight percent, about 5 to about 30 weight percent, about 6 to about 27 weight percent, about 7 to about 25 weight percent, about 8 about 23 percent by weight, about 9 to about 20 percent by weight, about 10 to about 18 weight percent, about 12 to about 36 weight percent, about 15 to about 40 weight percent). Examples of suitable fillers include, but are not limited to, glass fibers and minerals, such as precipitated calcium carbonate, molten calcium carbonate, talc, wollastonite, alumina trihydrate, wood flour, crushed nut shells, coconut shells, and shells rice and the like. HARDENERS Hardeners are agents that are beneficial for mixtures of polyhydroxyalkanoate because they help in 22/78 melt processing of polyhydroxyalkanoate mixtures in a variety of articles that have an improved level of hardness. The typical approach to hardening a polymer is to add a second polymer to the polymer to be hardened. The second polymer is selected to have a glass transition temperature typically from 20 ° C to about 60 ° C below that of the polymer to be modified (hardened). For example, U.S. Patent No. 5,763,532 (Exxon Chemicals) describes the use of elastic alpha-olefins to harden polypropylene. U.S. Patent No. 4,977,210 (BASF) refers to the use of ethylene-propylene polymers as hardeners for polypropylene. In both of these patents, the glass transition temperature of the curing agent is substantially below that of the polypropylene homopolymer. US Patent No. 5,859,137 (du Pont) discloses the use of ethylene ionomer resins to provide the hardening of polyamide resin, while US Patent No. 5,681,899 (Exxon) cites the use of a copolymer halogenated and a rubber component to provide similar improvements. Again, in both of these patents, the curing or mixing component has a low glass transition temperature in relation to the polymer to be cured. U.S. Patent No. 5,795,938 to BASF describes the use of a styrene-butadiene elastomer as a hardener for crystal polystyrene, and the 23/78 elastomer component also has a low glass transition temperature. Hardeners and impact modifiers for polymers have been mentioned in the literature. U.S. Patent No. 7,354,973 to du Pont describes the use of ethylene copolymers as hardeners specifically for polylactic acid. In the publication of U.S. Patent Application No. 2009/0191371, similar ethylene acrylate polymers were used as hardeners for polyhydroxybutyrate polymers. In these publications, the curing agents contain a high content of ethylene and, therefore, low glass transition temperatures. Furthermore, U.S. Patent No. 7,354,973 to du Pont discloses that these polymers provide a two-stage hardening mechanism as the clarity of the polyhydroxyalkanoate becomes impaired at relatively low additional levels. However, these hardening agents also seriously impair the biodegradability of polyhydroxyalkanoate. The use of a polymer with a low Tg as a hardener, as described above, provides a two-phase structure, in which the hardening polymer is distributed in a matrix of the polymer to be hardened. The stresses are then transferred from the most fragile polymer to the hardening polymer. Vinyl polyacetate homopolymer (PVAc) is not recognized as a hardening agent, as it has a Tg of 32 ° C and provides a fragile film by itself. More durable films can be produced from copolymers 24/78 polyvinyl acetate that includes monomers that reduce the glass transition temperature of the random vinyl acetate copolymer. But these are not traditionally considered to be hardeners for polyester-type resins, again, because their glass transition temperatures are typically much higher than those seen in traditional hardening technologies. Vinyl polyacetate (PVAc) has a Tg of about + 32 ° C, while PHA has a Tg of about + 7 ° C to about -30 ° C. The PVAc Tg, therefore, deters an individual from perceiving it as a potential hardener for PHAs in a typical two-phase system. In addition, PHB and PVAc are both often described individually as fragile polymers, so that the mixture of the two polymers would not be expected to provide a ductile material. However, PVAc has been studied in mixtures with polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-valerate copolymers, in terms of their effect on PHB crystallization (PHA is known to crystallize slowly). Such studies examined the miscibility of polyvinyl acetate polymers partially hydrolyzed by PHB and PVAc homopolymers (also known as vinyl acetate polymers with vinyl alcohol) and how these mixtures influence the crystallization rate of the PHB component. These publications discuss the morphology, the effect of the mixing components on the glass transition temperature and crystallization rates. None of them discuss the mechanical properties of such mixtures. 25/78 In general, PVAc was found to decrease the PHB crystallinity rate. For example, Kulkarni et al. (ANTEC 1995) found that PVAc decreases the PHB crystallization rate, and also decreases the PHB biodegradation rate under composting conditions. Specifically, the enzymatic degradation of PHB (by Penicillium funicolusim) was inhibited. This was seen at rates of just 10% PVAc. It has also been noted that the inclusion of PVAc reduces the crystallinity of PHBV (Chiu, HJ.J., 2006, Appl. Polym. Sci. 100: 980 to 988; Hay et al., 2000, Polymer 41: 5749 to 5757) . As presented in this document, the mixture of PVAc homopolymer or copolymer (Tg much higher than + 7 ° C, for example, + 32 ° C) with PHA (of about one Tg ~ + 7 ° C and below) provides a improvement of PHA hardening performance. This is unexpected as it does not follow the traditional hardening method. The vinyl acetate copolymers and homopolymers used in the present invention are preferably produced through the emulsion polymerization process with polyvinyl alcohol as the most common protective colloid, although nonionic stabilizers can be used. Vinyl acetate homopolymers and copolymers used in this invention can have molecular weights ranging from about 10,000 Daltons to about 1,000,000 Daltons and contain from about 0.01 weight percent to about 15 weight percent alcohol polyvinyl as the preferred colloid stabilizer. 26/78 In certain embodiments, the vinyl acetate copolymer or homopolymer contains about 0.5 weight percent to about 12.5 weight percent, about 0.75 to about 10 weight percent, about from 1 weight percent to about 8.5 weight percent, about 1.5 percent percent in weight at about 14 per percent in Weight, fence in 2 per percent in Weight, about 3 per percent in Weight, fence in 4 per percent in Weight, about 5 per percent in Weight, fence in 6 per percent in Weight, about 7 per percent in Weight, fence in 8 weight percent, about 9 weight percent, about weight percent, about 11 weight percent, about 12 percent by weight, about of 13 per percent in weight, or about 14 about 3 per percent in Weight, of alcohol polyvinyl. The hardeners in ; acetate in vinyl include one homopolymer or copolymer of vinyl acetate and at least one of the following monomers: ethylene (for example, up to 14 weight percent, for example, about 0.1 weight percent to about 14 weight percent, about 0.5 to about 13 weight percent, about 1 weight percent to about 12 weight percent, about 2 weight percent to about 11 weight percent, about 3 percent weight weight to about 10 weight percent,), (meth) acrylic esters (branched or unbranched alcohol esters having 1 to 15 carbon atoms, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, acrylate 27/78 norbornyl), vinyl esters having 1 to 12 carbon atoms in the carboxylic acid radical (eg vinyl propionate, vinyl laurate, alpha esters of alpha branched carboxylic acids that have 9 to 13 atoms carboxyl group-containing monomers (for example, acrylic acid, methacrylic acid, crontonic acid, itaconic acid, fumaric acid, maleic acid, and salts thereof), glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide, vinyl pyrrolidone and vinyl alcohol. POLYHYDROXIALCANOATES (PHAs) Polyhydroxyalkanoates are biological polyesters synthesized by a wide range of natural and genetically modified bacteria, as well as genetically modified plant crops (Braunegg et al., 1998, J. Biotechnology 65: 127 to 161; Madison and Huisman, 1999, Microbiology and Molecular Biology Reviews, 63:21 to 53; Poirier, 2002, Progress in Lipid Research 41: 131 to 155). These polymers are biodegradable thermoplastic materials, produced from renewable resources, with the potential for use in a wide range of industrial applications (Williams & Peoples, 1996, CHEMTECH 26: 38-44). Microbial strains useful for the production of PHAs include Alcaligenes eutrophus (renamed Ralstonia eutropha), Alcaligenes latus, Azotobacter, Aeromonas, Comamonas, Pseudomonads, and genetically modified organisms, including genetically modified microbes, such as Pseudomonas, Colstonia and Escherichia. 28/78 In general, a PHA is formed by the enzymatic polymerization of one or more monomer units within a living cell. More than 100 different types of monomers have been incorporated into PHA polymers (Steinbüchel and Valentin, 1995, FEMS Microbiol. Lett. 128: 219 to 228. Examples of monomeric units incorporated in PHAs include 2-hydroxybutyrate, lactic acid, glycolic acid, 3 -hydroxybutyrate (hereinafter called 3HB), 3-hydroxypropionate (hereinafter called 3HP), 3-hydroxyvalerate (hereinafter called in 3HV), 3-hydroxyhexanoate (hence in against called in 3HH), 3-hydroxyheptanoate (hence in against called in 3HHep) , 3-hydroxyoctanoate (hence in against called in 3HO), 3-hydroxynonanoate (hence in against called in 3HN), 3-hydroxydecanoate (hence in against called in 3HD), 3-hydroxydodecanoate (hence in against called in 3HDd) , 4-hydroxybutyrate (hence in against called 4HB), 4- -hydroxyvalerate (from here on called 4HV), 5-hydroxyvalerate (hereinafter called 5HV), and 6-hydroxyhexanoate (hereinafter called 6HH). The 3-hydroxy acid monomers incorporated in PHAs are the (D) or (R) isomers of 3-hydroxy acid with the exception of 3HP, which does not have a chiral center. In some modalities, PHA is a homopolymer (all monomer units are the same). Examples of PHA homopolymers include poly 3-hydroxyalkanoates (for example, poly 3-hydroxypropionate (hereinafter called P3HP), poly 3-hydroxybutyrate (hereinafter called PHB) and poly 3-hydroxyvalerate), poly 4-hydroxyalkanoates 29/78 (for example, poly 4-hydroxybutyrate (hereinafter called P4HB), or poly 4-hydroxyvalerate (hereinafter called P4HV)) and poly 5-hydroxyalkanoates (for example, poly 5-hydroxyvalerate (hereinafter hereinafter called P5HV)). In certain embodiments, the initial PHA is a copolymer (which contains two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. Examples of PHA copolymers include poly 3-hydroxybutyrate-co-3-hydroxypropionate (hereinafter called PHB3HP), poly 3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter called PHB4HB), poly 3-hydroxybutyrate-co-4-hydroxyvalerate (hereinafter called PHB4HV), poly 3-hydroxybutyrate-co-3-hydroxyvalerate (hereinafter called PHB3HV), poly 3-hydroxybutyrate-co-3hydroxyhexanoate (hereinafter called PHB3HH) and poly 3-hydroxybutyrate- co-5-hydroxyvalerate (hereinafter called PHB5HV). By selecting the types of monomers and controlling the ratios of the monomeric units in a given PHA copolymer, a wide range of material properties can be achieved. Although examples of PHA copolymers having different monomer units have been provided, PHA can have more than two different monomer units (for example, three different monomer units, four different monomer units, five different monomer units, six different monomer units). An example of a PHA that 30/78 has 4 different monomer units would be PHB-co-3HH-co3H0-CO-3HD or PHB-co-3-HO-co-3HD-co-3HDd (these types of copolymers ΡΗΆ are hereinafter called PHB3HX). Typically, where ο PHB3HX has 3 or more monomer units, the 3HB monomer is at least 70% by weight of total monomers, preferably 85% by weight of total monomers, more preferably greater than 90% by weight of total monomers, for example, 92 %, 93%, 94%, 95%, 96% by weight of the copolymer and the HX comprises one or more monomers selected from 3HH, 3HO, 3HD, 3HDd. The homopolymer (where all monomer units are identical) PHB and 3-hydroxybutyrate copolymers (PHB3HP, PHB4HB, PHB3HV, PHB4HV, PHB5HV, PHB3HHP, hereinafter called PHB copolymers) that contain 3-hydroxybutate and at least one other monoxide and at least of particular interest for production and commercial applications. It is useful to describe these copolymers by reference to their material properties as follows. Type 1 PHB copolymers typically have a glass transition temperature (Tg) in the range of 6 ° C to -10 ° C and a melting temperature T M between 80 ° C to 180 ° C. Type 2 PHB copolymers typically have a Tg of -20 ° C to -50 ° C and Tm of 55 ° C to 90 ° C and are based on PHB4HB, PHB5HV polymers with more than 15% 4HB, 5HV content , 6HH or mixtures thereof. In particular embodiments, the type 2 copolymer has a phase component with a Tg of -15 ° C to -45 ° C and no Tm. Preferred type 1 PHB copolymers have two monomer units that have a majority of their units 31/78 monomeric being 3-hydroxybutyrate monomer by weight in the copolymer, for example, more than 78% 3-hydroxybutyrate monomer. The preferred PHB copolymers for this invention are produced biologically from renewable resources and are selected from the following group of PHB copolymers: PHB3HV is a type 1 PHB copolymer where the content of 3HV is in the range of 3% to 22% by weight of the copolymer and preferably in the range of 4% to 15% by weight of the copolymer, for example : 4% of 3HV; 5% of 3HV; 6% in 3HV; 7% of 3HV; 8% of 3HV; 9% of 3HV; 10% 3HV; 11% in 3HV; 12% 3HV; 13% 3HV; 14% of 3HV; 15% of 3HV; 16% in 3HV; 17% of 3HV; 18% of 3HV; 19% of 3HV; 20% of 3HV; 21% in 3HV; 22% of 3HV; 23% of 3HV; 24% of 3HV; 25% of 3HV. 0 PHB3HP is a PHB copolymer type 1 < sm that the 3HP content is in the range of 3% to 15% by weight d < 2 copolymer and preferably in range of 4% to 15% in weigh 9 do copolymer, for example : 4% of 3HP; 5% of 3HP; 6% in 3HP; 7% 3HP; 8% 3HP; ! 9% of 3HP; 10% 3HP; 11% in 3HP; 12% 3HP; 13% 3HP; 14% 3HP; 15% of 3HP. 0 PHB4HB is a PHB copolymer type 1 " sm that the 4HB content is in the range of 3% to 15% by weight of the copolymer and preferably in the range of 4% to 15% by weight of the copolymer, for example: 4% of 4HB; 5% of 4HB; 6% of 4HB; 7% of 4HB; 8% of 4HB; 9% of 4HB; 10% 4HB; 11% of 4HB; 12% 4HB; 13% 4HB; 14% of 4HB; 15% of 4HB. PHB4HV is a PHB type 1 copolymer in which the 4HV content is in the range of 3% to 15% by weight of the copolymer and preferably in the range of 4% to 15% by weight of the 32/78 copolymer, for example: 4% 4HV; 5% of 4HV; 6% of 4HV; 7% of 4HV; 8% of 4HV; 9% of 4HV; 10% 4HV; 11% of 4HV; 12% of 4HV; 13% 4HV; 14% of 4HV; 15% 4HV; or 20% to 40% of 4HV. PHB5HV is a PHB type 1 copolymer in which the 5HV content is in the range of 3% to 15% by weight of the copolymer and preferably in the range of 4% to 15% by weight of the copolymer, for example: 4% of 5HV ; 5% of 5HV; 6% of 5HV; 7% of 5HV; 8% of 5HV; 9% of 5HV; 10% 5HV; 11% 5HV; 12% 5HV; 13% 5HV; 14% of 5HV; 15% of 5HV. Ο PHB3HH is a PHB type 1 copolymer in which the 3HH content is in the range of 3% to 15% by weight of the copolymer and preferably in the range of 4% to 15% by weight of the copolymer, for example: 4% of 3HH ; 5% 3HH; 6% 3HH; 7% 3HH; 8% 3HH; 9% 3HH; 10% 3HH; 11% 3HH; 12% 3HH; 13% 3HH; 14% 3HH; 15% 3HH; 16% 3HH; 17% 3HH; 18% 3HH; 19% 3HH; 20% 3HH; 21% 3HH; 22% 3HH; 23% 3HH; 24% 3HH; 25% of 3HH. Ο PHB3HX is a PHB type 1 copolymer in which the 3HX content is comprised of 2 or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HX content is in the range of 3% to 12% by weight of the copolymer and preferably in the range of 4% to 10% by weight of the copolymer, for example: 4% 3HX; 5% 3HX; 6% 3HX; 7% 3HX; 8% 3HX; 9% 3HX; 10% 3HX by weight of the copolymer. Type 2 PHB copolymers have a content of 3HB between 80% and 5% by weight of the copolymer, eg 80%, 33/78 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5% by weight of the copolymer. Ο PHB4HB is a PHB type 2 copolymer in which the 4HB content is in the range of 20% to 60% by weight of the copolymer and preferably in the range of 25% to 50% by weight of the copolymer, for example: 25% of 4HB ; 30% of 4HB; 35% of 4HB; 40% of 4HB; 45% of 4HB; 50% 4HB by weight of the copolymer. PHB5HV is a PHB type 2 copolymer in which the 5HV content is in the range of 20% to 60% by weight of the copolymer and preferably in the range of 25% to 50% by weight of the copolymer, for example: 25% 5HV; 30% of 5HV; 35% of 5HV; 40% of 5HV; 45% of 5HV; 50% 5HV by weight of the copolymer. Ο PHB3HH is a type 2 PHB copolymer in which the 3HH content is in the range of 35% to 95% by weight of the copolymer and preferably in the range of 40% to 80% by weight of the copolymer, for example: 40% of 3HH ; 45% of 3HH; 50% 3HH; 55% 3HH, 60% 3HH; 65% 3HH; 70% 3HH; 75% 3HH; 80% 3HH by weight of the copolymer. Ο PHB3HX is a PHB type 2 copolymer in which the 3HX content is comprised of 2 or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HX content is in the range of 30% to 95% by weight of the copolymer and preferably in the range of 35% to 90% by weight of the copolymer, for example: 35% 3HX; 40% 3HX; 45% 3HX; 50% 3HX; 55% 3HX; 60% 3HX; 65% 3HX; 70% 3HX; 75% 3HX; 80% 3HX; 85% 3HX; 90% 3HX by weight of the copolymer. 34/78 PHAs for use in the methods, compositions and pellets described in this invention are selected from: PHB or a type 1 PHB copolymer; a mixture of PHB PHA with a type 1 PHB copolymer in which the PHB content by weight of PHA in the PHA mixture is in the range of 5% to 95% by weight of the PHA in the PHA mixture; a mixture of PHB PHA with a type 2 PHB copolymer in which the PHB content by weight of the PHA in the PHA mixture is in the range of 5% to 95% by weight of the PHA in the PHA mixture; a mixture of PHA of a type 1 PHB copolymer with a different type 1 PHB copolymer and in which the content of the first type 1 PHB copolymer is in the range of 5% to 95% by weight of the PHA in the mixture of PHA; a PHA mixture of a type 1 PHB copolymer with a type 2 PHA copolymer wherein the content of the type 1 PHB copolymer is in the range of 30% to 95% by weight of the PHA in the PHA mixture; a mix from PHA in PHB with one copolymer in PHB type 1 it is a copolymer from PHB of type 2 in what the PHB content it is placed on at the interval 10% up to 90% by weight of PHA on mixture in PHA, in what the content of PHB copolymer of type it is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of the type 2 PHB copolymer is in the range of 5% to 90% by weight of the PHA in the PHA mixture. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB3HP in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the 35/78 PHA in the PHA blend and the 3HP content in PHB3HP is in the range of 7% to 15% by weight of PHB3HP. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB3HV in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the 3HV content in PHB3HV is in the range of 4% to 22% by weight of PHB3HV. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB4HB in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the 4HB content in PHB4HB is in the range of 4% to 15% by weight of PHB4HB. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB4HV in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the 4HV content in PHB4HV is in the range of 4% to 15% by weight of PHB4HV. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB5HV in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the 5HV content in PHB5HV is in the range of 4% to 15% by weight of PHB5HV. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB3HH in which the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the 3HH content in PHB3HH is in the range of 4% to 15% by weight of PHB3HH. The mixture of PHB PHA with a type 1 PHB copolymer is a mixture of PHB with PHB3HX in which the 36/78 PHB in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 3HX in the PHB3HX is in the range of 4% to 15% by weight of the PHB3HX. The PHA blend is a blend of a type 1 PHB copolymer selected from the group PHB3HV, PHB3HP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX with a second type 1 PHB copolymer that is different from the first type 1 PHB copolymer and is selected from the group PHB3HV, PHB3HP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX in which the content of the first type 1 PHB copolymer in the PHA mixture is in the range of 10% to 90% by weight of the total PHA in the mixture. The mixture of PHB PHA with a type 2 PHB copolymer is a mixture of PHB with PHB4HB in which the PHB content in the PHA mixture is in the range of 30% to 95% by weight of the PHA in the PHA mixture and the 4HB content in PHB4HB is in the range of 20% to 60% by weight of PHB4HB. The mixture of PHB PHA with a type 2 PHB copolymer is a mixture of PHB with PHB5HV in which the PHB content in the PHA mixture is in the range of 30% to 95% by weight of the PHA in the PHA mixture and the 5HV content in PHB5HV is in the range of 20% to 60% by weight of PHB5HV. The mixture of PHB PHA with a type 2 PHB copolymer is a mixture of PHB with PHB3HH in which the PHB content in the PHA mixture is in the range of 35% to 95% by weight of the PHA in the PHA mixture and the 3HH content in PHB3HH is in the range of 35% to 90% by weight of PHB3HX. The mixture of PHB PHA with a type 2 PHB copolymer is a mixture of PHB with PHB3HX in which the 37/78 PHB in the PHA mixture is in the range of 30% to 95% by weight of PHA in the PHA mixture and the 3HX content in PHB3HX is in the range of 35% to 90% by weight of PHB3HX. The PHA blend is a blend of PHB with a PHB type 1 copolymer and a PHB type 2 copolymer in which the PHB content in the PHA blend is in the range of 10% to 90% by weight of the PHA in the PHA mixture, the content of the PHB copolymer type 1 in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of the PHB copolymer type 2 in the The PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture. For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HV content in the PHA blend in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the 3HV content in the PHB3HV in the range of 3% to 22% by weight of the PHB3HV, and a PHBHX content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA blend in which the PHHX 3HX content is in the range of 35% to 90% by weight of PHBHX. For example, a PHA blend can have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HV content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HV content in the PHB3HV is in the range of 3% to 22% by weight of the PHB3HV, and a PHB4HB content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in PHB4HB is in the range of 20% to 60% by weight of PHB4HB. 38/78 For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HV content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HV content in the PHB3HV is in the range of 3% to 22% by weight of the PHB3HV, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, in which the 5HV content in PHB5HV is in the range of 20% to 60% by weight of PHB5HV. For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HB content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in the PHB4HB is in the range of 4% to 15% by weight of the PHB4HB, and a PHB4HB content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in PHB4HB is in the range of 20% to 60% by weight of PHB4HB. For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HB content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in the PHB4HB is in the range of 4% to 15% by weight of the PHB4HB, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, in which the 5HV content in PHB5HV is in the range of 30% to 90% by weight of PHB5HV. For example, a PHA blend can have a PHB content in the PHA blend in the range of 10% to 90% by weight of the 39/78 PHA in the PHA mixture, a PHB4HB content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in PHB4HB is in the range of 4% to 15% by weight of PHB4HB, and a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HX content in PHB3HX is in the range of 35% to 90% by weight of PHB3HX . For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HV content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HV content in the PHB4HV is in the range of 3% to 15% by weight of the PHB4HV, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, in which the 5HV content in PHB5HV is in the range of 30% to 90% by weight of PHB5HV. For example, a PHA blend can have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HH content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HH content in the PHB3HH is in the range of 3% to 15% by weight of the PHB3HH, and a PHB4HB content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 4HB content in PHB4HB is in the range of 20% to 60% by weight of PHB4HB. For example, a PHA blend can have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HH content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, in 40/78 that the content of 3HH in PHB3HH is in the range of 3% to 15% by weight of PHB3HH, and a content of PHB5HV in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, on what the content in 5HV on the PHB5HV is in the range in 20% 60% by weight of PHB5HV.For example, a mixture of PHA can Tue one content in PHB at mixture of PHA in the 10% at 90% in weight of PHA in the PHA mixture, a PHB3HH content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HH content in the PHB3HH is in the range of 3% to 15% by weight of PHB3HH, and a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, in which the 3HX content in PHB3HX is in the range of 35% to 90% by weight of PHB3HX . For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HX content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA blend, where the PHH3HX 3HX content is in the range of 35% to 90% by weight of PHB3HX. For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HX content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB4HB content in the PHA mixture in the 41/78 range of 5% to 90% by weight of PHA in the PHA mixture, where the content of 4HB in PHB4HB is in the range of 20% to 60% by weight of PHB4HB. For example, a PHA blend may have a PHB content in the PHA blend in the range of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HX content in the PHA blend in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, in which the 5HV content in PHB5HV is in the range of 20% to 60% by weight of PHB5HV. The PHA blend is a blend as presented in U.S. Patent Application Publication No. 2004/0220355, by Whitehouse, published on November 4, 2004, which is incorporated into the present invention in its entirety. Microbial systems for the production of the PHB PHBV copolymer are disclosed in U.S. Patent No. 4,477,654 to Holmes. Published Patent Application WO 02/08428, by Skraly and Sholl, describes systems useful for the production of the PHB copolymer PHB4HB. Processes useful for the production of PHB copolymer PHB3HH have been described (Lee et. Al., 2000, Biotechnology and Bioengineering 67: 240 to 244; Park et al., 2001, Biomacromolecules 2: 248 to 254). The processes for the production of PHB PHB3HX copolymers have been described by Matsusaki et. al., (2000, Biomacromolecules 1:17 to 22). 42/78 In determining molecular weight, techniques such as gel permeation chromatography (GPC) can be used. In the methodology, a polystyrene standard is used. Ο PHA may have a polystyrene weight equivalent molecular weight (in Daltons) of at least 500, at least 10,000, or at least 50,000 and / or less than 2,000,000, less than 1,000,000, less than 1,500,000, and less than 800,000. Preferably, in certain embodiments, PHAs generally have a weight average molecular weight in the range of 100,000 to 700,000. For example, the molecular weight range for PHB and type 1 PHB copolymers for use in this requirement is in the range of 400,000 Daltons to 1.5 million Daltons, as determined by the GPC method and the molecular weight range for copolymers of Type 2 PHB for use in application 100,000 to 1.5 million Daltons. In certain embodiments, the branched PHA can have a linear average molecular weight equivalent of about 150,000 Daltons to about 500,000 Daltons and a polydispersity index of about 2.5 to about 8.0. As used herein, the weight average molecular weight and the linear equivalent weight average molecular weight are determined by gel permeation chromatography, using, for example, chloroform as both eluent and diluent for PHA samples. The calibration curves for determining molecular weights are generated using linear polystyrenes as molecular weight standards and a 'log Molecular Weight versus elution volume' calibration method. RAMIFIED POLYHYDROXIALCANOATES 43/78 The term branched PHA refers to a PHA with branching chain and / or crosslinking two or more chains. Branching into side chains is also contemplated. Branching can be achieved by several methods. The polyhydroxyalkanoate polymer described above can be branched by branching agents by free radical-induced polymer crosslinking. In certain embodiments, PHA is branched prior to the combination in the method. In other embodiments, PHA is reacted with peroxide in the methods of the invention. The branching increases the melt resistance of the polymer. Polyhydroxyalkanoate polymers can be branched in any manner described in US Patent Nos. 6,620,869, 7,208,535, 6,201,083, 6,156,852, 6,248,862, 6,201,083 and 6,096,810, all of which are incorporated herein as a reference in its entirety. The polymers of the invention can also be branched according to any of the methods presented in International Patent Publication No. WO 2010/008447, entitled “Methods For Branching PHA Using Thermolysis or International Patent Publication No. WO 2010/008445, entitled “Branched PHA Compositions, Methods For Their Production, And Use In Applications, both of which were published in English on January 21, 2010, and assigned to the United States. These requirements are incorporated by reference in this document in their entirety. BRANCHING AGENTS 44/78 Branching agents, also called free radical initiators, for use in the compositions and methods described herein include organic peroxides. Peroxides are reactive molecules, and can react with linear PHA or previously branched PHA molecules by removing a hydrogen atom from the polymer's main chain, leaving a radical behind. PHA molecules that have such radicals in their main chains are free to combine with each other, creating branched PHA molecules. Branching agents are selected from any suitable initiator known in the art, such as peroxides, azo derivatives (e.g., azo-nitriles), peresters, and peroxycarbonates. Peroxides suitable for use in the present invention include, but are not limited to, organic peroxides, for example, organic dialkyl peroxides, such as 2,5-dimethyl-2,5di (t-butylperoxy) hexane, 2,5-bis (t-butylperoxy ) -2,5dimethylhexane (available from Akzo Nobel as TRIGANOX 101), 2,5-dimethyl-di (t-butylperoxy) hexino-3, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide di-t-amyl, t-amylperoxy-2-ethylhexylcarbonate (TAEC), t-butyl cumyl peroxide, n-butyl-4,4-bis (tbutylperoxy) valerate, 1,1-di (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5trimethylcyclohexane (CPK), 1,1-di (tbuthyloxy) cyclohexane, 1,1-di (t-amylperoxy) -cyclohexane, 2.2- di (t-butylperoxy) butane, ethyl-3,3-di (tbutylperoxy) butyrate, 2,2-di (t-amylperoxy) propane, ethyl- 3.3- di (t-amylperoxy) butyrate, t-butylperoxy-acetate, t 45/78 amylperoxyacetate, t-butylperoxybenzoate, tamilperoxybenzoate, di-t-butyldiperoxyphthalate, and the like. Peroxide combinations and mixtures can also be used. Examples of free radical initiators include those mentioned herein as well as those described in, for example, Polymer Handbook, 3rd Edition, J.Brandrup & EH Immergut, John Wiley and Sons, 1989, Ch. 2. Irradiation (for example, e-beam or gamma irradiation) can also be used to generate the PHA branch. The branching and crosslinking efficiency of the polymer (s) can also be significantly improved by dispersing organic peroxides in a crosslinking agent, such as polymerizable (ie, reactive) plasticizers. The polymerizable plasticizer should contain a reactive functionality, such as a reactive unsaturated double bond, which increases the overall branching and crosslinking efficiency. As discussed above, when peroxides decompose, they form very high energy radicals that can extract a hydrogen atom from the polymer's main chain. These radicals have short half-lives, thereby limiting the population of branched molecules that is produced during the active period of time. EPOXY FUNCTIONAL COMPOUNDS Functional epoxy compound, as used herein, is a compound with two or more epoxy groups capable of increasing the melt resistance of polyhydroxyalkanoate polymers by branching, for example, end chain branching. 46/78 Such epoxy functional compounds may include epoxy-functional styrene-acrylic polymers (such as, but not limited to, for example, JONCRYL® ADR-4368 (BASF), or MP-40 (Kaneka)), copolymers and acrylic and / or acrylic oligomers. polyolefin containing glycidyl groups incorporated as side chains (such as, but not limited to, for example, LOTADER® (Arkema), poly (ethylene glycidylacethacrylate-methacrylate)), and epoxy oils (such as, but not limited to, for example, epoxy oils of soy, olive, flax seed, palm, peanut, coconut, seaweed, cod liver oils, or mixtures thereof, for example, Merginat ESBO (Hobum, Hamburg, Germany) and EDENOL® B 316 (Cognis, Dusseldorf, Germany)). For example, reactive acrylic or functional acrylic crosslinking agents are used to increase the molecular weight of the polymer in the branched polymer compositions described herein. Such cross-linking agents are sold commercially. BASF, for example, markets multiple compounds under the trade name JONCRYL®, which are described in US Patent No. 6,984,694 to Blasius et al., “Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications, hereby incorporated by reference in their entirety. Such a compound is JONCRYL® ADR-4368CS, which is styrene glycidyl methacrylate and is discussed below. Another is MP-40 (Kaneka). Yet another is the Petra line with Honeywell, see, for example, U.S. Patent No. 5,723,730. Such polymers are often used in 47/78 recycling plastic (for example, recycling polyethylene terephthalate) to increase the molecular weight (or to simulate the increase in molecular weight) of the polymer being recycled. Such polymers often have the general structure: H 2 C Ri and Ra are H or alkyl Rs is alkyl x and v is 1 -20 z is 2-20 Du Pont de Nemours & Company markets multiple reactive compounds under the trade name Elvaloy®, which are ethylene copolymers, such as acrylate copolymers, elastomeric terpolymers, and other copolymers. One such compound is Elvaloy PTW, which is a copolymer of ethylene-n-butyl acrylate and glycidyl methacrylate. Omnova markets similar compounds under the trade names SX64053, SX64055, and SX64056. Other entities also supply these compounds commercially. Specific polyfunctional polymeric compounds with reactive epoxy functional groups are styrene-acrylic copolymers and oligomers that contain glycidyl groups incorporated as side chains. These materials are based on oligomers with styrene building blocks 48/78 and acrylate which have glycidyl groups incorporated as side chains. A high number of epoxy groups per oligomer chain is used, for example, 10, more than 15, or more than 20. These polymeric materials generally have a molecular weight greater than 3,000, specifically greater than 4,000, and more specifically greater than 6,000. These are commercially available from Johnson Polymer, LLC (now owned by BASE) under the trade name JONCRYL, material ADR 4368. Other types of polyfunctional polymeric materials with multiple epoxy groups are copolymers and oligomers of acrylic and / or polyolefin that contain glycidyl groups incorporated as side chains. A further example of such a polyfunctional carboxy-reactive material is a co- or terpolymer, including ethylene and glycidyl methacrylate (GMA) units, available under the trade name LOTADER® resin, marketed by Arkema. These materials can also comprise methacrylate units that are not glycidyl. An example of this type is poly (ethylene-glycidyl-methacrylate-co-methacrylate). Fatty acid esters or naturally occurring oils that contain epoxy (epoxidized) groups can also be used. Examples of naturally occurring oils are olive oil, flax seed oil, soybean oil, peanut oil, coconut oil, seaweed oil, cod liver oil, or a mixture of these compounds. Particular preference is given to epoxidized soybean oil (for example, Merginat® ESBO from Hobum, Hamburg, or Edenol® B 316 from Cognis, Dusseldorf), but others can also be used. 49/78 Other examples include poly (ethylene-glyceryl-acrylate-cometacrylate), ethylene-n-butyl acrylate-glycidyl methyl acetate copolymer poly (ethylene-co-glycidylmethacrylate) copolymers, poly (ethylene-co-methacrylate-cometacrylate) glycidyl), poly (ethylene-glycidyl methacrylate-ethylene co-methacrylate / vinyl acetate / carbon monoxide, and ethylene / n-butyl acetate / carbon monoxide or combinations). NUCLEATING AGENTS If desired, an optional nucleating agent is added to the PHA (for example, the branched PHA) to assist in its crystallization. The nucleating agents for various polymers are simple substances, metallic compounds, including composite oxides, for example, carbon black, calcium carbonate, synthesized silicic acid and salts, silica, zinc white, clay, kaolin, basic magnesium carbonate , talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumine, calcium silicate, organophosphate metal salts, and boron nitride; low molecular weight organic compounds that have a metallic carboxylate group, for example, metallic salts such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic, melissic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, monomethyl ester of terephthalic acid, acid 50/78 isophthalic and isophthalic acid monomethyl ester; high molecular weight organic compounds that have a metallic carboxylate group, for example, metallic salts such as: polyethylene containing a carboxyl group obtained by oxidation of polyethylene; polypropylene containing carboxyl group obtained by oxidation of polypropylene; olefin copolymers, such as ethylene, propylene and butene1, with acrylic or methacrylic acid; styrene copolymers with acrylic or methacrylic acid; olefin copolymers with maleic anhydride; and styrene copolymers with maleic anhydride; high molecular weight organic compounds, for example: Alpha-olefins branched at their carbon atom in position 3 and which have no less than 5 carbon atoms, such as 3,3 dimethylbutene-1,3-methylbutene1,3-methylpentene-1 , 3-methylhexene-1, and 3,5,5-trimethylhexene1; vinylcycloalkane polymers such as vinylcyclopentane, vinylcyclohexane, and vinylnorbornane; polyalkylene glycols, such as polyethylene glycol and polypropylene glycol; poly (glycolic acid); phosphoric or phosphorous acid and its metallic salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis (4-tert-butylphenyl) phosphate, and methylene bis- (2,4-tert-butylphenyl) phosphate; sorbitol derivatives, such as bis (p-methylbenzylidene) sorbitol and bis (petylbenzylidene) sorbitol; and thioglycolic anhydride, p-toluenesulfonic acid and its metallic salts. The above nucleating agents can be used either alone or in combination with each other. In particular embodiments, the nucleating agent is cyanuric acid. In certain embodiments, the nucleating agent can also be another 51/78 polymer (for example, polymeric nucleating agents, such as PHB). In certain embodiments, the nucleating agent is selected from: cyanuric acid, carbon black, talc mica, silica, boron nitride, clay, calcium carbonate, synthesized silicic acid and salts, organophosphate metal salts, and kaolin. In particular embodiments, the nucleating agent is cyanuric acid. In various embodiments, where the nucleating agent is dispersed in a liquid carrier, the liquid carrier is a plasticizer, for example, a citrus compound or an adipic compound, for example, acetylcitrate tributyrate (CITROFLEX® A4, Vertellus, Inc., High Point, NC), or DBEEA (dibutoxyethoxyethyl adipate), a surfactant, for example, Triton X-100, TWEEN-20, TWEEN-65, Span-40 or Span 85, a lubricant, a volatile liquid, for example, chloroform, heptane, or pentane, an organic liquid or water. In other embodiments, the nucleating agent is aluminum hydroxy disphosphate or a compound comprising a heteroaromatic nucleus containing nitrogen, as described in Published Patent Application No. US 2005/0209377 Al, which is hereby incorporated by reference in its entirety . In particular embodiments, the nucleating agent may include hydroxy aluminum phosphate or a compound comprising a heteroaromatic nucleus containing nitrogen. The nitrogen-containing heteroaromatic nucleus is pyridine, pyrimidine, pyrazine, pyridazine, triazine, or 52/78 imidazole. The nucleate may have a chemical formula selected from the group that 6 ' R R Formulai Rk ^ Á> R 1 ^ N -R 1 R 1x Formulas R 1 ^ NR 1 Formula4 Rt Formula 5 Formula 2 Formula 6, and combinations thereof, where each IR is independently H, NR 2 R 2 , OR 2 , SR 2 , SOR 2 , SO 2 R 2 , CN, COR 2 , CO 2 R 2 , conr 2 r 2 , no 2 , F, Cl, Br or I; and each R 2 is independently H or C 1 -C 6 alkyl. Another nucleating agent for use in the compositions and methods described in this document are ground as described in International Patent Publication No. WO 2009/129499, published in English on October 22, 2009, and which designates the United States, which is incorporated herein as a reference in its entirety. In summary, the nucleating agent is milled in a liquid carrier until at least 5% of the cumulative solid volume of the nucleating agent exists in the form of particles with a particle size of 5 microns or less. The liquid carrier allows the nucleating agent to be wet milled. In other embodiments, the nucleating agent is ground in a liquid carrier until at least 10% of the cumulative volume of solids, at least 20% of the cumulative volume of solids, 53/78 at least 30% or at least 40% to 50% of the nucleating agent can exist as particles with a particle size of 5 microns or less, 2 microns or less or 1 micron or less. In alternative modalities, the nucleating agents are ground by other methods, such as jet milling and the like. In addition, other methods are used that reduce the particle size. The cumulative solid volume of the particles is the combined volume of the particles in dry form in the absence of any other substance. The cumulative solid volume of the particles is determined by determining the volume of the particles before dispersing them in a polymer or liquid carrier by, for example, pouring them dry into a graduated cylinder or other suitable device for volume measurement. Alternatively, the cumulative solids volume is determined by the diffusion of light. ADDITIONS It should also be considered whether the composition includes other additives. With any compound based on polymeric resin, additives provide easier processing and a more desirable final appearance and properties for the compound. The additive can be any compound known to those of skill in the art that are useful in the production of polymeric articles. Exemplary additives include, for example, plasticizers (for example, to increase the flexibility of the polymeric composition), antioxidants (for example, to protect the polymeric composition from degradation by ozone or oxygen), 54/78 ultraviolet stabilizers (for example, to protect against weather conditions), lubricants (for example, to reduce friction), pigments (for example, to add color to the polymeric composition), flame retardants, fillers, antistatic agents, agents reinforcement, and / or mold release agents. Optimal amounts to be added will depend on several factors known to the person skilled in the art, for example, cost, desired physical characteristics of the polymeric composition (eg, mechanical strength), and the type of processing being performed (increasing, for example, considerations line speeds, cycle time, and other processing parameters). It is up to the professional to determine whether an additive should be included in a polymeric composition and, if so, what additive and the amount that should be added to the composition. For example, the compositions of the present invention may further comprise other additives, such as about 1 to about 10 weight percent of monomeric or polymeric plasticizer; about 0.1 to about 5 weight percent of process lubricants and thermal stabilizers; about 3 to about 40 weight percent of cargo; about 5 weight percent to about 40 weight percent reinforcing agents; about 0.5 weight percent to about 10 weight percent nanocomposite reinforcing agents; and / or about 1 to about 40 weight percent of flame retardants. Examples of suitable fillers include glass fibers and minerals, such as carbonate 55/78 precipitated calcium, molten calcium carbonate, talc, wollastonite, alumina trihydrate, wood flour, shell of crushed walnut, shell in coconut, bark of rice and similar Nuclear agentscan to be used for to control the rate at which O polymer of crystallizes. Plasticizers are used to aid processing, change the glass transition temperature and the composition module. Surfactants are generally used to dust, lubricate, reduce surface tension, and / or densify. Lubricants are typically used to reduce the stickiness of hot-processed metal surfaces. Binders can bond beneficially to other components in the polymer. Loads are commonly used to reduce cost and shine. Antioxidants can be used to prevent aging and fragility of the polymer. Impact modifiers are useful in rigid polymers to increase hardness. Pigments and dyes can be organic, or they can be minerals, like titanium dioxide, and they can be opacifying pigments, or coloring pigments. Clays are also useful as additives, for example, nano-clay or organically modified clay can be added to a polymeric composition. There are several types of clays used in polymeric compositions, including cationic or medium or high cation exchange capacity. The cation exchange capacity is generally reported as the number of interchangeable base milliequivalents that can be exchanged for 100 grams of 56/78 clay. The cation exchange capacity varies from about 50 to about 150, depending on the type of clay. Examples of clays that can be organically modified include sepiolite, atapulgite, montmorillonites, bentonites, saponite and nentronite. Organically modified clays are known in the art and are also described in US Patent No. 2,531,440. Examples include montmorillonite clay modified with ternary or quaternary ammonium salts. Nanoarclines are commercially available from Southern Clay Products, Inc. of Gonzales, Texas, USA (as, but not limited to, Cloisite®NA + (a natural montmorillonite), Cloisite® 93A & 30B (a natural modified montmorillonite with ternary ammonium salts) ), and Cloisite® 10A, 15A, 20A, and 25A (a natural montmorillonite modified by quaternary ammonium salts). Montmorillonite clay is the most common member of the smectite family of nano-clay. Smectites have a unique morphology, presenting a dimension in the nanometer range. The Montmorillonite clay particle is often called a platelet, which is a sheet-like structure in which the dimensions in two directions far exceed the particle's thickness. The length and width of the particles varies from 1.5 microns to a few tens of a micrometer. However, the thickness is only about one nanometer. These dimensions result in extremely high average aspect ratios (on the order of 200 to 500). Furthermore, the very small size and thickness indicate that a single 57/78 grams of clay can contain more than a million individual particles. The clay initially comprises clusters of platelet layers. The nano-clay becomes commercially useful if processed in an interlayer, which separates (defoliate) the platelets in the agglomerates. In an interlayer, the clay is mixed with an interlayer under conditions that cause the platelets to separate and the interlayer to enter the spaces between the platelets. The intercalant is often an organic or semi-organic chemical substance capable of entering the montmorillonite clay gallery and bonding to the surface of the platelets. An interlayer is, therefore, a clay-chemical complex in which the spacing of the clay gallery has increased, due to the process of surface modification by the substance (the interleaver). Under the appropriate conditions of temperature and shear, the platelet agglomerates are able to defoliate (separate), allowing the intercalant to penetrate between them, separating and defoliating them. Platelets can be defoliated (separated) by numerous processes. In a defoliation procedure, described in U.S. Patent No. 6,699,320, the process uses a dispersant to enter between the platelet layers of clay and separate them. In this process, the clay is mixed with a dispersant (for example, castor wax), and then heated in the cylinder of an extruder to a temperature above the melting point of the dispersant (for example, 82 ° C to 104 ° C in the case of castor wax). The heated mixture is then stirred, for example, with a vane screw 58/78 deep. This heating and stirring disperses the platelet layers and delaminates platelets from neighboring layers by allowing dispersant molecules to enter between the layers. The layers are considered to be defoliated when the separation between the platelet layers is large enough so that there is no longer enough attraction between the layers to cause uniform spacing between the layers. In the process described in U.S. Patent No. 6,699,320, the screw in the extruder moves the clay-wax mixture out of an extrusion die opening in the form of a hot aqueous paste. Two cooled chrome plated rolls are then used to calender the mixture to a predetermined thickness that is determined by the spacing between the rolls. The mixture is cooled to solidify the wax. The clay-wax mixture is then scraped from the rollers and falls like flakes on a conveyor belt. The flakes can be agitated so that their sizes are further reduced, used immediately, or stored. Due to the very small size of the clay particles, nanoclays are difficult to handle, and can present health risks. Therefore, they are sometimes processed in master batches, in which the clay is dispersed in a polymer resin at a high concentration. The portions of the master batch are then added in measured quantities to the polymer that does not contain nano clay, to produce a polymer that contains a precise amount of the nano clay. 59/78 A montmorillonite clay is Cloisite® 25A, which can be obtained from Southern Clay Products of Gonzales, Texas, USA. A typical dry particle size distribution of Cloisite® 25A is 10% less than 2 microns, 50% less than 6 microns, and 90% less than 13 microns. Other nano-clays are identified in U.S. Patent No. 6,414,070 (Kausch et al.), Which is incorporated herein by reference in its entirety, and PCT Patent Publications WO 00/66657 and WO 00/68312. APPLICATION OF COMPOSITIONS For the manufacture of useful articles, the hardened composition is typically processed at a temperature close to the crystalline point of the PHA to minimize the loss of molecular weight. Additives are chosen to be stable at these temperatures. While melting, the composition is processed into a desired shape, and subsequently cooled to shape the shape and induce crystallization. Such formats may include, but are not limited to, a fiber, filament, film, sheet, rod, tube, bottle, or other format. Such processing can be carried out using any technique known in the art, such as but not limited to extrusion, injection molding, compression molding, blow molding or blow molding (e.g., blown film, foam blowing), calendering, rotational molding (rotational molding), casting (for example, cast sheet, cast film) or thermoforming. The hardened PHA composition is used to create, without limitation, a wide range of useful products, for example, automotive products, consumer durables, 60/78 construction, electrical, medical, and packaging. For example, polymeric compositions are used to manufacture, without limitation, films (for example, packaging films, agricultural film, clown film, erosion control, alfalfa packaging, plastic film, food packaging, pallet packaging, packaging protective cover for automobiles and appliances, etc.), golf tee, covers and fasteners, agricultural supports and stakes, paper and edge coatings (for example, for cups, plates, boxes, etc.), thermoformed products (for example, trays , containers, lids, yoghurt pots, cup lids, plant pots, noodle bowls, moldings, etc.), accommodation (for example, for electronic items, for example, cell phones, PDA cases, music player cases , computer cases and the like), bags (for example, trash bags, shopping bags, food bags, compost bags, etc.), hygiene items (for example, diapers, feminine hygiene products, incontinence products disposable wipes, etc.), coatings for pelletized products (eg pelletized fertilizers, herbicides, pesticides, seeds, etc.), injection molding (writing instruments, utensils, disc cases, etc.), solution and spun fibers and melted-blown fabrics and non-woven fabrics (yarns, threads, tissues, upholstery, disposable absorbent articles), blow moldings (deep containers, bottles, etc.) and foam articles (glasses, bowls, plates, packaging, etc.) ). 61/78 Thermoforming is a process that uses thermoplastic films or sheets. The polymeric composition is processed into a film or sheet. The polymer sheet is then placed in an oven and heated. When it is soft enough to be formed, it is transferred to a mold and shaped into a shape. During thermoforming, when the softening point of a semi-crystalline polymer is reached, the polymer sheet begins to fall. The window between softening and deepening is usually narrow. Therefore, it may be difficult to move the softened polymer sheet into the mold quickly enough. The polymer branching, as described in this document, increases the melt resistance of the polymer so that the sheet is more readily processed and maintains its structural integrity. Measuring the depth of a polymer sample piece when it is heated is, therefore, a way of measuring the relative size of this processing window for thermoforming. Molded products include numerous types of different products and, for example, include products such as spoons, forks and disposable knives, buckets, bowls, lids, cup lids, yogurt pots and other containers, bottles and bottle-like containers, etc. Blow molding is similar to thermoforming and is used to produce deep products, such as bottles and similar products with deep interiors. 62/78 The hardened PHA compositions described in this document are provided in any form suitable for an intended application. For example, hardened PHA is supplied in a pellet form to subsequently produce films, coatings, molds or other articles, or films, coatings, molds and other articles are made directly as the hardened PHA is produced. ANNEALING Post-fabrication heat treatment (eg annealing) of polyhydroxyalkanoate film produced by the methods and compositions described in this document produces a film that increases puncture and tear resistance. Such increases are not seen in other polymeric films, for example, polyethylene. Such annealing is used to increase the hardness of injection moldings. For example, PHA films are treated for about 10 to about 120 minutes at temperatures of about 80 ° C to about 120 ° C. Such treatment improves the puncture resistance of the films by up to 16 times, while the tear resistance could be improved by up to 35 times (transverse direction) and up to 65 times (machine direction). Although several PHAs are capable of being processed on conventional processing equipment, many problems have been encountered with the polymers, which hinder their commercial acceptance. These include frailty and age-related frailty. For example, the mechanical properties of articles produced from 63/78 of polyhydroxyalkanoate polymers are known to change over time, during storage and ambient conditions. Specifically, impact hardness and stress elongation at break (and b ) are known to decrease systematically over time. The exact reasons for this decrease are not known. This age-related increase in frailty limits the commercial applications available for using the polymer. In addition, the crystallization kinetics of the polymer is poorly understood, and longer cycles of time (relative to polyethylene and polypropylene) are often necessary during the processing of these polymers, which further limits their commercial acceptance. Post-manufacture heat treatment (for example, annealing) provides benefits to the mechanical properties of PHA compositions. These mechanical properties include strength and tear resistance. As used in this context, annealing and heat treatment means a treatment where the polyhydroxyalkanoate polymer processed to form a product in the non-liquid form is subsequently (i.e., after the film is formed) heated over a period of time. This has been found to provide surprising and unexpected properties of puncture toughness and tear resistance in PHA films. Preferably, the flat film is heated to about 80 ° C to about 140 ° C for about 5 seconds to about 90 minutes, more preferably to about 90 ° C to about 130 ° C for about 10 minutes about 70 minutes, and with greater 64/78 preferably at about 110 ° C to about 125 ° C for about 15 minutes to about 60 minutes. This has been found to provide surprising and unexpected properties of puncture toughness, toughness and tear resistance in PHA films. Increased hardness is also seen in injection moldings. For example, flat polyhydroxyalkanoate film is annealed at 120 ° C for 10 seconds. This is accomplished, for example, online by forming the film in any of a variety of ways and then passing the film through an oven that is maintained at the appropriate temperature. The oven is long enough that, between entering and leaving the oven, the film is exposed to heat for the appropriate amount of time. Alternatively, the film is wound through the oven, for example, back and forth on a series of rolls inside the oven, so that the film is exposed to heat for the appropriate amount of time before leaving the oven. In practice, the actual time of the treatment as a whole may be longer. For the polyhydroxyalkanoate film that was collected in standard rolls prior to treatment, for example, the film inside the cylinder will not be immediately exposed to the temperature required to cause annealing and the film inside the roller will not exhibit the beneficial properties disclosed here. The entire roll must be kept at the necessary temperature for a time sufficient for the polymer inside the roll to experience the annealing temperatures. 65/78 Alternatively, the film could be exposed to the appropriate temperatures after being made, but before being rolled up on a roll. In this situation, the film only needs to be exposed to the annealing temperature for as long as necessary for the area to be treated to reach the appropriate temperature. The film is exposed to temperatures very close to the melting point of the polymer (s) that form (s) the film. In practice, however, this is best done with a flat film, since a large roll of film could start to stick to itself. Similar methods can be used for the annealing of injection moldings. Without wishing to be limited by theory, it is possible that, when the polyhydroxyalkanoate film is made, the crystallization is not completely complete and continues for some time afterwards. Late crystallization can cause internal shrinkage stresses, that is, a form of necking in at the molecular level. If so, then these stresses can reduce the puncture toughness and tear resistance of the film. As described here, heat treatment can relieve some of these internal stresses. The specific examples below are to be interpreted as merely illustrative and in no way as limiting the rest of the disclosure. Without further elaboration, it is believed that one skilled in the art can, based on the description presented here, use the present invention to the fullest. All publications here 66/78 cited are given as fully incorporated by reference. EXAMPLES Materials Vinyl polyacetate (PVAc) materials were supplied by Wacker Chemie AG and Kuraray America Inc. A brief description of each of the materials is given below: VINNEX® LL2504 (Wacker Chemie AG): copolymer of polyethylene vinyl acetate, T g = -7 ° C and very high molecular weight. VINNEX® LL2510 (Wacker Chemie AG): polyethylene vinyl acetate terpolymer, T g = 42 ° C and very high molecular weight. VINNAPAS® UW10F (Wacker Chemie AG): vinyl polyacetate homopolymer, T g = 44 ° C, PM = 330 to 430,000 g / mol. VINNAPAS® B60 (Wacker Chemie AG): vinyl polyacetate homopolymer, T g = 42 ° C, PM = 55 to 70,000 g / mol. The PHA materials used were a copolymer of 3-hydroxybutyrate and a 4-hydroxybutyrate (P3HB-4HB) with 8 to 14% 4HB or mixtures of PHA. The mixture of PHA No. 1 was composed of about 58 to 62% 3-hydroxybutyrate homopolymer, and about 38 to 42% 3-hydroxybutyrate and 4-hydroxybutyrate copolymer, where 4-hydroxybutyrate was approximately 8 to 14% in Weight. The mixture of PHA n ° 2 was composed of about 34 to 38% homopolymer of 3-hydroxybutyrate, 22 to 26% copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate, where 467/78 hydroxybutyrate was in 8 to 14% and 38 to 42% in copolymer in 3-hydroxybutyrate and 4-hydroxybutyrate, in that the 4- hydroxybutyrate was 25 to 33% by weight. MethodsEvaluation in Ductility / Hardness in Mixtures gives Invention Ductility is a mechanical property defined according to the extent to which a material can permanently deform under an applied stress (bending, stretching or compression) without fracturing. It is directly related to hardness, which is a measure of the amount of energy a material can absorb before fracturing. Hardness is usually measured by integrating the area under the stress-elongation curve during the tensile test. To determine the ductility or hardness of PHA / PVAc film mixes, they were first formulated in a Randcastle extruder at 170 ° C to produce a molded film approximately 0.2 to 0.5 mm thick and conditioned under conditions environments (20 to 25 ° C, 50 to 60% RH) for 7 days to fully develop crystallinity. Injection molded bars were also prepared using a Roboshot injection molder with front / intermediate / rear / nozzle / mold temperatures set at 165 ° C / 165 ° C / 160 ° C / 160 ° C / 60 ° C, blocking pressure of 758.42 MPa (110,000 psi), back pressure of 5.86 MPa (850 psi) and screw speed of 150 rpm. After injection molding, the bars 68/78 were dried at 50 ° C for 48 hours before the Traction and Izod notch test. Qualitative Tear Test for Films: The hardness of PHA / PVAc film mixes was assessed using a qualitative tear test. The side and edge of a film to be tested were first cut with a scalpel to a depth of 2mm, then the film was manually twisted 90 degrees around the cutting notch. The ease with which the film was ripped was observed. No tearing or considerable force required to propagate a tear was considered as an indication of a high degree of ductility or hardness. Test of Tensile Properties, Notched Izod Impact and Tear Resistance of Injection Molded Bars: The tensile modulus, strength and elongation of the molded bars were measured using the ASTM D638 method. The Izod impact with notch through pendulum was measured using the ASTM D256 method, while tear strength through pendulum was measured using the ASTM D1922 method. Measurement of Thermal Properties The glass transition (T g ) and the peak crystallization temperature (T c ) were measured using a TA Instruments Q100 Modulated Differential Scanning Calorimeter (MDSC) with autosampler. For each measurement, 8 to 12 mg of a mixing sample were weighed in an aluminum drum and sealed with an aluminum cap. The sample was then placed in the DSC under a nitrogen purge and analyzed using a 69/78 modulated heating-cooling. The heating / cooling range was -70 ° C to 200 ° C with a heating rate of 3 ° C / min and a cooling rate of 10 ° C / min. Modulation was performed using an oscillation of 1 ° C every 60 seconds. AT g was calculated from the modulated heating cycle by choosing the midpoint of the baseline deviation, while T c was determined from the cooling cycle by obtaining the peak temperature during sample crystallization. Example 1. High Module PHA Film Mixtures. In this example, three vinyl acetate polymers available from Wacker Chemie AG (Germany) were tested for their ability to harden P ° lihydroxyalkanoate. The vinyl acetate polymers used in the mixture included VINNEX® LL2510, VINNIPAS® B60 and VINNEX® LL2504. These three vinyl acetates vary in T g , molecular weight and composition. Its effect on the hardness of PHA film is shown in Tables a through c. It should be noted that the formulation components are supplied in weight percent. Table la. Polyhydroxyalkanoate formulations High Modulus Containing Ethylene-Acetate Terpolymer VINNEX® vinyl LL2510. Formulation 1 2 3 4 P3HB-4HB (8 to 14% of4HB) 97 87.7 78.2 59 Agent Master LotNuclear 3 2.6 2.3 1, 8 VINNEX® LL2510 0 19.5 19.5 39.2 Tear Hardness brittle hard Very hard Very hard 70/78 Midpoint of T g (° C) -11.8 -3.4 2.1 10.8 Peak T c (° C) ___________ 112.2 106, 9 105, 4 102.6 Table 1b. Formulations fin -z u. kz f J V z- f vPolyhydroxyalkanoate High Module Containing Homopolymer of Acetate from Vinila VINNAPAS® B60. Formulation 1 5 6 7 P3HB-4HB (8 to 14% of 97 87.7 78.2 59 4HB) Agent Master Lot 3 2.6 2.3 1.8 Nuclear JVINNAPAS® B609, 7 19, 5 39, 2 Tear Hardness smash- hard hard muchdiice hard Midpoint of T g (° C) -11.8 -4.7 -11.7 -12.3 T peak c (° C) 112.2 106, 0 106.7 104.4 Table lc. Polyhydroxyalkanoate formulations High Modulus Containing Copolymer ofVINNEX® vinyl LL2504. Ethylene Acetate in Formulation 1 8 9 10P3HB-4HB (8 to 14% of 97 87.7 78.2 594HB)Agent master batch 3 2, 6 2.3 1.8NuclearVINNEX® LL25049, 7 19, 5 39.2Tear Hardness smash- hard much much diicehard hardMidpoint of T g (° C) -11.8 -3.5 1.2 11.2T peak c (° C) 112.2 107.0 105.7 103.2 The master batch of nucleant contained cyanuric acid that had previously been formulated at a rate of 33% (by weight) in a 3-hydroxybutyrate-co-4-hydroxybutyrate base resin, and pelletized. The results achieved with the above formulations demonstrated that when the homopolymers or copolymers of vinyl acetate were added to high PHA mixtures 71/78 modulus, the hardness of these mixtures increased with the increasing content of vinyl polyacetate resin. All compositions showed a single glass transition temperature, indicating a high degree of miscibility between the polyhydroxyalkanoate and vinyl acetate polymer phases. Formulations containing VINNEX® LL2510 and VINNEX® LL2504 showed an increase in the glass transition temperature with the increasing content of vinyl acetate. Hardness also increased, contrary to what was expected from the usual immiscible phase approach to harden polymers. In all cases, the crystallization rate measured by DSC cooling showed a lower peak crystallization temperature and, therefore, a slower crystallization, although the reduction was not significant enough to impact the processing characterization of the formulations. Example 2. Lower Module PHA Film Mixtures. In this example, a lower modulus polyhydroxyalkanoate was selected for mixing with the vinyl acetate polymers. Tables 2a to c show the formulations produced, as well as the thermal and tearing properties for the films. Table 2a. Polyhydroxyalkanoate formulations Lower Module Containing Acetate Homopolymer VINNEX® vinyl LL2510. Formulation 11 12 13Mixture of PHA No. 2 97 87.7 78.2Agent Master Lot 3 2.6 2.3 14591.8 72/78 Nuclear VINNEX® L2510 0 9.7 19, 5 39, 6 Rip hard much extremely- extremely- hard mind mind hard hard Midpoint of T g (° C) -19, 9 -17.4 -11, 6 0.5 T peak c (° C) 104.4 105.8 100.7 97.5 Table 2b. Polyhydroxyalkanoate formulations Lower Module thanVINNAPAS® B60 vinyl. Contains Homopolymer of Acetate Formulation 11 15 16 17 PHA mix n ° 2 97 87.7 78.2 59 Agent Master Lot 3 2.6 2.3 1.8 Nuclear VINNAPAS® B60 0 9, 7 19, 5 39, 6 Tear Hardness hard extreme extreme extreme -mind mind -mind hard hard hard Midpoint of T g (° C) -19, 9 -16.8 -17.1 -17.4 T peak c (° C) 104.4 99, 8 _J ° 1.7 102.1 Table 2c. Polyhydroxyalkanoate formulations Lower Module thanVINNEX® vinyl LL2504. Contains Homopolymer of Acetate Formulation 11 18 19 20 PHA mix n ° 2 97 87.7 78.2 59 Agent Master Lot 3 2, 6 2.3 1.8 Nuclear VINNEX® LL2504 0 9, 7 19.5 39, 6 Tear Hardness hard much extreme- extreme- hard mind mind hard hard Midpoint of T g (° C) -19, 9 -16.2 -15.9 -15.7 T peak c (° C) 104.4 89, 5 100.3 96, 9 The master batch of nucleant was cyanuric acid that had previously been formulated at a rate of 33% (by weight) on a 3-hydroxybutyrate and 4-hydroxybutyrate base resin and pelletized. 73/78 In all cases, an improvement in Tearing Hardness was observed with the addition of vinyl acetate polymers even with an increase in the glass transition temperature for the mixtures. The addition of VINNAPAS® LL2510 showed the greatest impact on T g for the mixtures, while VINNAPAS® B60 showed the greatest impact on Tear Hardness. Crystallization rates were slightly slower for PHA / PVAc mixtures, however, not sufficient to affect conversion to manufactured products. Example 3. Injection Molding Formulations. The following formulations have been developed for injection molded articles. Table 3. Injection Molding Formulations. Formulation 21 22 23 24 Mixture of PHA n ° l 73 68 63 53 Master batch of 5 5 5 5 Nuclear Agent Baby powder 11 11 11 11 Calcium carbonate 10 10 10 10 VINNAPAS® B60 0 5 10 20 Concentrate of 1 1 1 1 ACRAWAX® C nucleating agent was cyanuric acid dispersed at a rate of 33% (by weight) in CITROFLEX® A4 plasticizer (CP Hall) and ground in the plasticizer. The calcium carbonate was MULTIFLEX-MM® (Specialty Minerals); the talc was FLEXTALC® 610D (Specialty Minerals); the ACRAWAX® C concentrate (Lonza) was 1: 1 pelletized ACRAWAX® C in a PHA mixture composed of about 38 to 42% 74/78 3-hydroxybutyrate homopolymer, and about 58 to 62% copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate, where 4-hydroxybutyrate was approximately 10 to 12%. Example 4: PHA / PVAc mixtures with Reactive Coupling 5 In this example, mixtures of high modulus PHA with PVAc were prepared in the presence of a peroxide agent (TRIGANOX® 131, Akzo Nobel). The general effect of peroxide was to facilitate the reactive coupling of polymers 10 of PHA and PVAc which improves the hardness of the mixture. The Table below shows the results of PVA grafting on the traction module, elongation, strength, as well as toughness and tear resistance of Izod with notch. Table 4. Effect of Peroxide Grafting on 15 Mechanical Properties of PHA / PVAc Mixtures. Formulation 25 26 27 28 29 30 Mixture of PHA n ° l 92 82 82 0 0 0 PHA mix n ° 2 0 0 0 92 82 82 VINNEX® UW10FS 0 10 10 0 0 0 VINNEX® LL2510 0 0 0 0 10 10 Nuclear Master Lot 3 3 3 3 3 3 CITROFLEX® A4 5 5 4.8 5 5 4.8 TRIGONOX® 131 0 0 0.2 0 0 0.2 Traction Module (MPA) 1108 1116 1241 460 473 494 Tensile Strength at Break (MPA) 18.4 21.1 23.2 18.2 24.0 24.5 Elongation at Break (%) 23 211 257 285 517 557 Notched Izod Impact (J / m (feet pound / inch)) 21.2(0.4) 31.8(0.6) 42.4(0.8) - - - Resistance totear (g / mil) - - - 10 26 80 75/78 Formulations 25 to 27 reflect the performance properties of a high modulus injection molding grade formulation without filling. The incorporation of VINNEX® UW10FS, a homopolymer of vinyl polyacetate with a mixture of PHA No. 1, provided an improvement in ductility and hardness, as observed by the greater elongation at break and the impact performance of Izod with notch. The incorporation of a small amount of TRIGANOX® 131 organic peroxide, to provide free radical coupling during the formulation operation, showed a further improvement in the ductility and hardness of the PHA / PVAc mixture. Formulations 28 to 30 represented film compositions based on a more elastomeric PHA composition, and improvements in tearing and tearing properties of the incorporation of VINNEX® LL2510, a vinyl acetate acetate terpolymer, were significant. The incorporation of peroxide as a reactive coupling agent showed an even greater improvement in elongation and hardness. Unlike the examples herein, or unless specifically stated otherwise, all numerical ranges, quantities, values and percentages, such as those for material quantities, elementary grades, reaction times and temperatures, ratios of quantities, and others , in the following portion of the specification and in the appended claims can be read as prefaced by the expression about, although the expression about may not appear expressly with the 76/78 value, quantity or range. Consequently, unless otherwise specified, the numerical parameters set out in the specification and in the appended claims below are approximations that may vary depending on the desired properties sought to be achieved by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted in light of the number of significant digits reported and through the application of common rounding techniques. Although the numerical ranges and parameters that establish the broad scope of the invention are approximations, the numerical values established in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains an error that necessarily results in the standard deviation found in its respective base test measurements. In addition, when numerical ranges are established here, these ranges are inclusive of the quoted range end points (ie end points can be used). When weight percentages are used here, the reported numerical values are relative to the total weight. In addition, it should be understood that any numerical range mentioned here is intended to include all the sub-ranges included here. For example, a range from “1 to 10 is intended to include all sub-ranges between (and which include) the minimum quoted value of 1 and the maximum quoted value of 10, that is, that has a minimum value equal to or greater than 77/78 that 1 and a maximum value equal to or less than 10. The terms one (1), one or one, as used herein, are intended to include at least one or one or more, unless otherwise indicated. otherwise. Any patent, publication, other disclosure material, in whole or in part, that is said to be incorporated by reference is incorporated here only to the extent that the incorporated material does not conflict with the definitions, statements or other material of existing disclosures set out in this description. As such, and to the extent necessary, the description, as explicitly stated here, replaces any conflicting material hereby incorporated by reference. Any material, or portion thereof, which is said to be incorporated herein by reference, however, which conflicts with the existing definitions, statements or other disclosure material set forth herein will only be incorporated to the extent that no conflict arises between the embedded material and the existing development material. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein are used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned here are incorporated by reference in their entirety. In case of 78/78 conflict, this specification, including definitions, will prevail. Furthermore, the materials, methods and examples are illustrative only and are not intended to be limiting. All the features presented in this specification can be combined in any combination. Each resource presented in this specification can be replaced by an alternative resource that serves the same purpose, an equivalent purpose or a similar purpose. Therefore, unless expressly stated otherwise, each feature presented is only an example of a generic series of equivalent or similar features. From the description above, one skilled in the art can easily verify the essential characteristics of the present invention and, without deviating from the spirit and scope of the same, can make several changes and modifications of the invention to adapt it to different uses and conditions. Therefore, other modalities are also within the scope of the attached claims. Although this invention has been shown and described particularly with reference to its preferred embodiments, those skilled in the art will understand that various changes in shape and details can be made therein without departing from the scope of the invention covered by the appended claims.
权利要求:
Claims (15) [1] 1. Method of forming a biodegradable polymeric composition, characterized by comprising combining: a) a biologically produced polyhydroxyalkanoate (PHA) polymer; b) a hardener comprising a vinyl acetate polymer comprising a vinyl acetate monomer ranging from 60 percent to 100 percent by weight of the vinyl acetate polymer and the remainder of the hardener selected from at least one of the following: (i) up to 14 percent ethylene by weight of the vinyl acetate polymer; (ii) (meth) acrylic esters; (Iii) vinyl esters having 1 to 12 carbon atoms in the carboxylic acid radical; (iv) a monomer containing carboxyl group selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acid Fumaric acid, maleic acid and its salts; (v) glycidyl methacrylate, hydroxyethyl methacrylate, acrylamide and vinyl pyrrolidone; and (vi) vinyl alcohol; and c) a nucleating agent; and 25 mix components (a), (b) and (c) in fusion to produce a homogeneous mixture, in which the method is carried out in the presence of a peroxide that reacts with PHA. [2] 2. Method, according to claim 1, characterized by the fact that 30 the vinyl acetate polymer is a vinyl acetate homopolymer; the vinyl acetate copolymer includes a poly (vinyl acetate) copolymer that has 84 to 99 percent Petition 870190126407, of 12/02/2019, p. 11/33 2/10 percent of vinyl acetate monomer by weight of the poly (vinyl acetate) copolymer and from 1 to 16 percent of acrylate and ethylene comonomers by weight of the poly (vinyl acetate); the poly (vinyl acetate) polymer is produced by emulsion polymerization; the hardener additionally comprises up to 15 weight percent polyvinyl alcohol which has 60 to 99.8 weight percent hydrolysis, optionally wherein the polyvinyl alcohol comprises 1 to 99 weight percent of a homopolymer of poly (vinyl acetate) and from 99 to 1 weight percent of a vinyl acetate copolymer or copolymer mixture; or the polyhydroxyalkanoate polymer component is in the form of a fine particle size powder and the poly (vinyl acetate) component is in the form of an emulsion, the components being combined in an aqueous process before the water is thermally removed. [3] 3. Method according to claim 1, characterized by the fact that the hardener additionally comprises up to 15 percent of a polyvinyl alcohol by weight of the hardener, in which the polyvinyl alcohol has 60 to 99.8 percent in hydrolysis grade weight. [4] 4. Method, according to claim 1, characterized by the fact that polyvinyl alcohol has a molecular weight of 10,000 Daltons to 1,000,000 Daltons and the polyvinyl alcohol component is soluble in cold water. [5] 5. Method according to claim 1, characterized by the fact that the biologically produced polyhydroxyalkanoate polymer is 50 to 90 percent by weight of the total composition, and in which the hardener is 10 to 50 percent by weight of the total composition; or Petition 870190126407, of 12/02/2019, p. 12/33 3/10 the hardener additionally comprises up to 15 percent of a polyvinyl alcohol by weight of the hardener, wherein the polyvinyl alcohol has 60 to 99, 8 weight percent hydrolysis grade. [6] Method according to any one of claims 1, 2 and 4, characterized in that 5 to 95 weight percent of the composition is the biologically produced polyhydroxyalkanoate polymer. [7] Method according to any one of the preceding claims, characterized by the fact that the biologically produced polyhydroxyalkanoate polymer is a homopolymer of poly (3-hydroxybutyrate), a poly (3-hydroxybutyrate-co-4-hydroxybutyrate), a poly (3-hydroxybutyrate-co-3-hydroxyvalerate), a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) or a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); or the biologically produced polyhydroxyalkanoate polymer is a homopolymer of poly (3-hydroxybutyrate), a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% content of 4-hydroxybutyrate, a poly (3-hydroxybutyrate -co3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content, a poly (3-hydroxybutyrate-co-5hydroxyvalerate) with 5% to 15% 5-hydroxyvalerate content or a poly (3-hydroxybutyrate-co-3 -hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content. [8] 8. Method according to any one of claims 1 to 6, characterized by the fact that the biologically produced polyhydroxyalkanoate is a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate); a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a Petition 870190126407, of 12/02/2019, p. 13/33 4/10 poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); or the biologically produced polyhydroxyalkanoate is a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% a 15% 4-hydroxybutyrate content; a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content; a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content; a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% content of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-co-3hydroxyvalerate) with 5% to 22% content of 3 -hydroxyvalerate; a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% with 3-hydroxyhexanoate content or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content. [9] 9. Method, according to claim 8, characterized by the fact that the biologically produced polyhydroxyalkanoate is a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) and the weight Petition 870190126407, of 12/02/2019, p. 14/33 5/10 of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of the polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3hydroxyhexanoate) and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b ); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of the polymer a) is 5% to 95% of the combined weight of the polymer a) and the polymer b); or a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); and optionally the weight of polymer a) is 20% to 60% of the combined weight of polymer a) and polymer b) and the weight of polymer b) is 40% to 80% of the combined weight of polymer a) and polymer b ). [10] Method according to any one of claims 1 to 6, characterized in that the biologically produced polyhydroxyalkanoate is a) poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-4- hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content; a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% content Petition 870190126407, of 12/02/2019, p. 15/33 6/10 5-hydroxyvalerate; a) a homopolymer of poly (3-hydroxybutyrate) mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) which has 5% to 50% 3-hydroxyhexanoate content; a) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% content of 4-hydroxybutyrate mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content ; a) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% 5-hydroxyvalerate content; a) a poly (3-hydroxybutyratoco-4-hydroxybutyrate) with 5% to 15% 4hydroxybutyrate content mixed with b) a poly (3-hydroxybutyratoco-3-hydroxyhexanoate) which has 5% to 50% 3hydroxyhexanoate content; a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content ; a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% 5-hydroxyvalerate content; a) a poly (3-hydroxybutyrate-3-hydroxyvalerate) with 5% to 22% 3hydroxyvalerate content mixed with b) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) that has 5% to 50% 3hydroxyhexanoate content; a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content; a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% content of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% of 5 Petition 870190126407, of 12/02/2019, p. 16/33 7/10 hydroxyvalerate; or a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% content of 3-hydroxyhexanoate mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) which has 5% to 50% content of 3 -hydroxyhexanoate; or the biologically produced polyhydroxyalkanoate is a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 2050% content of 4-hydroxybutyrate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 20% to 50% 5-hydroxyvalerate content and the weight of the polymer a) is 5% to 95% of the combined weight of the polymer a) and the polymer B); a) a poly (3-hydroxybutyrate) homopolymer mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that has 5% to 50% 3-hydroxyhexanoate content and the weight of the polymer a) is 5 % to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content mixed with b) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-4-hydroxybutyrate) with 5% to 15% 4hydroxybutyrate content mixed with b) poly (3-hydroxybutyrate-co5-hydroxyvalerate) with 20% to 50% 5-hydroxyvalerate and weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyratoco-4-hydroxybutyrate) with 5% to 15% 4hydroxybutyrate content mixed with b) a poly (3-hydroxybutyratoco-3-hydroxyhexanoate) which has 5% to 50% 3hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the weight Petition 870190126407, of 12/02/2019, p. 17/33 8/10 combined of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% of 5hydroxivalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that has 5% to 50% content 3-hydroxyhexanoate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content mixed with b) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20 to 50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content mixed with b) a poly (3-hydroxybutyrate-co-5-hydroxyvalerate) with 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); or a) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content mixed with b) a poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that has 5% to 50% of 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b). [11] 11. Method according to claim 10, characterized by the fact that the weight of polymer a) is 20% Petition 870190126407, of 12/02/2019, p. 18/33 9/10 60% of Weight polymer combination a) and polymer b) it's the weight of polymer b) is 40% to 80% of combined weight of polymer a) and12. of polymer b).Method, according with Any of them of claims 8 to 11, characterized in that the biologically produced polyhydroxyalkanoate is additionally mixed with polymer c) a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) with 20% to 50% 4-hydroxybutyrate content; the biologically produced polyhydroxyalkanoate is further mixed with c) a poly (3-hydroxybutyrate-5-hydroxyvalerate) with 20% to 50% 5hydroxyvalerate content; or the biologically produced polyhydroxyalkanoate is further mixed with c) a poly (3-hydroxybutyrate-3-hydroxyhexanoate) with 5% to 50% 3-hydroxyhexanoate content. 13. Method, of a deal with The claim 12, featured by the fact that weight of polymer c) is 5% a 95% of weight polymer Combined of polymer The), of polymer b) and polymer c), optionally wherein the weight of polymer c is 5% to 40% of the combined polymer weight of polymer a), polymer b) and polymer c). [12] 14. Method according to any one of the preceding claims, characterized by the fact that the nucleating agent is selected from cyanuric acid, carbon black, mica talc, silica, boron nitride, clay, calcium carbonate, synthesized silicic acid or a salt thereof, a metal salt of organophosphates and a kaolin; the nucleating agent comprises aluminum hydroxidiphosphate or a compound comprising a nitrogen-containing heteroaromatic core; optionally Petition 870190126407, of 12/02/2019, p. 19/33 10/10 where the heteroaromatic nucleus containing nitrogen is pyridine, pyrimidine, pyrazine, pyridazine, triazine or imidazole; the nucleating agent has a chemical formula selected from the group consisting of [13] 15. Article comprising the composition obtained by the method as defined in any one of the preceding claims, characterized by the fact that the article is optionally in the form of a film, blade, molding, fiber, filament, rod, tube, bottle, pellet or foam . [14] 16. Process characterized by comprising: forming an article using the method as defined in any of claims 1 to 14, optionally wherein the article is formed by molding, extruding or blowing the composition. [15] 17. Article characterized by being formed by a process as defined in claim 16.
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法律状态:
2017-10-03| B25A| Requested transfer of rights approved|Owner name: CJ RESEARCH CENTER LLC (US) | 2018-02-20| B25A| Requested transfer of rights approved|Owner name: CJ CHEILJEDANG CORPORATION (KR) | 2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2019-02-12| B06T| Formal requirements before examination [chapter 6.20 patent gazette]| 2019-09-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]| 2019-12-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2020-02-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/08/2010, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 US23736809P| true| 2009-08-27|2009-08-27| US61/237,368|2009-08-27| PCT/US2010/047014|WO2011031558A2|2009-08-27|2010-08-27|Toughened polyhydroxyalkanoate compositions| 相关专利
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