TW201042103A - Production of non-woven materials from polyhydroxyalkanoate - Google Patents

Abstract

Methods and compositions for making non-woven materials from polyhydroxyalkanoate polymers are provided. In certain aspects, the invention pertains to an extruded fiber comprising a polyhydroxyalkanoate polymer, a wet milled nucleating agent and a plasticizer, wherein the particle size of the wet-milled nucleating agent is about 20 microns and is dispersed in the polymer.

Description

201042103 • VI. INSTRUCTIONS: [RELATED APPLICATIONS] - This application claims the benefit of US Provisional Application No. 61/203,542, filed December 23, 2008. The present application also claims priority to International Application No. PCT/US2009/041023, which is assigned to the United States and filed on April 17, 2009, and is hereby incorporated by reference. All teachings of the above application are incorporated herein by reference. ❹ TECHNICAL FIELD OF THE INVENTION The present invention provides methods and compositions for making nonwoven materials from polyhydroxyalkanoate polymers. In some aspects, the present invention relates to an extruded fiber comprising a polyhydroxyalkanoate polymer, a wet-milled nucleating agent, and a plasticizer, wherein the wet-milled nucleating agent has a particle size of It is about 2 microns and is dispersed in the polymer. 〇 [Prior Art] Biodegradable plastics are an increasing substitute for industrial applications in non-biodegradable plastics or as a substitute for a variety of applications. One type of bio3 degrading polymer is poly(base) _ (ΡΗΑ) β. These polymers are synthesized by soil and microorganisms for use as cells (IV). (4) The preparation of polymers such as: is generally recognized by soil microorganisms as a food source. Therefore, in particular, the quotient of the abandonment of human A 4 & However, so far, it has been found that the PHA limited in the market can be purchased. Among them, only the copolymer poly 201042103 (3-hydroxybutyrate vinegar - total 3_ sulphuric acid vinegar) (pHBv) can be used in various halo Knowing the processing " in the wild and picking up the people, the processing, but on the ancient Xuan = things have found a variety of problems. These issues include, in some cases, the lack of sex, which limits the commercial applications that can be obtained using polymers. Dividing two η: holding and lowering the molecular weight will result in brittleness of the final product. In addition: the crystallization kinetics of the polymer is not well understood, and long processing times are often required during processing: no longer, further limiting. This problem in particular limits the use of such polymers in the context of non-woven materials. There is a need to address these issues. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber composition for use in certain specific (four) woven materials. The material, the thirsty grinding/extruding synthetic fiber comprises a polypyridyl acid-cooling polymer, a grinding nucleating agent and a plasticizer. In some specific nucleating agents, boron nitride is used. In the other embodiments, the 'nuclear two' nucleating agent is a nucleating composition. Meter. In other specific examples: , , =: the particle size of the nucleating agent is about 2 〇 :::: in the example, the fiber (four) mouth. In some concrete:: square meters gram) to about -. In the burning of vinegar polymer. The::: contains from about 75 wt% to about 95 wt% of the polymer group to about 50 microns. In a specific example, the fiber diameter is about. .1 micron disclosed herein to extrude Hyun-Halalic acid vinegar, thirst-cutting, including bio-generated polyhydroxy...-type grinding nucleating agent and plasticizer, #t the fiber has a reduction of about 150 kg to 201042103/ The weight average molecular weight of mo1. In other embodiments, the average molecular weight is set to at least about 2 〇〇kg/m, and at least about 25 〇k. In particular embodiments, the fiber contains between about 75 wt% and about % Wt%. Bio-produced polyhydroxybutyrate and between about 5% and about 15% of acetamidine; In certain embodiments, the fiber comprises between about 1% and about 1% by weight of the total composition of a nucleating agent or nucleating composition, such as between about 1% and about hopping. Nucleating agent between. n In some embodiments, the fiber has a molecular weight of from about 150 kg/mol to about 250 kg/mol. In any particular embodiment disclosed herein, the fibers have a molecular weight of up to about 150 kg/mo, for example about 16 〇 kg/m 〇 1, about kg/th, about 18 〇 & kg/m 〇1. The fibers can have a molecular weight of at least about 200 kg/mol. In a particular embodiment, the fibers can have a molecular weight of from about 16 G kg/mol to about g mol 166 kg/mol > 167 kg/mol ^ 168 kg/mol '169 kg/m〇1. In other embodiments, the fibers can have a molecular weight of at least about 25 〇 kg/mol. 〇 3 A specific example reveals a nonwoven web comprising any of the fibers disclosed herein. Disposable articles that do not include any of the fibers disclosed herein are also disclosed. Other features and advantages of the invention will be apparent from the description and appended claims. [Embodiment] This month provides a non-woven material made of bio-generated poly-based sulphuric acid ester (). The nonwoven material may include other polymers as appropriate, and includes a biodegradable or non-biodegradable polymer. Fibers made by the methods described herein, in particular, meltblown fibers, have reduced brittleness and improved physical properties such as resilience and elasticity. The various physical and rheological properties of polymeric materials depend on the molecular weight and distribution of the polymer. The molecular weight can be calculated in a number of different ways. Unless otherwise indicated, "molecular weight" means the weight average of eight. The "number average weight" (Mn) represents the arithmetic mean of the distribution and is the sum of the product of the molecular weight of each part multiplied by its molar fraction (rolling/ΣΜ). "Molecular weight retenti〇" is the percentage of the weight average molecular weight of the extruded fiber (IV) the weight average molecular weight of the starting material. The weight average m〇lecular (Mw) 2 is the sum of the product of the molecular weight of each part multiplied by its weight fraction (ΣΑΜ / ). Mw is generally greater than or equal to Mn. Mz is the z-average of the molecular weight distribution (ςλμΈλμ/). As used herein, "basis weight" is the weight per unit area of the fabric formed from the fibers described herein. It is measured in grams per square meter (GSM). "Crystallinity" as used herein refers to the presence of two-dimensional order at the atomic size level. In the polymer, the ordered range can be as small as about 2 nm in one (or more) crystallographic directions and usually less than 50 nm in at least one side of 201042103. Polymer crystals often do not show the perfectness typically exhibited by low molecular weight. Individually operable polymer crystals: polymer single crystal. # # As used herein, "embrittlement (derivation or overheating causes plasticizer loss to become brittle and easy to embrittlement over time)" is generally lost or reduced in toughness from the old. The fiber breaks. π exhausted in stress

The physical properties of the flexible or non-woven fabric can be reversed. In other words, after the stress is removed, the material can be returned to its original bear. , ° "The thermal stability of the polymer sample (thermal stabiii^" is measured in two different ways. Thermal stability is represented here by the "k" of the sample, which shows the change of Mw over time It can also be measured by the capillary stability of the melt (MCS), which shows the change of capillary shear viscosity over time. The tensile properties are based on ASTM Internati〇nal, ι 〇〇BHungry Harbor Drive, PO Box C700, West Conshohocken, PA Measured by ASTM _, Test Method a_Vulcanized Rubber and Thermoplastic Elastomers, supplied by 8-2959 USA. Tensile strength) refers to a measure of the ability of a polymer to withstand tensile stress. Tensile modulus (tensile moduius) is the ratio of stress to strain within a specified material's limits. [Strength (as used herein) Toughness) means the property by which a material can absorb energy; the amount of material per unit of material that breaks it, or the actual amount of material per unit of mass per 7 201042103. For example, tensile stress-strain curve) toughness It is typically proportional to the area under the negative. The load-elongation curve (the "elongation rate (E1〇ngat_)" of the materials ("elongation (five) coffee blllty)" "g is increased by the length of the renting knife 5 (b) the original length Percentage. When the tensile strength of the test material is measured, it is broken at a certain page. The two work = put together and measure the elongation relative to the mark made before the start of the test, and will It is expressed as the original gauge length of the white knife ratio. The peak elongation (peak el〇n_CH〇) refers to the maximum amount of length extending before the fracture. "Peak force (# f〇rC〇) system, refers to The maximum amount of force applied before breaking. "Max lQad" means the total superimposed weight of a sample (such as a fiber) that can be carried without breaking. 'The nucleating agent is in the polymer A test sword providing a site for crystal formation. The nucleating composition is a composition comprising a nucleating agent. Wet-milled into: The agent is a nucleation that has been ground to a particle size of less than 2 μm in diameter in a liquid carrier. In other embodiments, the nucleating agent has been wet milled to a diameter of from about 6 microns to about 20 microns. Particle size. The wet-milled nucleating agent is dispersed (mixed in the entire filament) in the composition, prepared as a nucleating particle having a carrier-concentrated person, and dispersed in a composition that is subsequently added to the preparation fiber = In the liquid carrier. 'The nucleating agents of the methods and compositions herein include boron nitride, trimeric acid or related compounds, carbon black, mica talc' vermiculite, clay, carbonated tantalic acid and salt Metal salt of organic phosphate ester, kaolin and other materials. In the special method and composition, the nucleating agent is boron nitride. In the group and method of the present invention, the composition and method of the invention can be used for strontium and germanium. Other nucleating agents known to the '' and b' technicians. Wet grinding means grinding or milling in the liquid-composition until the desired particles/e.g., liquid carrier is obtained.. ^ ^ It is different from the composition Micron sizing • or He-rolling type. For the purpose of this, for the purpose of this, it is usually continuously milled until the particle size is reduced. The air is pulverized by Φ and the compressed air is passed through the nozzle to accelerate to Supersonic speed _ _, 霄 体 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 At the meeting point of the nozzle

Ό Converging, and subjected to violent collisions, E.R., J cut and milled. The fine particles are transported to the sorting zone by the ascending airflow, and the Danxi essence is classified by centrifugal force, while the coarser material remains in the obstruction and the cavity. For example, this process can be used to reduce the size of the nucleating agent from 5 Å to less than 2 Å. • In a peptide of the present invention, the particle size is less than 20 microns after wet grinding. In the present invention, in his mind, after the wet milling, at least ... ha V 5 / ° of the cumulative solid volume of the nucleating agent exists in the form of particles having a particle size of 5 μm or less, in other forms. · # i Q In the eight-body example, the cumulative solid volume of the nucleating agent is 10% in the form of particles having a particle size of 5 microns or less. In other aspects, at least 20% of the cumulative solid volume of the nucleating agent is present as particles having a particle size of 5 microns. In other aspects, at least 30% of the cumulative solid volume of the nucleating agent is present as particles having a particle size of 5 microns. In other aspects, at least 4% or more of the cumulative solid volume of the nucleating agent is present in a 5 micro" particle size. In the foregoing aspect, the nucleating agent has a size of 20 microns or less. Or a particle size of i micron or less than 9 micrometers. 9 201042103 Obtained a fine particle size coalescence into larger particle size or method and composition. Form dispersion while nucleating agent with less particle 5 degradation during the compounding step is used for As used herein, the phrase "by cohesive force and/or adhesion to teach fabrics (n, w〇ven)" as used herein refers to a rule that is made from a collection of fibers that are randomly arranged. The manners are surrounded by each other) not = flat 4 constituents (wherein the m filaments are formed by melting the material as in the text herein. For example, the type, the "us, the processing" (melt processing) is formed and then Cooling to maintain the desired shape of the hot typical glare processing technology, including glare extrusion and injection into a fusion of the use of horse speed air to make the long-term fiber mesh fabric..... Press 曰卞. A 'I. One of the processes The process is illustrated in Figure i, which is a one-step process for spraying. The high-speed air in the crucible blows the molten thermoplastic resin from the tip of the extruder die to the conveyor or coil „^upupsc(10)) to form fine fibers and self-adhesive mesh ♦. The typical formula & consists of the following elements: compaction machine, leaf measuring chest, mold assembly, mesh formation and winding. The melt blowing process is a newer non-woven process, and the benefits are popular. This process is unique in that It is almost exclusively used to prepare microfibers: σ, 功 〇〇 〇〇 fiber size fibers. Meltblown fibers have a diameter of about 0.1 microns to about 50 microns. Meltblown microfibers are typically about 2 microns in diameter. In the range of up to about 4 μm and as small as about ° 1 μm and up to about 15 μm. Meltblown weave: Differences between other materials and other non-woven fabrics, such as softness, opacity and porosity The difference can generally be traced back to the difference in filament size. Also 201042103 The general characteristics of non-woven fabrics include (but are not limited to): random fiber orientation; low to medium mesh strength, - 妒古 ^ ^ ^ ^ ^ ^ ^ ^ 1 ^ ^ Inter-declaration opacity (with High coverage system; number) from about 8 g/m2 to about 350 g/m2, typically in the range of about 2〇g/m2 to -=200 g/m, the surface area available for good insulation and filtration characteristics a mesh that is structurally layered or overlapped and whose number of layers increases with basis weight; can be layered with other nonwoven structures and/or films, and can be prepared by co-extruding different polymers through different molds. The component meltblown is not woven. The market for meltblown fibers is enormous, and these fibers are used in products such as wiper barrier products and filtration products. Polyhydroxyalkanoate (PHA) is suitable for meltblown technology and is suitable for forming Different mesh types, and attracted many manufacturers' attention due to their biodegradability and bio-based sources. • Polyhydroxyalkanoate (PHA) 'The polymers (e.g., the matrix and/or carrier polymer) used in the methods and compositions described herein are polyhydroxyalkanoates (hereinafter referred to as PHA). Polyhydroxyalkanoates are biopolyesters synthesized from a variety of natural and genetically engineered bacteria and genetically engineered plant crops (Braunegg et al., (1998), 65: 127-161; Madison and Huisman, 1999, Microbiology). And Molecular Biology Reviews, 63: 21-53; Poirier, 2002, Progress in Lipid Research 41: 13 1 -15 5 ). These polymers are biodegradable thermoplastics that are produced from regenerative resources' with the potential to be used in a variety of industrial applications (Winiams)

And Peoples, Ci/Five Open 26:38-44 (1996)). Biological strains suitable for the production of PHA include the eutrophic bacillus () (renamed the genus Ralstonia (and)), the widely produced π 201042103 bacterium (J/cWgewe·? /aiws), azozo (Jzo/okc/er), Aeromonas (Jeromowiz·?), Pseudomonas (ComamowiZ·?), Pseudomonas (Piewi/omowW), and genetically engineered organisms , including genetically engineered microorganisms such as Pseudomonas (Piewi/owowas), Ralstonia (Τ?α/·5ίο«ζ'β), and Escherichia coli (Escherichia coli). In general, PHA is formed by enzymatic polymerization of one or more monomer units within living cells. More than 100 different types of monomers have been incorporated into PH A polymers (Steinbtichel and Valentin, FjEMS A/7cro6fo/. Zeii 128; 219-228 (1995)). Examples of the monomer unit incorporated in PHA include 2-hydroxybutyrate, lactic acid 'glycolic acid, 3-hydroxybutyrate (hereinafter referred to as HB), 3-hydroxypropionate (hereinafter referred to as 3HP), 3 - hydroxyvalerate (hereinafter referred to as 3HV), 3-hydroxyhexanoate (hereinafter referred to as 3HH), 3-hydroxyheptanoate (hereinafter referred to as 3HHep), 3-hydroxyoctanoate (hereinafter referred to as 3HO) , 3-hydroxydecanoate (hereinafter referred to as 3HN), 3-hydroxydecanoate (hereinafter referred to as 3HD), 3-hydroxydodecanoate (hereinafter referred to as 3HDd), 4-hydroxybutyrate (hereinafter It is called 4HB), 4-hydroxyvalerate (hereinafter referred to as 4HV), 5-pivalic acid vinegar (hereinafter referred to as 5 Η V ), and 6-based hexanoic acid S (hereinafter referred to as 6 ΗΗ). The 3-hydroxy acid monomer incorporated into the oxime is a (D) or (R) 3-hydroxy acid isomer, except for the 3HP which does not have a chiral center. In some embodiments, 'PHA can be a homopolymer (all monomer units are the same). Examples of the PHA homopolymer include poly-3-hydroxyalkanoates (for example, poly-3-hydroxypropionate (hereinafter referred to as P3HP), poly-3-hydroxybutyrate (hereinafter referred to as PHB), and poly-3-hydroxyvaleric acid. Ester) 'poly 4-hydroxyalkanoate (for example poly 12 201042103 4-hydroxybutyrate (hereinafter referred to as P4HB) or poly 4-hydroxyvalerate (hereinafter referred to as P4HV)) and poly 5-hydroxyalkanoate (e.g., poly 5-hydroxyvalerate (hereinafter - referred to as P5HV)). In some embodiments, the PHA can be a copolymer (containing two or more different monomer units) in which different monomers are randomly distributed in the polymer chain. Examples of the PHA copolymer include poly-3-hydroxybutyrate-co-3-hydroxypropionate (hereinafter referred to as PHB3HP), poly-3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as PHB4HB) , poly-3-hydroxybutyrate-co--4-hydroxypentanoate (hereinafter referred to as PHB4HV), poly-3-hydroxybutyrate-co-3-hydroxyvalerate S (hereinafter referred to as PHB3HV), Poly 3-hydroxybutyrate-co-3-hydroxyhexanoate (hereinafter referred to as PHB3HH) and poly-3-hydroxybutyrate-co--5-hydroxyvaleric acid ester (hereinafter referred to as PHB5HV). A variety of material properties can be obtained by selecting the monomer type and controlling the ratio of the units in the specified PHA copolymer. Although an example of a PHA copolymer having two different monomer units has been provided, the PHA may have two or more different monomer units (for example, three different monomer units, four different monomer units, and five different monomer units). , 6 different monomer units). Examples of PHAs having 4 different monomer units are PHB-total-3HH-total-3HO-total-3HD or PHB-total-3-HO-total-3HD-total-3HDd (these types of PHA copolymers below) Called PHB3HX). Typically, if PHB3HX has 3 or more monomer units, the shell|J 3HB monomer accounts for at least 70 wt% of all monomers, preferably 85 wt% of all monomers, and preferably accounts for all monomers. 90 wt% or more, for example, 92 wt%, 93 wt%, - 94 wt%, 95 wt%, 96 wt% of the copolymer, and HX contains one or more monomers selected from the group consisting of 3HH, 3HO, 3HD, 3HDd. 13 201042103 Homopolymer (all monomer units are the same) PHB and 3-hydroxybutyrate copolymer containing 3-hydroxybutyrate and at least one other monomer (PHB3HP, PHB4HB 'PHB3HV, PHB4HV, PHB5HV, PHB3HH P 'hereinafter referred to as PHB copolymers' has received particular attention regarding commercial production and applications. It is useful to describe such copolymers by reference to their material properties as follows. Type 1 PHB copolymers typically have a glass transition temperature (Tg) in the range of from 6 °C to -10 °C and a melting temperature TM between 80 °C and 180 °C. The Type 2 PHB copolymer typically has a Tg of from -20 ° C to -50 ° C and a TM of from 55 ° C to 90 ° C. Preferably, the Type 1 PHB copolymer has two monomer units, wherein the majority of the monomer units are 3-hydroxybutyrate monomers, such as greater than 78% 3-hydroxybutyrate, by weight of the copolymer. body. Preferred PHB copolymers of the present invention are bioreactive from regenerative resources and are selected from the group of PHB copolymers: PHB3HV is a Type 1 PHB copolymer wherein the 3HV content is in the range of from 3 wt% to 22 wt% of the polymer, And preferably in the range of 4 wt% to 15 wt% of the copolymer, for example: 4% 3HV, 5% 3HV, 6% 3HV, 7% 3HV, 8% 3HV, 9% 3HV, 10% 3HV, 11% 3HV, 12% 3HV. PHB3HP is a Type 1 PHB copolymer wherein the 3-HP content is in the range of from 3 wt% to 15 wt% of the copolymer, and preferably in the range of from 4 wt% to 15 wt% of the copolymer, for example: 4% 3HP, 5% 3HP, 6% 3HP, 7% 3HP, 8% 3HP, 9% 3HP, 1%% 3HP, 11% 3HP, 12% 3HP. PHB4HB is a Type 1 PHB copolymer in which the 4HB content is in the range of from 3 wt% to 15 wt% of the copolymer 'and preferably in the range of from 4 wt% to 15 wt% of the copolymer, for example: 4% 4HB, 5% 4HB, 6% 4HB, 7% 14 201042103 4HB, 8% 4HB, 9% 4HB, 10% 4HB, 11% 4HB, 12% 4HB, 13% 4HB, 14% 4HB, 15% 4HB. - PHB4HV is a Type 1 PHB copolymer in which the 4HV content is in the copolymer of 3 wt ° /. Up to 15 wt%, and preferably in the range of 4 wt ° / 〇 to 15 wt % of the copolymer, for example: 4% 4 HV, 5% 4 HV, 6% 4 HV, 7% 4 HV, 8% 4 HV 9% 4HV, 1〇% 4HV, 11% 4HV, 12% 4HV, 13% 4HV, 14% 4HV, 15% 4HV. PHB5HV is a Type 1 PHB copolymer wherein the 5HV content is in the range of from 3 wt% to 15 wt% of the copolymer crucible, and preferably in the range of from 4 wt% to 15 wt% of the copolymer, for example: 4% 5HV, 5% 5HV, 6% 5HV, 7% 5HV, 8% 5HV, 9% 5HV, 10% 5HV, 11% 5HV, 12% 5HV, 13% 5HV, 14% 5HV, 15% 5HV. PHB3HH is a Type 1 PHB copolymer in which the 3HH content is in the range of from 3 wt% to 15 wt% of the copolymer, and preferably in the range of from 4 wt% to 15 wt% of the copolymer, for example: 4% 3HH, 5% 3HH, 6% 3HH, 7% 3HH, 8% 3HH, 9% 3HH, 10% 3HH, 11% 3HH, 12% 3HH, 〇13% 3HH, 14% 3HH, 15% 3HH. PHB3HX is a type 1 PHB copolymer, wherein the 3HX content is composed of two or more monomers selected from the group consisting of 3HH, 3HO, 3HD and 3HDd, and the 3HX content is in the range of 3 wt% to 12 wt% of the copolymer, And preferably in the range of 4 wt% to 10 wt ° /〇 of the copolymer, for example: 4% 3HX, 5% 3HX, 6% 3HX, 7% 3HX, 8% 3HX, 9 by weight of the copolymer % 3HX, - 10% 3HX. The Type 2 PHB copolymer has a 3HB content between 80 wt% and 5 wt% of 15 201042103 of the copolymer, such as 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt% of the copolymer, 50 wt%, 45 wt0 / 〇, 40 wt%, 30 wt0 / 〇, 10 wt% 〇 PHB4HB is a type 2 PHB copolymer, wherein the 4HB content is in the range of 20 wt% to 60 wt% of the copolymer, and Preferably, it is in the range of from 25 wt% to 50 wt% of the copolymer, for example, 25% 4HB, 30% 4HB, 35% 4HB, 40% 4HB, 45% 4HB, 50% 4HB by weight of the copolymer. PHB5HV is a Type 2 PHB copolymer in which the 5HV content is in the range of 20 wt% to 60 wt% of the copolymer, and preferably in the range of 25 wt% to 50 wt% of the copolymer, for example, by copolymer Weight, 25% 5HV, 30% 5HV, 35% 5HV, 40% 5HV, 45% 5HV, 50% 5HV. PHB3HH is a Type 2 PHB copolymer in which 3HH is in the range of 35 wt% to 95 wt% of the copolymer, and preferably in the range of 40 wt% to 80 wt% of the copolymer, for example, by weight of the copolymer Calculated, 40% 3HH, 50% 3HH, 60% 3HH, 70% 3HH, 80% 3HH. PHB3HX is a type 2 PHB copolymer in which the 3HX content is composed of two or more monomers selected from the group consisting of 3HH, 3HO, 3HD and 3HDd, and the 3HX content is in the range of 30 wt% to 95 wt% of the copolymer. And preferably in the range of 35 wt% to 90 wt% of the copolymer, for example, by weight of the copolymer, 35% 3HX' 40% 3HX' 50% 3HX ' 60% 3HX ' 70% 3HX ' 80% 3HX , 90% 3HX. The PHA used in the method, composition and granules described in the present invention is selected from the group consisting of: PHB or Type 1 PHB copolymer; PHA blend of PHB and Type 1 PHB copolymer, wherein PHA is blended with PHA The PHB content is in the range of 5 wt% to 95 wt% of the PHA in the PHA blend; 16 201042103 PHA blend of PHB and type 2 PHB copolymer, wherein the weight of the PHA in the PHA blend The PHB content is in the range of 5 wt% to 95 wt% of the PHA in the PHA blend; the PHA blend of the type 1 PHB copolymer and the different type 1 PHB copolymer, and the first type 1 PHB copolymer The content of the substance is in the range of 5 wt ° / 〇 to 95 wt % of PHA in the PHA blend; the PHA blend of the type 1 PHB copolymer and the type 2 PHA copolymer, wherein the content of the type 1 PHB copolymer is PHA blend in the range of 30 wt% to 95 wt% of PHA; PHA blend of PHB with type 1 PHB copolymer and type 2 PHB copolymer, wherein the PHB content is 1 in PHA in the PHA blend. In the range of wt% to 90 wt%, wherein the type 1 PHB copolymer content is in the range of 5 wt% to 90 wt% of the PHA in the PHA blend, and wherein the type 2 PHB copolymer content is in the PHA blend. 5 wt% to 90 wt% range of PHA Inside. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHBP, wherein the PHB content of the PHA blend is in the range of 5 wt〇/〇 to 90 wt% of the PHA in the PHA blend. The 3HP content in the PHBP is in the range of 7 wt% to 15 wt% of the PHBP. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHB3HV, wherein the PHA content of the PHA blend is in the range of from 5 wt% to 90 wt% of the PHA in the PHA blend, and The 3HV content in PHB3HV is in the range of 4 wt% to 22 wt% of PHBV. The PHA blend of PHB and type 1 PHB copolymer may be a blend of PHB and PHB4HB, wherein the PHA content of the PHA blend is in the range of 5 wt% to 90 wt% of the PHA in the PHA blend, and The 4HB content of 17 201042103 in PHB4HB is in the range of 4 wt% to 15 wt% of PHB4HB. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHB4HV, wherein the PHA content of the PHA blend is in the range of 5 wt% to 90 wt% of the PHA in the PHA blend, and The 4HV content in PHB4HV is in the range of 4 wt% to 15 wt% of PHB4HV. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHB5HV, wherein the PHA content of the PHA blend is in the range of 5 wt/〇 to 90 wt% of the PHA in the PHA blend. And the 5HV content in PHB5HV is in the range of 4 wt% to 15 wt% of PHB5HV. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHB3HH, wherein the PHA content of the PHA blend is in the range of from 5 wt% to 90 wt% of the PHA in the PHA blend, and The 3HH content in PHB3HH is in the range of 4 wt% to 15 wt% of PHB3HH. The PHA blend of PHB and Type 1 PHB copolymer may be a blend of PHB and PHB3HX, wherein the PHA content of the PHA blend is in the range of from 5 wt% to 90 wt% of the PHA in the PHA blend, and The 3HX content in PHB3HX is in the range of 4 wt% to 15 wt% of PHB3HX. The PHA blend may be a blend of a Type 1 PHB copolymer selected from the group consisting of PHBP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH, and PHB3HX with a second Type 1 PHB copolymer, the second Type 1 PHB The copolymer is different from the first type 1 PHB copolymer and is selected from the group consisting of PHBP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX, wherein the content of the first type 1 PHB copolymer in the PHA blend is blended. The range of 10 wt% to 90 wt% of all PHA in the compound. 18 201042103 The PHA blend of PHB and Type 2 PHB copolymers can be a blend of PHB and PHB4HB, wherein the PHB content of the PHA blend is between 30 wt% and 95 wt% of the PHA in the PHA• blend. Within the range, and the 4HB content in PHB4HB. is in the range of 20 wt% to 60 wt% of PHB4HB. The PHA blend of PHB and Type 2 PHB copolymer may be a blend of PHB and PHB5HV, wherein the PHB content of the PHA blend is in the range of 30 wt% to 95 wt% of the PHA in the PHA blend, And the 5HV content in PHB5HV is in the range of 20 wt% to 60 wt% of PHB5HV. The PHA blend of PHB and Type 2 PHB copolymer may be a blend of PHB and PHB3HH, wherein the PHB content of the PHA blend is in the range of 35 wt% to 95 wt% of the PHA in the PHA blend. And the 3HH content in PHB3HH ' is in the range of 35 wt% to 90 wt% of PHB3HX.

The PHA blend of PHB and Type 2 PHB copolymer may be a blend of PHB and PHB3HX, wherein the PHB content of the PHA blend is in the range of 30 wt% to 95 wt% of the PHA in the PHA blend, And the 3HX content in PHB3HX is in the range of 35 wt% to 90 wt% of PHB3HX. 0 PHA blend can be a blend of PHB with type 1 PHB copolymer and type 2 PHB copolymer, wherein the PHB content of the PHA blend is between 10 wt% and 90 wt% of the PHA in the PHA blend. In the range, the PHA blend type 1 PHB copolymer content is in the range of 5 wt% to 90 wt% of PHA in the PHA blend, and the type 2 PHB copolymer content in the PHA blend is blended in PHA The range of 5 wt% to 90 wt% of the PHA in the compound. - For example, the PHA blend may have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, 19 201042103 PHA 5 in the PHA blend PHB3HV content in the PHA blend in the range of wt% to 90 wt%, wherein the 3HV content in PHB3HV is in the range of 3 wt% to 22 wt% of PHB3HV, and 5 wt% of PHA in the PHA blend The PHBHX content in the PHA blend in the range of % to 90 wt%, wherein the 3HX content in PHBHX is in the range of 35 wt% to 90 wt% of PHBHX. For example, the PHA blend can have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, and 5 wt ° of the PHA in the PHA blend. The content of PHB3HV in the PHA blend in the range of 90 wt%, wherein the 3HV content in PHB3HV is in the range of 3 wt% to 22 wt% of PHB3HV, and 5 wt% of PHA in the PHA blend. The PHB4HB content in the PHA blend to a range of 90 wt%, wherein the 4HB content in PHB4HB is in the range of 20 wt% to 60 wt% of PHB4HB. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, 5 wt% of the PHA in the PHA blend to PHB3HV content in the PHA blend in the range of 90 wt%, wherein the 3HV content in PHB3HV is in the range of 3 wt% to 22 wt% of PHB3HV, and 5 wt% to 90 of PHA in the PHA blend. The PHB5HV content in the PHA blend in the wt% range, wherein the 5HV content in the PHB5HV is in the range of 20 wt% to 60 wt% of the PHB5HV. For example, the PHA blend can have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, 20 201042103 5 wt of PHA in the PHA blend. PHB4HB content in the PHA blend in the range of % to 90 wt%, wherein the 4HB content in PHB4HB is in the range of 4 wt% to 15 wt% of -PHB4HB, and 5 wt% of PHA in the PHA blend The PHB4HB content in the PHA blend in the range of % to 90 wt%, wherein the 4HB content in PHB4HB is in the range of 20 wt% to 60 wt% of PHB4HB. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, and 5 wt% of the PHA in the PHA blend. PHB4HB content in the PHA blend to a range of 90 wt%, wherein the 4HB content in PHB4HB is in the range of 4 wt% to 15 wt% of PHB4HB, and 5 wt% of PHA in the PHA blend The PHB5HV content in the PHA blend to the range of 90 wt% and wherein the 5HV content in the PHB5HV is in the range of 30 wt% to 90 wt% of PHB5HV. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt ° / Torr of the PHA in the PHA blend, 〇 5 in the PHA blend. PHB4HB content in the PHA blend in the range of wt% to 90 wt%, wherein the 4HB content in PHB4HB is in the range of 4 wt% to 15 wt% of PHB4HB, and 5 wt% of PHA in the PHA blend The PHB3HX content in the PHA blend in the range of % to 90 wt% and wherein the 3HX content in PHB3HX is in the range of 35 wt% to 90 wt% of PHB3HX. - For example, the PHA blend may have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, 21 201042103 PHA 5 in the PHA blend PHB4HV content in the PHA blend in the range of wt% to 90 wt%, wherein the PHB4HV tenth HV content is in the range of 3 wt% to 15 wt% of PHB4HV, and 5 wt% of PHA in the PHA blend The PHB5HV content in the PHA blend in the range of % to 90 wt%, wherein the 5HV content in the PHB5HV is in the range of 30 wt% to 90 wt% of the PHB5HV. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, 5 wt% of the PHA in the PHA blend to PHB3HH content in the PHA blend in the range of 90 wt%, wherein the 3HH content in PHB3HH is in the range of 3 wt% to 15 wt% of PHB3HH, and 5 wt% to 90 of PHA in the PHA blend. The PHB4HB content in the PHA blend in the range of wt%, wherein the 4HB content in PHB4HB is in the range of 20 wt% to 60 wt% of PHB4HB. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, 5 wt% of the PHA in the PHA blend to PHB3HH content in the PHA blend in the range of 90 wt%, wherein the 3HH content in PHB3HH is in the range of 3 wt% to 15 wt% of PHB3HH, and 5 wt% to 90 of PHA in the PHA blend. The PHB5HV content in the PHA blend in the wt% range, wherein the 5HV content in the PHB5HV is in the range of 20 wt% to 60 wt% of the PHB5HV. For example, the PHA blend can have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, 22 201042103 5 wt of PHA in the PHA blend. The PHB3HH content in the PHA blend in the range of % to 90 wt%, wherein the 3HH content in the PHB3HH is in the range of 3 wt% to 15 wt% of the PHB3HH, and 5 wt% of the PHA in the PHA blend. The PHB3HX content in the PHA blend in the range of % to 90 wt%, wherein the 3HX content in PHB3HX is in the range of 35 wt% to 90 wt% of PHB3HX. For example, the PHA blend can have a PHB content in the PHA blend in the range of from 10% to 90% by weight of the PHA in the PHA blend, 5 5 wt of PHA in the PHA blend. PHB3HX content in the PHA blend in the range of % to 90 wt%, wherein the 3HX content in PHB3HX is in the range of 3 wt% to 12 wt% of PHB3HX, and 5 wt% of PHA in the PHA blend The PHB3HX content in the PHA blend to the range of 90 wt%, wherein the 3HX content in PHB3HX is in the range of 35 wt% to 90 wt% of PHB3HX. For example, the PHA blend can have a PHB content in the PHA blend in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, and 5 wt% of the PHA in the PHA blend. a PHB3HX content in the PHA blend to a range of 90 wt%, wherein the 3HX content in PHB3HX is in the range of 3 wt% to 12 wt% of PHB3HX, and 5 wt% of PHA in the PHA blend to The PHB4HB content in the PHA blend in the range of 90 wt%, wherein the 4HB content in PHB4HB is in the range of 20 wt% to 60 wt% of PHB4HB. - For example, the PHA blend may have a PHB content in the PHA blend in the range of from 10 wt% to 90 wt% of the PHA in the PHA blend, 23 201042103 PHA 5 in the PHA blend PHB3HX content in the PHA blend in the range of wt% to 90 wt%, wherein the 3HX content in PHB3HX is in the range of 3 wt% to 12 wt% of PHB3HX, and 5 wt% of PHA in the PHA blend The PHB5HV content in the PHA blend in the range of % to 90 wt%, wherein the 5HV content in the PHB5HV is in the range of 20 wt% to 60 wt% of the PHB5HV. The PHA conjugate can be a blend as disclosed in U.S. Published Application No. US 2004/0220355, the entire disclosure of which is incorporated herein by reference. A microbial system for the production of a PHB copolymer, PHBV, is disclosed in U.S. Patent 4,477,654, the entire disclosure of which is incorporated herein. PCT Patent Publication No. WO 02/08428 to Skraly and Sholl describes a system suitable for producing PHB copolymer PHB4HB. Suitable methods for producing the PHB copolymer PHB3HH have been described (Lee K, Biotechnology and Bioengineering, 67: 240-244 (2000); Park et al, Biomacfomolecules, 2: 248-254 (2001)). The method of producing the PHB copolymer PHB3HX has been described by Matsusaki et al. (^fomacromo/ecM/es, 1: 17-22 (2000)).

In the measurement of the molecular weight, a technique such as gel permeation chromatography (GPC) can be used. In this method, polystyrene standards are used. The PHA may have a polystyrene equivalent weight average 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. . In some embodiments, preferably, the PHA generally has a weight average molecular weight in the range of from 100,000 to 700,000. For example, the molecular weight ranges of the PHB 24 201042103 and Type 1 PHB copolymers used in the present application range from 400,000 Daltons to 1.5 x 10 6 Daltons as determined by the GPC method, and are used in the present application. The type 2 ruthenium copolymer has a molecular weight ranging from 100,000 Daltons to 1.5 Χ 106 Daltons. In certain embodiments, when the nucleating agent additionally comprises a polymer, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a ruthenium or a type 1 ruthenium copolymer, such as ruthenium, osmium, iridium, PHB3HV, PHB4HV, PHB5HV, ΡΗΒ3ΗΗ or ΡΗΒ3ΗΧ.更 In a more specific embodiment, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently PHB; PHB3HV, wherein the 3HV content is between 2 wt% and 22 wt ° / 聚合物 of the polymer In the range; ΡΗΒ3ΗΡ, wherein 3HP content is in the range of 3 wt% to 15 wt% of the polymer; PHB4HB, wherein 4HB content is in the range of 3 wt/〇 to 15 wt% of the polymer; PHB4HV, wherein 4HV content In the range of 3 wt% to 15 wt% of the polymer; PHB3HH, wherein the 3HH content is in the range of 3 wt% to 15 wt% of the polymer; or PHB3HX, wherein 3HX content is 3 wt% in the polymer t) Up to 12 wt%. The indicated percentage ranges from the weight percent of monomer to the total weight of the polymer. For example, for PHB4HB having a 3% to 15% 4HB content, 3% to 15% by weight of the total PHB4HB polymer is 4-hydroxybutyrate. In certain embodiments, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a blend of PHB and a type 1 PHB copolymer, the type 1 PHB copolymer Selected from the following group · PHB3HV, wherein the 3HV content is in the range of 2 wt ° /〇 to 22 wt% of the polymer; PHB3HP, 25 201042103 wherein 3HP content is in the range of 3 wt% to 15 wt% of the polymer PHB4HB, wherein 4HB content is in the range of 3 wt% to 15 wt% of the polymer; PHB4HV, wherein 4HV content is in the range of 3 wt% to 15 wt% of the polymer; PHB3HH, wherein 3HH content is in the polymer 3 wt% to 15 wt%; or PHB3HX, wherein the 3HX content is in the range of 3 wt% to 12 wt% of the polymer. In certain embodiments, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a blend of PHB and a Type 2 PHB copolymer selected from the group consisting of Group: PHB4HB, wherein 4HB content is in the range of 20 wt% to 60 wt% of the polymer; PHB3HH, wherein 3HH content is in the range of 35 wt% to 90 wt% of the polymer; PHB5HV, wherein 5HV content is copolymerized In the range of 20 wt% to 60 wt%; or PHB3HX, wherein the 3HX content is in the range of 30 wt% to 90 wt% of the copolymer. In a more specific embodiment, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a) PHB and b) a blend of PHB4HB having a 5% to 15% 4HB content; PHB and b) a blend of PHB3HV having a 5% to 22% 3HV content; a) a blend of PHB and b) PHB3HH having a 3% to 15% 3HH content; a) PHB and b) having 3% a blend of PHB3HX to a 12% 3H content; a) a blend of PHB and b) having a 5% to 15% 5 HV content of PHB5HV; a) a PHB4HB having a 5% to 15% 4HB content and b) having 5 a blend of PHB3HV with a % to 22% 3HV content; a) a blend of PHB4HB having a 5% to 15% 4HB content and b) a blend of PHB3HH having a 3% to 15% 3HH content 26 201042103; or a) having 5 % to 22% of the 3-hydroxyvalerate content of PHB3HV and b) a blend of polyPHB3HV having a 3% to 15% 3HH content. - In other specific embodiments, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a) a blend of PHB and b) PHB4HB, and the weight of polymer a) is polymerized 5% to 95% by weight of the combination of a) and polymer b); a) a blend of PHB and b) PHB3HV, and the weight of polymer a) is the combined weight of polymer a) and polymer b) a blend of 5% to 95%; &)?1« and 1))?1^31111, and the weight of the polymer 〇a) is 5% by weight of the combined weight of the polymer a) and the polymer b) To 95%; a) a blend of PHB4HB and b) PHB3HV, and the weight of polymer a) is from 5% to 95% by weight of the combined weight of polymer a) and polymer b); a) 'PHB4HB and b) a blend of PHB3HH, and the weight of polymer a) is from 5% to 95% by weight of the combined weight of polymer a) and polymer b); or a) a blend of PHB3HV and b) PHB3HH, and polymer a The weight of the polymer comprises from 5% to 95% by weight of the combined weight of polymer a) and polymer b). In other specific embodiments, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a) PHB and b) a blend of PHB4HB having a 20%-60% 4-HB content. a) PHB and b) a blend of PHB5HV having a 20% to 60% 5HH content; a) a blend of PHB and b) PHB3HH having a 35%-95% 3-HH content; a) having 3 % to 15% of the 4HB content of PHB4HB and b) a blend of PHB4HB with 20%-60°/〇4HB; a) PHB4HB with 3% to 15% 4-hydroxybutyrate content and b) with 20% a blend of PHB5HV to 60% 5HV content; a) a blend of PHB4HB having a content of 3% to 15% 4HB and b) a blend of PHB3HX having a content of 30%-90°/〇3HX of 27 201042103; a) having 3% to 22% 3HV content of PHB3HV and b) blend of PHB4HB having a 20%-60°/〇4HB content; a) PHB3HV with 3% to 22% 3HV content and b) 20% to 60% a blend of 5 HV content of PHB5HV; a) a blend of PHB3HV having a 3% to 22% 3 HV content and b) a PHB3HH having a 35%-90% 3-HH content; a) having 3. /. PHB3HH with a content of 15% 3HH and b) a blend of PHB4HB with a content of 20%-60% 4HB; a) PHB3HX with a content of 3% to 12% 3HX and b) PHB4HB with a content of 20%-60% 4HB a blend; a) a blend of PHB3HX having a 3% to 12% 3H content and b) a PHB5HV having a 20% to 60% 5HV content; a) having 3. /. a blend of PHB3HH with 15% 3HH content and b) PHB5HV with 20% to 60% 5-HV; a) PHB3HH with 3% to 15% 3HH content and b) with 30% to 90% 3HX content a blend of PHB3HX; or a) a blend of PHB3HH having a 3% to 15% 3HH content and b) a PHB3HH having a 35%-90% 3HH content. In a more specific embodiment, the carrier polymer and/or matrix polymer or polymer (if applicable) are each independently a blend of PHB with a Type 1 PHB copolymer and a Type 2 PHB copolymer, wherein the PHA blends The PHB content in the PHA blend is in the range of 10 wt% to 90 wt% of the PHA in the PHA blend, and the PHA blend type 1 PHB copolymer content is 5 wt/〇 to 90 in the PHA blend. Within the range of wt%, and the content of the type 2 PHB copolymer in the PHA blend is in the range of from 5 wt% to 90 wt% of the PHA in the PHA # compound. In the specific example described in the description of polymer a) and b) or a blend of two polymer components, the copolymer blend comprises polymer a) and polymerization. And b), wherein the weight of the polymer a) is from 2% to 6% by weight of the combined weight of the polymer (VIII) and the polymer b), and the weight of the polymer b) is ^ σ a) and the polymer b) 40% to 80% of the combined weight. In other embodiments, the blend of the polymer described herein (eg, comprising polymer a) and polymer b) or otherwise blending the two polymer components) comprises a third Polymer-polymer c), the polymer c) is PHB4HB having a content of 20% to 60% 4HB. In other embodiments, the blend of the polymer described herein (eg, comprising polymer a) and polymer b) or otherwise blending the two polymer components) comprises a third Polymer-polymer c), the polymer c) is pHB5Hv having a content of 2% to 6% by 5HV. In other specific examples, the blend of the polymer blends described herein (eg, comprising polymer a) and polymer b) or otherwise describing the blend of the two polymer components) comprises a third Polymer-polymer c), the polymer c) is PHB3hh having a content of 5% to 5% by 3hh. In other embodiments, the copolymer blend comprises polymer a), polymer b), and polymer c). In a particular embodiment, wherein the weight of polymer e) is from 5% to 95% by weight of the combined polymer of polymer a), polymer b) and polymer c). In other embodiments, the weight of polymer c) is from 5% to 40% by weight of the combined polymer of polymer a), polymer b) and polymer c). Biodegradable aromatic-aliphatic polyester PHA It can be combined with another polymer or several other polymers. For example 29 201042103

It may be combined with - or a plurality of biodegradable aromatic wax polyesters. The specific composition is discussed, for example, in the "M96 Wegradable PGlyester Biends", which is filed on May 6 测, the entire disclosure of which is incorporated herein by reference. The non-biodegradable aromatic polyester is synthesized by polycondensing a genomic diol with an aromatic diremediation acid. The aromatic ring is resistant to hydrolysis' thereby preventing biodegradability. Polyethylene terephthalate (ΡΕΤ) and polybutylene terephthalate (Bin) are formed by polycondensation of an aliphatic diol and terephthalic acid. The biodegradability of the aromatic polymer can be changed by adding a monomer which is not resistant to hydrolysis, an aliphatic diol or a diacid group. The addition of such hydrolysis sensitive monomers produces a weak point of solution. The glutinous glutinous glutamate can also be prepared by polycondensation of a quinone-based alcohol with a noble compound of an aromatic and aliphatic dicarboxylic acid by gt «« γ 1 K J J straw. For example, upgrading PBT by adding an aliphatic dibasic acid produces polysuccinic acid/p-phenylene b-butane bisacetate (PBST) (as butanediol and succinic acid as aliphatic diols and An alternative to benzodiazepines. Another example is the family of poly-supplements sold under the trade name BK) MAX® (du P), which is based on PET and various aliphatic acid monomers (such as dimethyl glutaric acid). Diethylene glycol polymerization. In the synthesis of polyadipate/terephthalate (PBAT), the butanol is a diol, and the acid is adipic acid and p-dibenzoic acid. Commercial examples include ECOFLEX 8 (BASF) and ε_γ ^ (^ coffee,). The ECOFLEX has a smelting temperature (Tm) of about 110 C as measured by differential scanning calorimetry (DSC). Another example is polyadipate/butylene terephthalate (PTMAT) synthesized from butanediol and adipic acid 30 201042103 and terephthalic acid. Biodegradable polymers therefore include polyesters containing aliphatic components. One of the poly- vinegars is an ester polycondensate containing an aliphatic component and a poly(hydroxycarboxylic acid). The ester poly-condensate may include a diacid/glycol aliphatic polyester (such as polybutylene succinate, polybutylene succinate-co-adipate) 'aliphatic/aromatic polyester (such as a terpolymer prepared from butylene glycol, adipic acid and terephthalic acid). Poly(hydroxycarboxylic acid) includes lactic acid-based homopolymers and copolymers, polybutyl butyrate (PHB) or other polyhydroxyalkanoate homopolymers and copolymers. Such polyhydroxyalkanoates 包括 include copolymers of PHB with longer chain length monomers such as c6_Ci2 and longer. Examples of biodegradable aromatic-aliphatic polyesters thus include, but are not limited to, PET and PBT with aliphatic diacids, diols or incorporated into the polymer backbone to render the copolyester biodegradable or decomposable. Various copolyesters via base acids; and various derivatives derived from monobasic acids (eg, succinic acid, glutaric acid, adipic acid, sebacic acid, sebacic acid or derivatives thereof, such as alkyl esters, acid chlorides or Aliphatic polyesters and copolyesters of anhydrides, diols such as ethylene glycol, propylene glycol, hydrazine, 4-butanediol, hydrazine, 6-hexanediol or hydrazine, 4-cyclohexanol.实例 An example of a commercially available di-branched/glycol aliphatic polyester by showa High

Polybutylene succinate/butylene adipate copolymer sold by Polymer Company, Ltd. (T〇ky0, Japan) under the BIONOLLE® 1000 and BIONOLLE® 3000. Examples of commercially available aromatic-aliphatic copolyesters are poly(adipate-co-p-benzoic acid dibutylate) sold by Chemical as EASTAR BI0® copolyester or by BASF as ec〇flex8. . The biodegradable aromatic-aliphatic polyester can be a copolyester. It may itself be a blend of such polyesters or copolyesters. 31 201042103 PHA and Biodegradable Formula - Aliphatic Polyacetate The PHA and biodegradable aromatic-aliphatic polyester can be combined to prepare a blend of polymers. Such blends are discussed, for example, in U.S. Patent Application Serial No. 61/050,896 ("Biodegradable p〇lyester Blends") and PCT Patent Publication No. WO 2009/137058, filed May 5, 2008. The entire teachings of this specification are incorporated herein by reference. The amount of PHA in the overall blend can be about! Wt%, about 5 wt〇/〇, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about % wt%, about 35 wt%, about 40 wt%, about 45 wt%, About 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 7 wt%, about 75, about 8 〇, about 85 wt%, about 90 wt%, about 95 wt%, or about 99 Wt%. As will be appreciated by those skilled in the art, the choice and amount of each polymer will affect the softness, hardness, texture, toughness and other characteristics of the final product. Typically, the PHA component will be about 10% in the blend based on the total weight of the total polymer component. To 95/. Preferably, from about 15% to about 85%' more preferably from about 2G% to about the amount. Each of the polymer components may contain a single polymer material or a blend of two or more of the above materials. For example, and the pHA component can be converted to a blend of PHA materials as described above. Likewise, the biodegradable aromatic-aliphatic polyester group can be a mixture or blend of biodegradable aromatic-aliphatic polyesters. Methods of making and using thermoplastic compositions are well known to those skilled in the art, and skilled artisans will appreciate that the biodegradable blends I of the present invention are useful in a variety of applications, and further, as known to those skilled in the art, It may contain - or a plurality of additives 'eg plasticizer 'nucleating agent' filler, anti-32 201042103 oxidant, UV stabilizer burner and/or antistatic agent. Lubricants, Slip/Tackifier Pigments, Resistant Preparation, and Process Biodegradable Blend Compositions Biodegradable blend compositions can be prepared using any of the art known, including the addition of biodegradable to thermoplastic materials. Polyester II will (4) Degradable aromatic-aliphatic polyester vinegar added to the thermoplastic substance in the form of dry biodegradable two. Degradation (4) Formulation

The optimum amount to be added should be based on various factors known to the skilled person, such as cost, desired physical characteristics of the thermoplastic (e.g., mechanical strength), and the type of processing being performed (peeling, for example, considering line speed, circulation). Number of times and other processing parameters). It is also contemplated whether the thermoplastic composition includes potting additives such as plasticizers, stabilizers, pigments, fillers, reinforcing agents and/or mold release agents. In general, however, the biodegradable aromatic aliphatic polyester may be included in the thermoplastic composition such that the composition 3 has from about 5% to about 95% 'e.g., from about 5% to about 5% by weight based on the total weight of the composition. 9G%, from about 2G% to about 8% by weight of biodegradable aromatic aliphatic polyester. In certain embodiments of the invention, the composition contains from about 1% to about 1%, such as from about 1% to about 5%, of a biodegradable aromatic-ratrix polyester. Branched Chain Polyhydroxyalkanoates The branched chain pHA compositions used in the methods and compositions described herein improve the melt strength of PHA, a property required for a variety of polymer product applications. Melt strength is a rheological property that can be measured in a variety of ways. One amount of G G is the polymer storage modulus measured at the solution processing temperature. 33 201042103 In certain embodiments, a branched polyhydroxyalkanoate polymer is used to prepare a nonwoven material as described herein. These branched polyhydroxyalkanoates have better thermal stability than unbranched polyhydroxyalkanoate polymers. The polyhydroxyalkanoate polymer is made into a branch using a parenting agent (also referred to as an adjuvant) containing two or more reactive functional groups such as an epoxy group or a double bond. The characteristics of this 4 parental agent § Zhou Lang polymer. These characteristics include, but are not limited to, melt strength or toughness. One type of crosslinking agent is an "epoxy-functional compound." As used herein, "epoxy-functional compound" is intended to include having 2 or more oximes sufficient to increase the degree of aggregation by causing the polyhydroxy sulphonate polymer to branch (eg, end-force branching) as described above. A compound of an epoxy group having a solution strength of a sukidonic acid polymer. When an epoxy functional compound is used as a crosslinking agent in the disclosed process, a branching agent is optionally employed. Thus, a specific example of a branch includes reacting a starting polyhydroxyalkanoate polymer (pHA) with an epoxy functional compound. Alternatively, another method of branching comprises reacting the starting polyhydroxyalkanoate polymer, a branching agent, with an epoxy functional compound. Alternatively, another method of branching involves reacting the starting PHA with an epoxy functional compound in the absence of a branching agent. The epoxy functional compounds may include epoxy functional styrene-acrylic polymers such as, but not limited to, for example, j〇ncryl® adR_4368 (BASF) or MP-40 (Kaneka), containing as side chains. Incorporated glycidyl acrylic and/or polyolefin copolymers and polymeric polymers such as, but not limited to, for example, LOTADER® (Arkema), poly(ethylene-glycidyl methacrylate-co-methacrylate) )), and epoxidized oil (such as (but not limited to 34 201042103) such as epoxidized soybean oil, eucalyptus oil, linseed oil, oil, peanut oil, coconut oil, algae oil, cod liver oil or mixtures thereof, for example • MERGINAT® ESBO (Hobum, Hamburg, Germany) and EDENOL® B 316 (Cognis, Dusseldorf, Germany)). For example, reactive acrylic acid or a functional acrylic crosslinker is used to increase the molecular weight of the polymer in the branched polymer composition described herein. These crosslinkers are commercially available. For example, BASF sells a variety of compounds under the trade name "JONCRYL®", which is described in U.S. Patent No. 6,984,694 to the name of "Loligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications. This patent is incorporated herein by reference in its entirety. One such compound is JONCRYL® ADR-4368CS, which is glycidyl styrene methacrylate and is discussed below. The other is MP-40 (Kaneka). The other is the "Petra" series from Honeywell, see, for example, U.S. Patent No. 5,723,730. These polymers are commonly used in plastic recycling (e.g., for recirculating recycled polyethylene terephthalate) to increase the molecular weight of the polymer being recycled (or to simulate an increase in molecular weight). These polymers often have the following general structure: 35 201042103

H2c

Rl and R2 are independently H or alkyl R3 is alkyl X and Y is 1-20 ζ is 2-20. The base is CVCs. Without wishing to be bound by theory, the salty epoxy functional acrylic acid can produce poly Sg. Branching, and effectively repairing the mussel damage (specifically, melt strength G, decreased) of the molecular weight of the polyester in the extruder. The epoxy functional compound can also increase the thermal stability of the polyhydroxyalkanoate polymer by preventing it from breaking. Pont·Ι· du Pont de Nemours & Company sells the active compound of the formula under the trade name Elvaloy®, which is an ethylene copolymer such as a acrylate copolymer, an elastomeric binary copolymer and other copolymers. One such compound is Elvaloy PTW which is a copolymer of ethylene-n-butyl acrylate and methacrylic acid glycidyl alcohol. 〇mnova sells similar compounds under the trade names "SX64053", "SX64〇55" and "SX64056". Other entities also sell these compounds. The specific polyfunctional polymeric compound having a reactive epoxy group is a styrene-acrylic acid copolymer and oligomer containing a glycidyl group incorporated as a side chain of 36 201042103. A number of suitable examples are described in "Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, and applications" by Blasius et al., which is incorporated herein by reference in its entirety. in. These materials are based on oligomers having styrene and propionate structural units having a glycidyl group incorporated as a side chain. A higher number of epoxy groups can be used per oligo chain, for example at least 10, greater than 15 or greater than 20. Such polymeric materials generally have a molecular weight greater than 3,000, specifically greater than 4 Å and more specifically greater than (9) (VIII). Such materials are available from Johns〇n p〇lymer, LLC (currently owned by BAM) under the trade name J0NCRYL®, ADR 4368. Other types of polyfunctional polymer materials having a plurality of epoxy groups are propanolic acid and/or polybutanyl copolymers containing glycidyl groups incorporated as side chains and oligomerization = polyfunctional carboxyl group activity Another example of the material is a copolymer comprising a unit of ethylene and:: C: acid glycidol vinegar (GMA) or a ternary congregation, a trader which can be sold by Arkema; a trader of the same τ sold by the name LOTADER® Resin purchase of this # material can be further Taiwan will be r ( ( (a) not glycidyl methacrylic acid co-methyl acrylate). W-based acrylic acid-glycid vinegar - an example of an oil containing an epoxy group (an oil which is epoxidized, a fatty acid ester of glutaryl hexahydrate or a natural one, A) is also used. A mixture of palm oil, peanut oil, flaxseed oil, and larger compounds. Especially preferred are production =, cod liver oil or this..., oxidized soybean oil (for example, 37 201042103 from Hobum, Hamburg's Merginat® ESBO or from Cognis , Edenol® B 3 1 6 ) of Dusseldorf, but other oils may also be used. As used herein, "epoxy-functional compound" is intended to include having a polyhydroxyalkanoate capable of being branched by a terminal chain as described above. A compound of epoxy functional group having a polymer strength. The epoxy functional compounds may include an epoxy functional styrene-acrylic polymer such as, but not limited to, for example, JONCRYL® ADR-4368 (BASF) Or MP-40 (Kaneka)), acrylic acid and/or polyfeene copolymers and oligomers containing glycidyl groups incorporated as side chains (such as, but not limited to, for example, LOTADER® (Arkema), poly ( Ethylene_methyl propyl Acid glycidyl ester _ co-mercapto acrylate)), and epoxidized oil (such as, but not limited to, for example, epoxidized soybean oil, olive oil, linseed oil, palm oil, peanut oil 'coconut oil algae oil, cod liver oil Or a mixture thereof, such as Merginat® ESBO (Hobum, Hamburg, Germany) and Edenol® B 316 (c〇gnis, Dusseldorf, Germany) o In general, it appears that a compound having a terminal epoxy group may be located than an epoxy group. Compounds elsewhere on the molecule perform better. Nucleating agents are selected from the group consisting of boron nitride, melamine stone, clay 'carbonic acid, the nucleating agent acid or related compound of the methods and compositions herein, carbon black, Mica talc synthesizes tannic acid and salt, organic phosphate-brown metal salt 'kaolin and possibly other materials. In a specific composition and method, the nucleating agent is boron nitride. In a preferred embodiment, medium wet grinding nucleation The agent will produce a nucleating agent that is wet milled. The liquid carrier has a nucleating agent that is significantly lower than the particle size obtained by standard jet milling 38 201042103. In some embodiments, the sizing agent Wet grinding to less than 20 microns. 湿 Wet grinding can be carried out, for example, in a KD5 Dyno type grinder, which is a horizontal grinder with a mixing volume capacity of 1 · 5 liters. Any equivalent grinder can be used. KD5 The Dyno mill can be used in batch or continuous loop mode. The mixing horizontal chamber accommodates a central horizontal axis to which is attached a polyurethane paddle stator that provides a wraparound drive 0 to agitate Grinding media (typically, for example, ceramic beads of 0.4 mm to 1.2 mm, having a narrow size distribution range). As described herein, the mixing chamber can be filled with mm-0.8 mm zirconia beads to a volumetric capacity of about 8% to 85% by volume. The shaft speed can be set to, for example, 24 rpm. The liquid medium (carrier) can be pumped through the chamber while agitating the beads. This operation achieves a grinding action. The residence time is controlled by the external flow rate of the liquid medium. The milling efficiency is controlled by the bead size, the number of revolutions per minute of the shaft, and the retention phase of the material in the chamber (i.e., related to the flow rate). The liquid is discharged from the grinder via an angular slot die which is sufficiently small to retain the grinding media (beads) while allowing liquid to flow through the gap (typically, for example, less than 5% to 25% of the diameter of the grinding media). Nucleating agents for various polymers may include simple substances; metal compounds 'including composite oxides' such as carbon black, carbon strontium calcium, synthetic tannins and salts, vermiculite zinc white, clay, kaolin, alkaline magnesium carbonate, Mica, talc, ''day algae earth, dolomite powder, titanium oxide, zinc oxide, cerium oxide, barium sulfate, sulfuric acid, oxidized Shao, Shixi (four), metal salt of organic phosphate and boron trioxide; with metal tannic acid a low molecular organic compound of a salt group, such as 'such as caprylic acid, toluic acid, heptanoic acid, citric acid, dodecanoic acid, fourteen 39 201042103 alkanoic acid, palmitic acid stearic acid, behenic acid, wax Metal salts of acid, montanic acid, icosonic acid, present formic acid, p-t-butylbenzoic acid, terephthalic acid, p-benzene-formic acid monomethyl sulphate, isophthalic acid and monomethyl isophthalate a high molecular organic compound having a metal carboxylate group, for example, a metal salt such as the following: a thiol-containing polyethylene obtained by oxidizing polyethylene, a carboxyl group-containing polypropylene obtained by oxidizing polypropylene, an olefin (such as ethylene, propylene and 1-butene) and Copolymer of acrylic acid or mercaptoacrylic acid, copolymer of styrene and acrylic acid or methacrylic acid, copolymer of olefin and maleic anhydride, and copolymer of styrene and maleic anhydride; polymer organication a person, for example, an olefin having a branch at the 3-position carbon atom and having not less than 5 carbon atoms, such as 3,3-dimercaptobutene-L3·decylbutene-丨, 3-methylpentane Alkene-1,3-methylhexene-1 and 3,5,5-trimethylsulfonium-hexene; vinylcycloalkane (such as vinylcyclopentane, vinylcyclohexane and vinyl thiophene) a polymer of (vinylnorbornane)); a polyalkylene glycol such as polyethylene glycol and polypropylene glycol; poly(glycolic acid); cellulose; a cellulose ester; and a cellulose ether; a phosphoric acid or a phosphorous acid and a metal salt thereof, such as Diphenyl phosphate, diphenyl phosphite, metal salt of bis(4-t-butylphenyl)phosphate and bis-p*-butylphenyl)methylene phosphate; sorbitol derivatives, such as Bis(p-metriphenyl) sorbitol and bis(p-ethylbenzylidene) sorbitol; and sulfur = glycolic anhydride, p-toluenesulfonic acid and Its metal is flawed. The above nucleating agents may be used singly or in combination with each other. In some embodiments, the nucleating agent: two other poly(s) (e.g., polymeric nucleating agents such as PHB). The amount of the nucleating agent in the liquid carrier is from $wt% to 50% by weight of the nucleating agent-liquid carrier composition, preferably in the combination of the nucleating agent and the liquid carrier. 2 0 201042103 wt% to 45 Wt%, better accounted for 3〇~% to 4〇wi%, and the best accounted for w(9). Liquid carriers are typically used in combination with a nucleating agent. The liquid carrier allows full grinding of the nucleating agent. After wet grinding the nucleating agent in a liquid carrier, and then adding an appropriate amount of liquid carrier nucleating agent to the polymer to be processed. Generally, those skilled in the art of polymer compounding know from experience that nucleating agents and liquid carriers (ie, plasticizing agents, surfactants, etc.) are suitable for use, so it is possible to set ten for their characteristics. The ratio of nucleating agent to liquid carrier required. The choice of liquid carrier is important because when a nucleating agent is added, the carrier becomes the integral component of the cerium in the polymer formulation. In the poly-3-aminobutyric acid vinegar composition, for example, when a plasticizer is often used to change the glass transition & degree and modulus of the composition, it is also possible to use a surfactant, for example, in an injection. Lubricants can also be used in molding applications. The M, the interface/tongue agent and the lubricant can therefore all be used as a liquid carrier for the grinding nucleating agent. π你凤例包==The liquid carrier of the grinding nucleating agent can be a plasticizer. The actual adjacent to the plasticizer [methylhydrazine limited) ortho-dicarboxylic acid compound (including but not limited to: the present formic acid ", phthalic acid diethylene, phthalate 5 曰, neighbor 2 Dihexyl formate, m. - 7 r μ. β-di-n-octyl octyl ester, phthalic acid ester - monoisooctyl formate, dioctanoic acid phthalate ... ^ phthalic acid diisoindole vinegar , phthalate, styrene, bismuth - 酉 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Benzyl phthalate, S, S, octyl phthalate 41 201042103 Octyl phthalate, octyl phthalate, n-hexyl phthalate Ester, n-octyl phthalate and ruthenium phthalate), phosphate compounds (including but not limited to tridecyl phenyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl phosphate) , toluene diphenyl phosphate and triethyl phosphate), adipic acid compounds (including but not limited to dibutoxyethoxyethyl adipate (DBEEA), adipic acid II Ester, diisooctyl adipate, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, n-octyl adipate, n-heptyl adipate and n-heptyl adipate Azelaic acid adipate), azelaic acid compounds (including but not limited to dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate and butyl phthalate) Azelaic acid compound, citric acid compound (including but not limited to) triethyl citrate, triethyl citrate, tributyl citrate, tributyl citrate and acetonitrile citrate Octyl ester), glycolic acid compounds (including but not limited to ethyl methyl phthalate, ethyl ethyl phthalate, ethyl butyl phthalate) Ethyl esters, trimellitic acid compounds (including but not limited to trioctyl trimellitate and trimellitic acid tris(n-octyl n-decyl ester)) phthalate isomer compounds (including But not limited to) monooctyl isophthalate and dioctyl terephthalate), ricinoleic acid compounds (including but not limited to ethionyl hydrazine) Methyl oleate and ethyl ketone are said to be "poly" compounds (including but not limited to polypropylene adipate and polypropylene phthalate), epoxidized soybean oil, ring Oxidized butyl stearate, epoxidized octyl stearate, gasified paraffin, gasified fatty acid esters, fatty acid compounds, vegetable oils, pigments and acrylic compounds. The plasticizers can be used singly or in combination with each other. 42 201042103 In some specific examples, a liquid carrier for a wet nucleating agent may be a surfactant. Surfactants are typically used to remove dust, lubricate, reduce surface tension and/or thicken. Examples of surfactants include, but are not limited to, mineral oil, castor oil, and soybean oil. One mineral oil surfactant is Drake(R) 134 available from Penreco (Dickinson, Texas, USA).

MaXsperse W-6000 and W-3000 solid surfactants are self-contained

Obtained from Polymer Additives (Piedmont, South Carolina, USA). Ο

Q Surfactants may also include detergents such as Trit〇n (9), TWEEN®-20, TWEEN®-65, Span-40 and Span 86. The anionic surfactant includes: an aliphatic carboxylic acid such as dodecanoic acid, myristic acid, palmitic acid, stearic acid, and oleic acid; a fatty acid soap such as a sodium or potassium salt of the above aliphatic carboxylic acid; - mercapto-N-methylglycinate, N_mercapto-N-mercapto-/3-alanine, N-mercapto glutamate, polyoxyethylene alkyl ether buffer, hydrazine Peptide, alkyl benzene sulfonate, alkyl naphthalene sulfonate, naphthoate _ fumarin polycondensation product, melamine sulfonate-formalin polycondensation product, succinic acid disuccinate, continued Sulfonic acid diester, polyoxyethylene alkyl sulfosuccinic acid di-salt, alkyl sulfonate, a-olefin sulfonate, N-mercaptomethyl taurate, 5-sulfo Dimethyl phthalate sodium salt, sulphated oil, higher alcohol sulphate salt, polyoxyethylene alkyl ether sulphate' second higher alcohol ethoxy oxy sulfate vinegar, polyoxyethylene sulfhydryl sulphate sulphate Monoglysulfate, fatty acid alkanoate sulphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, alkyl phosphate, alkylamine bistridecyl sulfo Di sodium salt, dioctyl sulfosuccinate sodium salt, dihexyl sulfosuccinate sodium salt, dicyclohexyl sulfosuccinate sodium salt, dipentyl sulfobutyl 43 201042103 diacid sodium salt, Diisobutylene succinic acid (tetra), decylamine oxime polyoxyethanol, sulfosuccinic acid ethoxylated alcohol half ester disodium salt, sulfosuccinic acid ethoxylated decyl diester II (tetra), Isodecyl succinyl succinate di-sodium salt N. Dodecyl sulfosuccinamine disodium salt, N_(1,2.didecylethyl)_N-octadecyl quinone The tetrasodium salt, the oxidized mono-t-cylylene diphenyl bis-diester acid disodium salt or the oxidized mono-dodecyldiphenyldisulfonic acid disodium salt, and the naphthalene sulfonate sodium salt neutralize the condensation product. In other embodiments, the liquid carrier is a lubricant. For example, lubricants commonly used in polymer processing can also be used as a liquid carrier for wet milling nucleating agents. Lubricants are commonly used to reduce adhesion to hot metal surfaces and may include polyethylene, paraffinic oil, and paraffin as well as metal stearates. Other lubricants include stearic acid, amidoxime, (iv), metal (iv) salts and rebel. Typically it will be between about 1 Wt% to about 1 wt% of the compound. /. Typically, from about 0 7 wt% to about 0.8 wt% of the lubricant is added to the polymer. Solid lubricants may heat up and melt during wet milling. In other embodiments, the liquid carrier is a volatile solvent or organic solvent. In these specific examples, the volatile solvent is flashed off during subsequent compounding of the polymer leaving a nucleating agent. Agents useful in the present invention include alcohols such as ethanol, propanol, isopropanol and the like. Examples of organic solvents useful in the methods and compositions of the present invention include, but are not limited to, n-pentane, n-hexane, isohexane, n-heptane 'n-octane, isooctane, n-decane' 2, 2-Dimercaptobutane, petroleum ether, petroleum essence, sputum/by oil, kerosene, petroleum spirit, naphtha, 2-pentanyl, mixed pentene, hexamethylene, fluorenylcyclohexane Benzene, toluene, xylene, ethylbenzene, diethylbenzene, 44 201042103 cumene, pentylbenzene, dipentylbenzene, trimerene, tetraphenylbenzene, dodecylbenzene, di-dodecylbenzene, Amyl toluene, coal coke naphtha, solvent naphtha, p-isopropyl toluene, anthraquinone, tetralin, decalin, biphenyl, diamyl, turpentine, terpene, p-menthane, pine oil, Camphor oil, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethane, di-ethane, oxime, oxime

Di-ethane, 1,1,2-di-ethane, m2-tetrachloroethane, ^22 four-air ethylene, pentachloroethane, hexachloroethane, partial ethylene, hydrazine, 2-two Chloropropanol, chlorobutane, chloropentane, mixed chloropentane, dichloropentane, chlorohexane, ethylhexyl chloride, bromodecane, ethyl bromide, dibromoethane, tetrabromoethane, chlorine Methyl bromide, bromine ethane, benzene, o-benzene, hydrazine, trichlorobenzene, bromobenzene, o-dibromobenzene, o-toluene, p-chlorophenyl, α-chloronaphthalene, gasified naphthalene, fluorine Methyl chloride, di-air difluorodecane, fluorotrichloromethane, trifluoromonobromodecane, difluoroethane, and 1'1'2-digas-1'2'2-trifluoroethane; Erqi B, isopropyl ether, n-butyl ether, diisoamyl ether, n-hexyl ether, methyl strepyl ether, ethyl phenyl ether, n-butyl phenyl ether, amyl phenyl ether, o-tolyl Ether, m-phenyl phenyl ether, p-phenyl phenyl ether, p-tert-butylphenyl n-pentyl ether, ethyl phenyl hydrazine, 1,4-one smoldering, dioxin burning, biting, Kushiro 'dioxolane, 2 methyl 11 fumon, tetrahydrofuran, cineole, formal, diacetone, methyl acetone Mercaptoethyl ketone, methyl n-propyl ketone, methyl n- ketone, decyl isobutyl ketone, decyl n-pentyl ketone, decyl n-hexyl hydrazine, diethyl ketone, ethyl n-butyl Ketone, di-n-propyl-, di-isobutyl ketone, 2,6 8 tridecyl 4-indole, acetone oil, acetone propyl ketone, isopropylidene ketone, phorone (ph_ne) 'isophor Ketone (isoph〇rone), cyclohexamine, methylcyclohexanone, acetophenone, acetophenone, camphor, methyl formate, ethyl citrate, 45 201042103 propyl formate, n-butyl formate, formic acid Isobutyl ester, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, isoamyl acetate, acetic acid Isoamyl vinegar, methoxybutyl acetate, second hexyl acetate, 2-ethylbutyl acetate, decyl isobutyl sterol acetate, 2-ethylhexyl acetate, cyclohexyl acetate , methylcyclohexyl acetate, phenyl decyl acetate, decyl propionate, ethyl propionate, n-butyl propionate, isoamyl propionate, decyl butyrate, ethyl butyrate, n-butyl succinate , isoamyl butyrate, oxyiso Ethyl acetate, butyl stearate, pentyl vinegar, ethyl acetate, ethyl acetate, isoamyl isovalerate, lactic acid δ, ethyl lactate, butyl lactate, lactic acid Ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate phenyl phthalate, ethyl cinnamate, decyl salicylate Acid octyl ester, diethyl oxalate, dibutyl oxalate, diamyl oxalate, malonic acid diacetate, dibutyl tartrate, tributyl citrate, dioctyl sebacate, adjacent Dimethyl benzoate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, nitromethane, nitrate Ethyl ethane, nitropropane, nitrobenzene, nitrophenyl oxime ether, monodecylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, aniline, methylamine, acetamide , acetonitrile 'benzonitrile, pyridine, mercaptopyridine, dimercaptopyridine 'quinoline, morpholine, carbon disulfide, dimethyl sulfoxide, propane oxime, triethyl phosphate, polyethylene glycol 'polypropylene glycol, polybutadiene Table alcohols and poly-alcohols gas. These organic solvents may be used singly or in combination with each other. An advantage of using a volatile liquid is that the liquid will flash off and be removed during processing in the extruder. This may be advantageous for applications where it is desirable to have virtually no plasticizer or surfactant in the final polymer product 46 201042103. In other embodiments, liquid carriers for wet milling nucleating agents. 2. Water: The advantage of using water is that it will also flash out during processing as a volatile solvent. In addition, no residue is left and it is found that the influence on the chemical properties of the polymer itself is minimal or no effect. In other embodiments, a mixture of the above carriers for wet milling a nucleating agent. For example, the liquid carrier can be a mixture of one or more surfactants, one or more volatile, catalyzed carriers or water. The liquid carrier can also be a mixture of one or more plasticizers/, surfactants, volatile liquid carriers or water. The general liquid carrier can be prepared by considering the polymer processing technology in the case of polymerization. For example, if the polymer is a small amount of plasticizer or surfactant, it is generally familiar with polymer, =! Prepare = a liquid carrier of a plasticizer or surfactant. In the specific examples of the volatility of flashing during processing, the nucleating agent is wet-grinded as described in PCT Patent Publication No. 09/129499, and is & The Hai patent is made in the form of a full-text I. In the concrete example, the 'nucleating agent' step comprises a polymer and is then referred to as a nucleus, and a compound. In these specific examples, the poly-character in the nucleating composition is referred to as the "carrier polymer" to be referred to as the polymer when the carrier polymer is also present in the fiber composition (as distinguished from the polymer). The carrier polymer is included in the composition; / polymer") The polymer used to disperse the nucleating agent 201042103. In some cases, a nucleating agent is formed in a nucleating particle: a nucleating agent and a nucleating agent and a liquid carrier polymer to promote crystallization of the composition: the granule is a polymer distributed in the matrix method and composition. For use in the preparation of: or a polymer as used in the compositions of the invention. Fiber and non-woven fabrics In some specific examples, it is temporarily taken from the group of people: the earth, the s material and the carrier polymer are the same. In other specific examples, the viscosity of the matrix polymer and the carrier polymer are not pj 0 polymer composition. In general, it has been found that the viscosity of the solution of the (4) (tetra) compound should be maintained. The melt viscosity of the starting material is preferably from about 8 Pascal seconds (pa sec) to about 11 G G Pascal seconds. The term viscous viscosity system as used herein is tested by ASTM D3835 ( ASTM Internati〇nal, 1〇〇 Η _ 〇Γ

Drive, PO Box C700, West Conshohocken, PA, 19428-2959 U S A ) to measure. Although the starting material preferably has a melt viscosity of from about 800 Pascals per second to about 1 Pascals per second, the weight average molecular weight of the fibers after extrusion is obtained for fibers having soft fibers (i.e., fibers having reduced brittleness). Non-woven materials are also very important. Extrusion fibers having a molecular weight of less than 1 〇〇 kg/mol were found to be brittle. Preferably, the fibers have a molecular weight of at least about 1 50 kg/mol, more preferably at least about 1 80 kg/mol, even more preferably at least about 200 kg/mol, and most preferably at least about 250 kg/mol after extrusion. For example, it has been found that polyhydroxybutyrate in combination with a plasticizer has the following "feel" (subjective softness) with respect to the following molecular weight retention: 48 201042103 Table 1 · The feel of the fabric is 83,047 189 is crispy? 1,874 23:2 g Crisp 123,682 2Q1 Crisp 157,045 35 7 Soft 167,148 38.0 Soft-iliz225__36.1___ Stupid Ο The relationship between the starting material and the molecular weight of the extruded fiber can also be expressed according to the molecular weight retention rate. That is, the weight average molecular weight of the extruded fiber is a percentage of the weight average molecular weight of the starting material. For example, an extruded fiber having a molecular weight of 235 kg/m〇i prepared from a starting material having a molecular weight of 420 kg/m〇1 can be called It has a molecular weight retention of 56%. However, a starting material having a very high molecular weight may have a low molecular weight retention, and if the molecular weight of the extruded fiber is sufficiently high, soft fibers are still produced. Similarly, if the starting material has a relatively low molecular weight, then the molecular weight retention is required to be relatively high to produce fibers and dimensions having a sufficiently high molecular weight. Understanding the relationship between these variables is necessary to understand the extent to which the residence time and temperature in the extruder are controlled. The wet milling of the nucleating agent does not alter the molecular weight maintained by the fiber. It has been found that the viscosity and the softness of the resulting fabric are reduced. Others have attempted to reduce the viscosity to better drive the polymer formulation through the mold by reducing the molecular weight of the polymer, for example by increasing the thermal degradation of the polymer. However, it has been found that increasing thermal degradation or lowering the molecular weight, while making it easier to squeeze the polymer through the mold, has the added effect of producing brittle fibers or not producing fibers at all. Instead, adding a plasticizer and maintaining the melt viscosity (or at least reducing thermal degradation) as described herein increases the viscosity, allowing extrusion through the fine mold, 49 201042103 and still produces fibers that are soft and brittle. In some embodiments, the specific plasticizer is ethylene tri-n-butyl vinegar (CITR® FLEX8A4). Further, a plasticizer known to be suitable for use in the present invention is diisodecyl adipate (DINA). Examples of other plasticizers include the plasticizers described above. The plasticizers can be used singly or in combination with each other. The biodegradable nonwoven material described in the present invention can be prepared by any method known in the art for preparing a nonwoven fabric. For example, non-woven fabrics can be prepared by spraying as described below in the implementation of your ". The operation and adjustment of such equipment is well within the knowledge of those skilled in the art of preparing nonwoven materials. For example, the net bag can contribute to back pressure and shear heat. Screens of high mesh size are typically used for the nozzle system 2'. However, it has been found that coarser screens perform better, such as 60 mesh or 180 mesh, or 110 mesh or 13 mesh or even 90 mesh.

. The die hole size can be about 25 〇 μηι. The compressed air can be heated to, for example, 220 C. The line speed can be increased by heating the collector belt or the winding roller. The machine should be rinsed with, for example, polypropylene. For example, the polymeric composition may also include a nucleating agent, optionally selected to aid in the crystallization of the polymeric composition. However, due to the smaller diameter of the fibers, particulate nucleating agents should not be used. In the poly-3-hydroxybutyrate composition, for example, a plasticizer is often used to change the glass transition temperature and modulus of the composition, but a surfactant such as the interfacial activity described above may also be used. Agent. 50 201042103

The nonwoven composition and fibers described herein may further comprise an additive such as a surfactant and clay. The polymeric composition can include one or more. Surfactants. Surfactants are typically used to remove dust, lubricate, reduce surface tension and/or thicken. Examples of surfactants include, but are not limited to, mineral oil, castor oil, and soybean oil. One mineral oil surfactant is Drakeoi 34 available from Penrec(R) (Dickinson, Texas, USA). Maxsperse 〇 W_6〇0〇 and W-300〇 solid surfactants from Chemax Polymer

Obtained by Additives (Piedmont, South Carolina, USA). Nonionic surfactants having HLB values in the range of from about 2 to about 16 can be used, examples being TWEEN-20, TWEEN-65, Span-40, and Span 86. Anionic surfactants include aliphatic carboxylic acids such as dodecanoic acid, myristic acid, palmitic acid, stearic acid, and oleic acid; fatty acid soaps. Another component that is selected according to the situation is a nano-clay (nan〇clay) or an organically modified Q clay. There are several types of clay used in the polymeric composition, including cationic or polymeric or local cation exchange capacity. The cation exchange capacity is generally reported in milliequivalents per 100 grams of exchangeable salt base exchangeable. The cation exchange capacity can vary from about 50 to about depending on the type of clay. Examples of clays which can be organically modified include sepiolite, magnesia bentonite, montmorillonite, bentonite, saponite and stellite. Organically modified clays are known in the art and are also described in U.S. Patent No. 2,53,440. Examples include smectite clays modified with tertiary or quaternary ammonium salts. Nano-grade clay can be obtained from G〇nzales, Texas, USA, 51 201042103

Southern Clay Products, lnc_ purchased (such as (but not limited to) CLOISITE® NA+ (natural montmorillonite), CLOISITE® 93a and 3〇b (natural montmorillonite modified with tertiary ammonium salts) and CL〇ISITE® 1〇A, l5A, 2〇A and 25 A (natural montmorillonite modified by a quaternary ammonium salt)). Montmorillonite clay is the most common member of the smectite family of nano-clay. The sapphire has a unique morphology' characteristic of one size in the nanometer range. Smectite clay particles are often referred to as platelets, which are flake-like structures in which the dimensions in both directions far exceed the particle thickness. The length and width of the particles range from 1.5 micrometers to a few tenths of micrometers. However, the thickness is only about}, and the size of the D'm produces the average aspect ratio of the pole (about qiao). In addition, the extremely small size and thickness means that one gram of clay can contain more than one million individual particles. The clay originally contained a small layer of agglomerates on the moon layer. If the nano-scale clay is processed into an intercalate, ^ ^ ^ ^ ^ ^ ^ separation (exfoliation) small in the agglomerate is commercially suitable 'the inter-process substance is in the separation of the pieces and the body is loyal , clay and cool make the space between the clips into the space between the small pieces. Interstitial materials are often able to enter the interlayer structure of smectite clay and are therefore clay. Chemical or semi-organic chemicals. The surface of the intercalation material is attributed to the increase in the inter-layer spacing of the clay by the material enamel process. Under the condition of suitable dish and shearing, the material between the oyster and the center enters it, so that J:, , ·. This is enough to peel off (separate), allowing it to separate and peel off. The film can be peeled off by a variety of processes. Patent No. M99,32 ”" is described in a US stripping process that uses a dispersant between the layers of the clay sheet and separates it. In this process, the clay disc dispersant (such as ramie wax) is mixed, and the '^ s ^ picker is added to the barrel of the extruder to the temperature of the melting point of the dispersant (82〇r ln4〇r, again I, for example, in the case of I hemp, with L -104 c ). The heated mixture is then agitated using, for example, a sputum female ice threaded screw. This heating and priming will disperse the lamellae and stratify the dies with adjacent layers by passing the dispersant molecules between the layers. When the inter-layers of the dice are sufficiently large that there is no longer sufficient attraction between the layers to make the spacing between the layers uniform, the layers are considered "exfoliated". The screw in the extruder in the process described in U.S. Patent No. 6,699,320 causes the clay/clay mixture to be removed from the extrusion die opening in the form of a heat aggregate. The mixture is then calendered to a predetermined thickness using two cooled plating drums, the thickness being determined by the spacing between the rolls. The mixture is cooled to solidify the wax. The clay soil mixture is then scraped from the crucible and dropped onto the conveyor belt in the form of a sheet. The rollable sheet α is stepped down to its size, and I use it immediately or store it. Because clay particles are extremely small in size, nano-scale clay is difficult to handle and may pose a health risk. Therefore, it is sometimes processed into a "mother mixture" in which clay is dispersed in a polymer resin at a high concentration. Each parent mixture is then added by weight measurement to a polymer containing no nano-sized clay to produce a polymer containing a precise amount of nano-sized clay.

One type of smectite clay is Cloisite® 25A, available from Southern Clay Products of Gonzales, Texas, USA. The typical dry particle size distribution of Cloisite® 25A is 10% less than 2 microns, 5% by less than 6 microns, and 90% less than 13 microns. 53 201042103 Other non-rice clays are disclosed in U.S. Patent No. 6,414,070 (Kausch et al. Identification in No. 683. Annealing Post-manufacture heat treatment (e.g., annealing) of the compositions described herein produces compositions having improved physical properties, such as edging. By way of example, the pHA composition is treated at a temperature of about 8 (rc to about 12 generations for about 10 minutes, about 120 minutes. This treatment improves the 'knifeness of the fiber or the non-woven fabric. Another improved physical property The physical aging of the fiber is reduced by the annealing temperature compared to the untreated condition. Although various PHAs can be processed on conventional processing equipment, it has been found that the polymer hinders its commercial technology. Problems such as brittle r-generation and aging-related enthalpy.

The machine of the I-made article is alive andlt;14 P + I p ^ 〇 is moved at any time during storage under environmental conditions. In particular, impact motility and tensile elongation at break = systemic decline over time. The exact cause of this reduction is unknown: Use. 'Additional increase _ can _ polymer obtained commercial should be equal to the polymer period; need == learning is not well understood, and in processing this 嫉,, requires a longer cycle time (relative to polyethylene and poly石 ':- Steps limit its commercial acceptability. The heat after manufacture is large) to provide benefits to the mechanical properties of the PHA composition. j如退茂产# This article does not disclose 'annealing' and 'heat treatment' means that after the polymerization, it will be heated for a period of time. This treatment has been found to provide surprising and unexpected toughness characteristics. More than about the gift, about 5 seconds to about 9 〇: weaving: or mesh heating to about café

Up to about 13 Gt, lasting about 1 G, knowing that it is better to heat up to about 90 ° C to bribe to about 125 t: "Ma about 7 min, and optimally heated to about 25 C, for about 15 minutes to about 60 minutes. This can be achieved, for example, by using multiple cloths, and then forming the fiber < mesh cloth 1 to form a fiber or mesh cloth over the oven at an appropriate temperature. The oven is long enough to come with the ant

It is heated for a suitable amount of time. Or:: Between the entering and leaving the box, the oven, for example, on the series of rollers in the oven, back and forth, == heat the fiber or mesh for a suitable amount of time before the oven. To produce a suitable article, the materials described herein are produced at a temperature above the crystalline melting point of the thermoplastic material but at a lower temperature, and at the decomposition point of any component of the composition. Alternatively, the pre-prepared composition of the present invention is prepared as early as ', to the temperature. This processing can be carried out using any technique known in the art for nonwoven materials. The inventive polymeric composition can be used to produce, but is not limited to, a wide variety of suitable products' such as automotive, consumer, durable, construction, f, medical, and packaging products. For example, polymeric compositions can be used to make, but are not limited to, non-woven fabrics and articles made from nonwoven materials, such as filters, insulating materials, and disposable garments and rags. The invention is further described in the following examples, which are not to be construed as limiting the scope of the invention defined by the scope of the claims. EXAMPLES Test Methods 55 201042103 Measuring the molecular weight of a polymer The molecular weight of the ruthenium (GPC) is estimated by, for example, using a Waters Alliance system equipped with a refractive index from the Lishui detection state. The average molecular weight (Mw) or the number of 詈 詈 v v v 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 The column group is, for example, a system of PLGell0 micron Mixed_B (p〇iymerLabs,

Amhem, MA) column, pumped as a mobile phase of chloroform at 1 ml/min. The column string was calibrated with narrowly distributed polystyrene standards. The PHA sample was dissolved in chloroform at a concentration of 20 mg/ml at 6 〇C. The Xiao G.2 micron Teflon (made (10)) syringe was passed through the sample. A 50 microliter injection volume was used for analysis. Eight analyze the chromatogram with a software such as Waters Emp0Wer Gpc. The amount of knives and PD are reported as polystyrene equivalent molecular weight. When the field measures a molecular weight of more than about 1 million, the GPC method becomes inaccurate for a polymer having such high molecular weight by flow injection polymerization.

A knife-to-finish (FIPA) system (from, for example, Viscotek Corp, Houston, TX's) was used to estimate the weight average molecular weight. The polymer solution is eluted via a single low volume size exclusion to separate the polymer, solvent and impurities. The detection system consists of a refractive index, light scattering, and viscosity group. The polymer sample was dissolved in chloroform at a concentration of 2 〇 mg/ml at 60 c. The sample was filtered using a 0.2 micron Teflon syringe filter. At 45. 〇 操 乍 PA FIPA unit ‘! The flow rate of 〇ml/min uses a tetrahydrofuran mobile phase. A 100 microliter injection volume was used for analysis. The chromatogram is analyzed using, for example, the Viscotek Omni-Sec software. Absolute Mw is reported in grams/mole. 56 201042103 For PHA polymers, A is related to rpr佶 'W (as measured by FIPA) by dividing the GPC value by approximately 13 (as measured by (4) 2 equivalents). Polyethylene. Measurement of thermal stability. Measurement of polymer-like properties in two different ways. In this paper, the sample is "k^疋. changes in thermal stability. It can also be buried" to demonstrate MW over time. J wrong by the capillary capillary stability of the melt capillary stability (-the amount ' Ο shift change. Mao,,, field B shear viscosity with time mg) in the DSC "(")' to make polymer samples (for example 2 mg) was exposed to the sample cup in a DSC test chamber (eg ta instrument-mi and heated for G minutes, 5 minutes and) and in a chloroform file. Disassemble the required concentration for cooling. Using a GPC amount ^; gel permeation chromatography (GPC), the GPC was used to measure the polymer, relative to the control, and the molecular weight average. The slope of the reciprocal (i/Mw) of the weight average molecular weight of the present 相对 relative to the line of the gate m is the ratio of 7 per gram of gram per minute: goodness. The smaller the "k", the better the thermal stability. . Ten samples. Thermal stability of the mouth ί The thermal stability of the sample is measured by capillary rheology test. Capillary rheometers are typically used to measure the viscosity of plastic bristles associated with shear rates (typically seconds). However, ΡΗ 0.1 to 10,000 / viscosity is complex, because under the test conditions: Stage reaction: will lead to the degree of relaxation associated with the residence time of the refining ^ knife set down this... by measuring the amount of time in various residence times Body viscosity is reversed by 57 201042103 to zero time (this is described in ASTM D3835-08, ASTM International, 100 Barr Harbor Drive, P〇 Box C700, West Conshohocken, PA, 19428-2959 USA). In the tests used herein, measurements were taken at 180 °C. Prior to the start of the test, the material was preheated for 240 seconds (4 minutes) and a capillary die with a diameter of ο." claws and a length of 30 mm was used. The measured visual viscosity (as measured by pressure and velocity) ) decreases as the dwell time in the rheometer increases. When plotting the measured apparent viscosity (at a 100/sec apparent shear rate) versus time, the slope of the best fit line is used. As another indicator of thermal stability, this slope is called "melt capillary stability" or MCS. The value of PCT is negative because the viscosity decreases with time, and the larger the value (i.e., the smaller the value), the worse the thermal stability. In other words, the closer the negative number is to zero, the more healing is needed, and the larger the negative number, the less desirable. Measurement of Gl using a torsional melt rheometry The torsional rheometry was used to measure the melt strength of the polymer. For the sake of simplicity, G will be used herein as a measure of "melt strength" which is measured at a strong frequency of 0.25 rad/s (unless otherwise indicated G, the higher the higher the melt strength). All oscillating rheology measurements were performed using a TA Instruments AR2000 rheometer (using a strain amplitude of j%). First, the dry granules (or powder) were molded into a 25 mm diameter disc with a thickness of approximately 12 〇. 〇Micron. A disk sample was molded in a compression molding machine set at about 165 t: a molding time of about 3 sec. Then these molded discs were placed on an AR2 〇〇 () rheometer. Between the mm parallel plates, equilibrated at 180., and then cooled to 16 〇t for the frequency test of 58 201042103. Using a gap of 800 μm to 9 μm, depending on the normal applied by the polymer The viscosity of the PHB is 16 〇. The lower measured is - about 10 g/cm3, which is used in all calculations. Specifically, the sample disc is set at 18 ( Between the plates of the parallel plate rheometer of rc. After the final gap is reached, the excess material is scraped off from the side of the platen. Cool the sample to 16Gt:, followed by a frequency sweep (from 625 rad/s to 〇_1〇rad/s); avoid making the frequency lower, as these lower frequency measurements take longer Significant degradation occurred. Sample loading, gap adjustment and over-trimming were performed on a press plate set at 18 〇<t, which took approximately 21⁄2 minutes. This was controlled within ±1 〇 seconds to reduce variability and sample degradation. To the lowest. Completed from l8〇t: cooled to 160 C (test temperature) in about 4 minutes. Exposure to i 80 will ensure complete melting of the polymer, while testing at 160 °C ensures minimal degradation during measurement During the frequency sweep at 16 0 C, collect the following data related to the measurement frequency: |η*| or complex viscosity, G, or elastic modulus (impact on the elasticity or solid sample of viscosity)' and G" or Loss modulus (impact on viscosity or liquid U-like effect). As used herein, G1 measured at a strong frequency of 0·25 rad/s (unless otherwise indicated) is used as a measure of "melt strength". The higher the G, the higher the melt strength. With ASTM D383 5 ( ASTM International, 1〇〇 Barr

Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959 USA) Measure melt viscosity. Tensile properties were measured according to ASTM D412 - Test Method A_Vulcanized Rubber and 59 201042103 Standard Test Method for Thermoplastic Elastomers (ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959 USA). Example 1. Preparation of soft non-woven fibers from PHB and CITROFLEX® A4 plasticizer In this example, a PHB nonwoven material was prepared using a 6-inch melt-blown line generally used for the preparation of PHA fabrics. The line used a mold having a 0.025 吋 die hole diameter (120 holes). Table 2. Other parameters of the meltblown line design Horizontal pipe mold and collector distance 23吋_25吋Extruder screw compression ratio 3 Extruder screw metering section channel depth to barrel diameter ratio 10 extruder screw diameter 1.25" extruder screw design 3 areas typical material dosage 81b / hr typical solution retention time 7 minutes melt filtration no roll speed can vary from 5 seconds to 2 minutes will have 90% PHB and 10% plasticization The resin formulation of CITROFLEX® A4 (tri-n-butyl citrate) was sent to the extruder. After exposure to 180 ° C for 5 minutes, the resin formulation had a D3835 (as ASTM International, 1〇). 〇Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959 USA) measured the melt viscosity of 924 Pascal seconds and a weight average molecular weight of 420 kg/mol. Use 2 screens with 60 and 180 mesh The size of the net package and the mold is a ι 21 hole mold with a hole of 0.010 吋 (25 0 μηη). The air gap is set to 〇〇6 〇吋. 60 201042103 The conditions used are shown in Table 3 below. Table 3. For preparation Conditional control point setting of mesh cloth Condition ppppppp 0505\555 5524-^555 11 1X 11 11 11 11 11 170 C 165〇C 145〇C 150. NA 160°C 160°C 160°C 26-30 350-400 400〇F-415〇F (204〇C-213〇C) 5-8 psi 4.5 g/min 85 cm Screw zone 1 Screw zone 2 - Screw zone 3 C zone die zone 1 Mold zone 2 Mold zone 3 Mold zone 4 Screw speed (rpm) Pressure ( Psi) Air Temperature 〇 Air Rate Yield The distance between the mold and the collector belt is a soft continuous web with a fiber diameter in the range of 2 microns to 5 microns and a basis weight of 20 GSM to 160 GSM. The remaining Mw of the polymer is 235. Kg/mol gave a molecular weight retention of 56%. The residual crystallinity was 51%. The strength of the samples from 6 identical operations was tested and the tensile/elongation curves are presented in Figure 2. An overview of the mechanical properties is presented in Table 4. Table 4. Mechanical properties of six non-woven samples Thickness (mm) Air permeability (cfin) PMI (micron) Basis weight (g/m2) Fiber diameter (micron) Alcohol permeability 4-value force ( Machining direction) Peak elongation (machining direction) Average SD Average value D bubble average SD gas seven flat SD average SD level broken (Lbs.)% 1.52 0.08 25.90 2.70 29.91 15.71 141.20 8.42 2.14 5.11 1 1.98 3.39 fiber structure photographs presented in Figure 3. Example 2 • Elevated Temperature Exposure Effect on the preparation of non-woven fibers from PHB and CITROFLEX® A4 61 201042103 Plasticizers used with 90% polyhydroxybutyrate and 10% CITROFLEX® A4 (ethylene tri-n-butyl citrate) A resin formulation to prepare a non-woven fabric. After 5 minutes at 1880 ° C, the formulation had a melt viscosity of 924 Pascal seconds and a weight average molecular weight of 420 kg/mol. The crystallization started at 102 ° C and the peak crystallization temperature was 93.5 ° C. The material was sent to the same extruder as used in Example 1. Two mesh packages with 60 and 180 mesh sizes were used and the mold was a 121-hole mold with 0.010 inch (250 μm) holes. The air gap is set to 0.060. The processing conditions used are provided in Table 5 below. Table 5. 90% PHB: 10% CITROFLEX® Α4 Processing conditions Control point setting Operating conditions Screw zone 1 160°C 161°C Screw zone 2 160°C 160°C Screw zone 3 155〇C 170°CC zone 155〇 C 157〇C Mold area 1 ΝΑ 169〇C Mold area 2 155〇C 154〇C Mold area 3 155〇C 156〇C Mold area 4 160°C 162〇C Screw speed (rpm) 18 Pressure (psi) 312 Air Temperature 395T Air Rate 8 psi Yield 4.5 g/min These higher temperature exposures and longer residence times (15 spindles per minute) make the fibers begin to become significantly rougher and more brittle. The molecular weight retention rate is reduced to below 40%. The molecular weight of the three extruded fiber samples was 167 kg/mol, 159 kg/mol and 157 kg/mol. The strength of the samples from 6 identical operations was tested and the stretch/elongation 62 201042103 curve is presented in Figure 4. The test sample has a basis weight of 30 GSM. The peak force in the machine direction was 0.77 lbs and the peak elongation was 1.65%. Average fiber. Diameter 2 microns with a standard deviation of 9 microns. The fiber feels rough. • Example 3. Preparation of non-woven fibers from PHB and DINA Non-woven fabrics were prepared using a formulation having 85% polyhydroxybutyrate and 15% DINA (diisononyl adipate). After 5 minutes at 1880 ° C, the formulation had a melt viscosity of 1058 Pascal seconds. The peak crystal of this formulation at 10 ° C per minute was 83 ° C and the temperature at which crystallization started was 98 ° C. 〇 Two nets with 60 and 180 mesh sizes were used and the mold was a 121-hole mold with 0.010 inch (250 μm) holes and an air gap of 0.060 吋. The processing conditions used are as follows. Table 6. 85% PHB: 15% DINA Processing Conditions Control Point Setting Operating Conditions Screw Zone 1 150°C 148〇C Screw Zone 2 1550〇C 154〇C Screw Zone 3 120°C 128〇CC Zone 145〇C 147 . . Mold area 1 ΝΑ 128〇C Mold area 2 155〇C 158〇C Mold area 3 155〇C 153〇C Mold area 4 145 V 145〇C Screw speed (rpm) 30 Pressure (psi) 182 Air temperature 42〇F Air Rate 5 psi The fibers made from this formulation are more brittle and their softness is reduced. Example 4. Effect of processing conditions on the preparation of non-woven fibers from PHB copolymers and CITROFLEX® A4 plasticizers using 90% polyhydroxyalkanoate copolymer and 10% CITROFLEX® A4 (tri-n-butyl citrate acetate) The tree of the moon is formulated to come to 63 201042103 to prepare no fabric. The polyhydroxyalkanoate copolymer was 60% polyhydroxybutyrate and 40% poly(3-hydroxybutyrate-co-4-hydroxybutyrate). The formulation has a weight average molecular weight of 92.855 kg/mol. The material was sent to the same extruder as used in Example 1. A 200 mesh mesh bag was used and the mold was a 121 hole mold having a 0.025 bore. The air gap is set to 0.030 吋. The processing conditions used are provided in Table 7 below. Table 7. 90% PHB: 10% CITROFLEX® Α4 Processing Conditions Control Point Setting Operating Conditions Screw Zone 1 170 °C 179〇C Screw Zone 2 170°C 168〇C Screw Zone 3 170. . 181 ° C C area 170. . 169〇C Mold area 1 ΝΑ NA Mold area 2 170°C 171°C Mold area 3 170°C 170°C Mold area 4 170°C 171°C Screw speed (rpm) 200 Pressure (psi) 107 Air temperature 330〇 F Air Rate 11 psi The processing temperature and back pressure are extremely high relative to Examples 1 and 2. Produces rough and brittle fibers. The molecular weight retention was 22%. Example 5 A ruthenium blend blend having a wet-milled nucleating agent and a plasticizer is based on an enamel resin having the following composition: 36% Ρ3ΗΒ, 24% (3ΗΒ-11% 4ΗΒ), 40% (3ΗΒ) -3 0% 4ΗΒ). Wet-milled boron nitride (ΒΝ) (dispersion D218, 18% BN in Citraflex® 4, Vertellus) and tri-n-butyl citrate (Citraflex A4) Mix, dry blend and add to the resin. It was found that the particle size of BN was less than 20 microns (optical microscopy data). 64 201042103 The formulation of the compound is presented in Table 8. Table 8 Composition of the compound used for the nonwoven material: Ingredients~"-% PHA ~----- 86 Tri-n-butyl succinate 5 is dispersed in tri-n-butyl citrate Zinc-fired boronized carbide (BN), 18% BN 5 was compounded on a 27 mm MAXX Leistritz twin-screw extruder with the following temperature characteristics: 1〇 zone set to 170〇C/170〇C/165 〇C/165〇C/165〇C/160〇C/160〇C/160〇C/160°C/15 5°C. The extrusion rate was set at 6 lbs/hr and the extruder was operated at 2 rp rprn. _ The compound has the following melt viscosity at 18 (TC: 284 Pascal seconds after 5 minutes 198 Pascal seconds after 10 minutes, melt stability is -0.0723. See Figure 5. For the preparation of meltblown non-woven fabric The compound was extruded on a single screw extruder with a screw diameter of 5 〇 mm and an L/D ratio of 30. The die hole has a direct control of 300 μm. The screw temperature is 185 and the transition temperature is 18 (rc) And the temperature of the mold is 180. It is thinned by hot air at a temperature of 〇C-22 (TC at a pressure of 〇_3 7 kg/cm2. The distance between the mold and the collector is 6 〇cm-65 cm 'The yield is 70 g/min. The fiber network is found to be less brittle' and the embrittlement is not significant after 4 months of storage. The fibers are not annealed. Under these conditions, the following fibers are formed. Network (average fiber diameter 45 microns): see 圊 6. Example 6 p3iiB polymer compound with wet-milled nucleating agent and plasticizer based on P3HB resin. Wet milling by wet grinding Boron (dispersion D21 8,16% BN in citrate 65 201042103 三 tri-n-butyl citrate (Citraflex A4, Vertellus), Sub-diameter less than 20 microns) was mixed with tri-n-butyl citrate (Citraflex A4), dry blended and added to the resin. Formulations are presented in Table 9. Table 9 for compounds of non-woven materials Composition: Ingredient % PHB 75 Tri-n-butyl phthalate 20 Wet-milled BN in dispersion of tri-n-butyl citrate, 16% BN 5 27 mm MAXX Leistritz twin-screw using the following temperature characteristics Mixing on the extruder: 1〇 zone is set to 175〇C/175〇C/175〇C/175〇C/170〇C/170〇C/170〇C/170〇C/180°C/ 18 〇 ° C. The extrusion rate was set to 6 〇 lb / hr and the extruder was operated at 1 〇〇 rprn. The compound had the following melt viscosity at 18 (TC: 517 Pascal seconds after 5 minutes) 278 Pascal seconds after ί, the melt stability was _〇124. The solvent spray conditions were the same as described in Example 5. The fibers were significantly harder and more brittle than the fibers of Example 5. It has been improved by the recent development of a combination of nitrating-based plasticizers in a citrate-based plasticizer, and grinding and displacing the side particles in the plasticizer. And a nucleating agent enables the crystallinity of the PHA polymer to be reduced to introduce it into the meltblowing process. These PHA resins provide better physical properties for the fiber and its network. The lower hardening tends to be less aging associated with aging, with greater elasticity and significantly stronger (more toughness). ',, ' 66 201042103 Example 7 compares the PHA composition with the softness described in Example 1. Non-woven fabric, a compound A (YK0808 18-5) containing 90% PHB and 10% Citraflex A4 (ethylene tri-n-butyl citrate) was sent to an extruder with L/d=27 and a screw compression ratio of 3. The extruder has two mesh packages having mesh sizes of 60 and 180 and the mold contains 121 holes having a diameter of 0.010 inch (250 μm). The air gap is set to 0.060 吋. Extrusion conditions:

Table 10 Control points Settings* Operating conditions Screw zone 1 150. . 170°C Screw zone 2 155〇C 165〇C Screw zone 3 120°C 145〇C C zone 145〇C 150°C Mold zone 1 ΝΑ NA Mold zone 2 155〇C 160°C Mold zone 3 155. . 160 ° C mold area 4 155 〇 C 160. . Screw speed (rpm) 26-30 Pressure (psi) 350-400 Air temperature 400〇F-415〇F (204〇C-213〇C) Air rate 5-8 psi Output rate 4.5 g/min Mold and collector The distance between the belts is 85 cm. The tensile data of the original fibers relative to the aged fibers over 3.5 months are presented below: Table 11 New aging 3.5 months thickness average (mm) 1.52 +/- 0.08 basis weight (GSM) 141.2+/ -8.42 Fiber Diameter C/rni) 2.14+/-5.11 Peak Force MD (lb) 1.98 1.66-1.28 67 201042103

I Peak Elongation MD (〇/〇) I 3 _I 2.41-1.9 I The data shows that the peak force required to break the fiber network is reduced by up to 35% after 3.5 months of environmental aging. The peak elongation is also reduced by up to 44%. Compound B was prepared using a pha resin having the following composition: 36% P3HB, 24% (3HB-11% 4HB), 40% (3HB-30% 4HB). The wet-milled boron nitride (dispersion D218, 18% BN in CITROFLEX® A4 Vertellus) is mixed with tri-n-butyl citrate (CITROFLEX® A4). Dry blending and addition to the resin. The particle size of BN was found to be below 20 microns (optical microscopy data). Compound a is the softest and has the smallest fiber diameter (average of 2 microns). This compound also forms a thick non-woven fabric having a thickness of about 1 - 5 2 mm. The tensile retention of the thick materials is sufficiently high. These fibers are suitable for applications where softness is a critical feature (such as rags). The formulation of the compound is presented in Table 12. Table 12 Composition of the compound for the non-woven material: _ Ingredient % PHA 86 Ethylene tri-n-butyl citrate 9 Wet-milled BN ' 18% BN 5 dispersed in tri-n-butyl citrate The following compounds were prepared as described in Example 6: Table 13 PHB, compound A-1 'Aging 4 months compound B, average aging thickness (mm) 0.26 0.35 ^ basis weight (GSM) 100 164 Fiber Diameter (/xm) 40 40 — — — — Peak Force MD (lb) 0.6 1.9 Peak Elongation MD (%) 1.74 8.6 Maximum Load (N) 2.67 8.61 These fibers have a diameter of approximately 40 microns and are in Table 12 The fiber phase 68 201042103 is harder than fabric. These fibers are suitable for use in filters, insulation or sound insulators, corrosion control and overlay control materials. These fibers form a significantly thinner network and because of their thicker thickness, they tend to become brittle with ageing. This data indicates that after similar aging and under the same fiber geometry, the compound B fiber can withstand 8.6 N or force while the compound A-1 breaks at 2.67 N. Tensile properties were measured in accordance with ASTM D412, Test Method A - Standard Test Method for Vulcanized Rubber and Thermoplastic Elastomers (ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, 〇 PA, 19428-2959 USA). The tension mold is a semi-C type. The elongation rate is 10 mm/min. For comparison, these fibers were prepared on the same equipment. The fibers of Compounds A-1 and B were significantly coarser and significantly easier to embrittle. 'Example 8: Copolymer for preparing meltblown fibers and non-woven fabrics by wet-grinding nucleation composition The following formulations and blends having two or more formulations are suitable for use in the preparation of fibers and The fibers of the invention in non-woven applications. A wet-grinding nucleating agent (18% BN) la poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 8% 4 of the formulation copolymer in tri-n-butyl acetyl citrate -Hydroxybutyrate content 1 ° / 〇 -10% by wet milling of boron nitride lb ί poly (3 · hydroxybutyrate - co--4-hydroxybutyrate) 11% 4-pyridic acid vinegar content 1°/〇-10% wet-milled boron nitride lc poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 15% 4-hydroxybutyrate content 1%-10% wet Grinding boron nitride 2a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) 8% 5-pyrutonic acid g content 1 ° / 〇 -10% by wet milling boron nitride 2b poly (3-hydroxybutyrate-co--5-hydroxyvalerate) 11% 5-perglycolic acid g content 1%-10% by wet milling of boron nitride 2c poly(3-butyric acid vinegar - total -5-pivalic acid vinegar) 15% 5-hydroxyvalerate content 1 ° / 〇 _ 10% by wet milling of boron nitride 3a poly (3-hydroxybutyrate - co--3-hydroxy pentyl Acid ester) 8 1%-10% by wet grinding of boron nitride 69 201042103 % 3-glycosylation g content 3b poly(3-pyrubic acid vinegar-co-3-glycosyl acid g) 11% 3-hydroxyvalerate content 1%-10% by wet research Boron nitride 3c poly(3-hydroxybutyrate-co-3-hydroxyvalerate) 15% 3-hydroxyvalerate content 1%-10% wet-milled boron nitride 4a poly(3-hydroxybutyrate Acid ester-co-3-hydroxyhexanoate) 8% 3-hydroxyhexanoate content 1°/〇-10% by wet milling of boron nitride 4b poly(3-hydroxybutyrate-co-3-hydroxyl Hexanoate) 11% 3-hydroxyhexanoate content 1%-10% by wet milling of cerium 4c poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) 15% 3-Phase The hexanoate content of 1% to 10% by wet milling of the nitriding butterfly may additionally contain a plasticizer such as acetamidine tri-n-butyl hydrazine. In addition to the above formulations, a two component blend of the copolymers of the formulation may also be prepared, for example, a copolymer of 丨a may be combined with poly(3-hydroxybutyrate) or 2a, 2b, 2c, The copolymer of 3a, 3b, 3c, 4a, 4b or 4c is blended, and the resulting composition further comprises 1% to 10% of the wet-milled boron nitride (i 8 分散 dispersed in tri-n-butyl citrate). /〇BN). All numerical ranges, amounts, values, and percentages (such as amounts of materials, amounts of elements, reaction times and temperatures, ratios of amounts, and others) are included in the remainder of the specification, unless otherwise specified herein. And the scope of the accompanying patent application can be regarded as the prefix "about", even if the term "about" is not explicitly related to the value, unless otherwise stated, the following description and the accompanying application Numerical parameters are approximations that vary depending on the desired characteristics sought to be obtained by the present invention. At a very low level, τ, and not as a claim to limit the equivalent of the claimed invention, the numerical parameters should be interpreted at least according to the number of significant digits reported and by applying the technique of rounding. Although the numerical ranges and parameters set forth in the broad scope of the invention are approximate, the values recited in the specific embodiments are reported as accurately as possible. However, any numerical value inherently contains errors that are necessarily caused by the standard deviations seen in its potential individual test measurements. Moreover, when numerical value 2 is set forth herein, such ranges include the ends of the ranges, as well as the endpoints. When weight percentages are used herein, the reported values are related to the total weight.

Also, it is to be understood that any numerical range recited herein is intended to include all sub-ranges For example, the scope of Γ 〇 〇 意 意 意 意 意 意 意 意 介于 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之Equal to or J to a maximum of 10. "A" or "an" as used herein is intended to include "at least one" or "or". Any patent, publication, or other disclosure that is incorporated herein by reference in its entirety or in its entirety is in the extent of the extent And in this context, the term "and to the extent necessary" as set forth herein is intended to supersede any conflicting material herein by reference.任: 称 乍 并入 并入 并入 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 , , , In. There is no degree of inconsistency between the materials and unless otherwise defined, the language has the same academic meaning as commonly understood by all of the techniques and artisans used in the context of the present invention 71 201042103. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the following description is suitable for the methods and materials. All publications, patents, patents, and other references mentioned herein are hereby incorporated by reference in their entirety. In the case of conflict, this manual (including definitions) will be the main one. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting. The present invention has been shown and described with reference to the preferred embodiments thereof, and it is understood by those skilled in the art that various changes in form and details may be made without departing from the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [Simplified illustration of the drawings] Fig. 1 is a view showing a general solution of a solvent spray process. Figure 2 is a graph showing the general non-woven tensile strength/elongation curve for six samples without 90% PHB and 1 〇〇/0 CITR 〇 FLEX® A4 plasticizer. Figure 3 is a photomicrograph showing fibers prepared from 90% PHB and 1% by weight Citr〇flex@ a4 plasticizer. Figure 4 is a graph showing the general non-woven tensile strength of six samples with 90% PHB and 1 〇〇/0 CITR 〇 FLEX® A4 plasticizer. Fig. 5 is a graph showing the relationship between the apparent melt viscosity (pa-s) of the fibers produced in Example 5 with respect to the residence time. Figure 6 is a photomicrograph showing the fibers produced in Example 5. 72 201042103 [Main component symbol description] None 73

Claims (1)

201042103 VII. Shenqing patent scope: 1. An extruded and meltblown fiber comprising a polyhydroxyalkanoate polymer, a wet-milled nucleating agent and a plasticizer, wherein the wet-grinding nucleating agent The particle size is less than about 20 microns and is dispersed in the polymer. 2. The fiber of claim 1, wherein the nucleating agent is boron nitride. 3. The fiber of claim 1 or 2, wherein the fiber comprises from about 75 wt% to about 95 wt% of a polyhydroxyalkanoate polymer. 4. The fiber of claim 2, 2, or 3, wherein the fiber has a weight average molecular weight of at least about 1 50 kg/mol. The fiber according to any one of claims 1 to 4, wherein the plasticizer is tri-n-butyl citrate. 6. The fiber of any one of clauses 1 to 5, wherein the fiber has a diameter of from about 1 micron to about 5 micron. The fiber of any one of clauses 1 to 6, wherein the fiber has a diameter of from about 2 microns to about 5 microns. 8. The fiber of any one of clauses 1 to 7 wherein the nucleating agent comprises between about 1% and about 1% by weight of the total composition. 9. The fiber of any one of claims 1 to 8, which has a basis weight of from about 20 GSM to about 160 GSM. The fiber of any one of clauses 1 to 9, wherein the polyhydroxyalkanoate polymer is a poly(3-hydroxybutyrate) homopolymer, poly(3-hydroxybutyric acid) Ester-co-4-hydroxybutyrate), poly(3.hydroxybutyrate·co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-5-hydroxyvalerate) or poly (3_74 201042103 hydroxybutyrate-co-3-hydroxycaproate). 11. The fiber of any one of clauses 1 to 9, wherein the polyhydroxyalkanoate polymer is a poly(3-hydroxybutyrate) homopolymer having from 5% to 15% 4 -Polyhydroxybutyrate content of poly(3-hydroxybutyrate-co-4_hydroxybutyrate), poly(3-hydroxybutyrate- conjugated with 5% to 22% 3-hydroxyvalerate content -3-hydroxyvalerate), having from 5% to 15% of 5-hydroxyvalerate containing poly(3-hydroxybutyrate-co-5-hydroxyvalerate), or having from 3% to 15% Poly(3-hydroxybutyrate-co-3_hydroxycaproate) of 3-hydroxyhexanoate content. 12. The fiber of any one of the preceding claims, wherein the polyhydroxyalkanoate is: a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3- a blend of hydroxybutyrate-co-4-hydroxybutyrate; a) poly(3-hydroxybutyrate) homopolymer and b) poly(3-hydroxybutyrate-co-3_hydroxyl a blend of valerate; a) a blend of a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate); Poly(3-hydroxybutyrate co-_4_hydroxybutyrate) and b) poly(3-hydroxybutyrate-co-3_hydroxyvalerate) doped & a) poly(3- a blend of butylbutyrate _4_by butylbutyrate) with &) poly(3_ butylbutyrate-co-3 hydroxyhexanoate); or a) poly(3_ A blend of hydroxybutyrate-co-3-hydroxyvalerate and b) poly(3-hydroxybutyrate-co-3_hydroxyhexanoate). The fiber of any one of clauses 1 to 9, wherein the polyhydroxyalkanoate is: a) a poly(3-hydroxybutyrate) homopolymer and b) having 5% to a blend of 15% 4-hydroxybutyrate content of polyfluorene-hydroxybutyrate-co-hydroxybutyrate; a) poly(3-hydroxybutyrate) homopolymer and b) having 5% to Blend of 22% 3-hydroxyvalerate content poly(3_hydroxybutyrate-total 75 201042103 hydroxyvalerate); a) poly(3-hydroxybutyrate) homopolymer and b) a blend of 3% to 15% 3-hydroxyhexanoate content of poly(3-hydroxybutyrate-co-3_hydroxyhexanoate); a) having a 5% to 15% 4-hydroxybutyrate content Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and b) poly(3-hydroxybutyrate-co-3-hydroxyl group with 5% to 22% 3-hydroxyvalerate content a blend of valerate; a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) having a 5% to 15% 4-hydroxybutyrate content and b) having 3% to A blend of 15% 3-hydroxyhexanoate content of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)·'or a) has 5% to 22% 3-hydroxyvalerate Amounts of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and b) poly(3-hydroxybutyrate-total-3-) having a content of 3% to 15% 3-hydroxyhexanoate A blend of hydroxycaproate). 14. The fiber of claim 12 or 13, wherein the polyhydroxyalkanoate is: a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate) a blend of -co--4-hydroxybutyrate), and the weight of the polymer a) is from 5% to 95% by weight of the combination of the polymer a) and the polymer b); a) poly(3- a mixture of a hydroxybutyrate) homopolymer and b) poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and the weight of the polymer a) accounts for the polymer a) and polymerizes 5% to 95% by weight of the combined b); a) poly(3-hydroxybutyrate) homopolymer and b) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) And the weight of the polymer a) is from 5% to 95% by weight of the combination of the polymer a) and the polymer b); a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate a blend of b) poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and the weight of the polymer a) is the combined weight of the polymer a) and the polymer b) 5% to 95%; a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and b) poly 76 201042103 (3-hydroxybutyrate-co-3_hydroxyhexanoate) It And the weight of the polymer a) is from 5% to 95% by weight of the combined weight of the side polymer a) and the polymer b); or a) poly(3-hydroxybutyrate-co-3-hydroxyl) a blend of valerate) and b) poly(3-'hydroxybutyrate-co--3-hydroxyhexanoate) and the weight of the polymer a) comprises the polymer a) and the polymer b) The combined weight ranges from 5% to 95%. 15. The fiber of the invention of claim 12, 13 or 14 wherein the weight of the polymer a) is from 20% to 60% by weight of the combined weight of the polymer a) and the polymer b), and The weight of the polymer b) is from 40% to 80% by weight of the combined weight of the polymerized material and the polymer b). 1 6. The fiber of claim 2, wherein the polypyrrolate is: a) a poly(3-hydroxybutyrate) homopolymer and b) from 2% to 50% a blend of poly(3-hydroxybutyrate-co-4_hydroxybutyrate) having a 4-hydroxybutyrate content; a) a poly(3-hydroxybutyrate) homopolymer and b) 2〇% to 50°/. a blend of 5-pivalic acid ester-containing poly(3-butyric acid ester-co-5-pyridyl valerate); a) poly(3-hydroxybutyrate) homopolymer and b a blend of poly(3-hydroxybutyrate-co-3_hydroxyhexanol) having a 5% to 50% 3·hydroxycaproate content; a) having from 5% to 15% 4 Polyhydroxybutyrate content of poly(3-hydroxybutyrate-co-4_hydroxybutyrate) and b) poly(3-hydroxybutyrate) having a 20% to 50% 4-hydroxybutyrate content a blend of -co-4-hydroxybutyrate; a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) having a 5% to 15% 4-hydroxybutyrate content and b) a blend of poly(3-hydroxybutyrate-co-5-hydroxyvalerate) having a content of 20% to 50% 5-hydroxyvalerate; a) having from 5% to 15. /. 4-hydroxybutyrate content of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and b) poly(3-77 201042103 hydroxyl group) having a content of 5% to 50% 3-hydroxyhexanoate a blend of butyrate-co-3-hydroxyhexanoate; a) poly(3-hydroxybutyrate-co-3-hydroxyvalerate with a 5% to 22% 3-hydroxyvalerate content And (b) a blend of poly(3-hydroxybutyrate-co--4-hydroxybutyrate) having a content of 20% to 50% 4-hydroxybutyrate; a) having from 5% to 22 % 3-hydroxyvalerate content of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and b) poly(3-hydroxybutane) having a 20% to 50% 5-hydroxyvalerate content a blend of ester-co-5-hydroxyvalerate; a) having from 5% to 22. /. 3-hydroxyvalerate content of poly(3-butylidene-co-glycolic acid vinegar) and b) 5% to 50% 3-hexyl hexanoate content of poly(3 - a blend of butylbutyrate-co-3-hexylhexanoate, a) a poly(3_pyridylbutyrate- conjugate having a content of 3% to 15% 3-hexyl hexanoate -3-hydroxyhexanoate) and b) a blend of poly(3-arginine vinegar-co--4-butyric acid vinegar) having a content of 20% to 50% 4-hydroxybutyrate; a) poly(3-hydroxybutyrate-co-3_hydroxycaproate) having a content of 3% to 15% 3-hydroxyhexanoate and b) having 20% to 50% 5-perylvalerate a blend of poly(3-formylbutyrate-co-5-hydroxyvalerate) or poly(3-hydroxybutyrate- conjugated with 3% to 15% 3-hydroxyhexanoate content • 3-Hydroxyhexanoate) and b) a blend of poly(3-hydroxybutyrate-co-3_hydroxyhexanoate) having a 5% to 50% 3-hydroxyhexanoate content. The fiber of any one of the preceding claims, wherein the polyhydroxyalkanoate is: a) a poly(3-hydroxybutyrate) homopolymer and b) having 20% to a blend of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) having a concentration of 50% 4-hydroxybutyrate, and the weight of the polymer a) accounts for the polymer a) and the polymer b) 5% to 95% by weight of the combined weight; a) polyhydroxybutyrate) homopolymer and b) having a content of 20% to 50% 5-hydroxyvalerate 78 201042103 Poly(3-light-based butyric acid) a blend of vinegar-co--3 - via hydrazide, and the weight of the polymer a) is from 5% to 95% by weight of the combination of the polymer a) and the polymer b); a) a (3-butyric acid) homopolymer and b) a blend of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a content of 5% to 50% 3-hydroxycaproate And the weight of the polymer a) is from 5% to 95% by weight of the combination of the polymer a) and the polymer b); a) having a concentration of 5% to 15% of 4-hydroxybutyrate (3-hydroxybutyrate-co-4-hydroxybutyrate) and b) poly(3-hydroxybutyrate) having a 20% to 50% 4-hydroxybutyrate content - a total of _4_ butyl phthalate) and the weight of the polymer a) is from 5% to 95 by weight of the combined weight of the polymer a) and the polymer b). /. a) poly(3-butylidene-co-4-butyrate) having a 5% to 15% 4-butyrate content and b) having 20% to 50% 5-hydroxyl a compound of valerate poly(3-hydroxybutyrate-co-5-hydroxyvalerate), and the weight of the polymer a) is the combined weight of the polymer a) and the polymer b) 5% to 95%; a) Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) having a 5% to 15% 4-hydroxybutyrate content and b) having 5% to 50% 3 a blend of poly(3-hydroxybutyrate-co-3-ethyl 3 hexyl hexanoate) having a hydroxycaproate content, and the weight of the polymer a) comprises the polymer a) and the polymer b a combination of 5% to 95% by weight; a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) having a 5% to 22% 3-hydroxyvalerate content and b) having 20 a blend of poly(3-butyrate-co-4-hydroxybutyrate) having a butylbutyrate content of from 50% to 50%, and the weight of the polymer a) is the polymer a 5% to 95% by weight of the combination with polymer b); a) Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) having a content of 5% to 22% 3-hydroxyvalerate And b) have 20% to 50% 5-hydroxyl a compound of valerate poly(3-hydroxybutyric acid 79 201042103 ester-co--5-per valerate), and the weight of the polymer a) accounts for the polymer a) and the polymer b) 5% to 95% by weight of the combination; a) Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) having a content of 5% to 22% 3-hydroxyvalerate and b) having 5% a blend of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) to a content of 50% 3-hydroxyhexanoate, and the weight of the polymer a) accounts for the polymer a) and polymerize 5% to 95% by weight of the combined weight of b); a) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a content of 3% to 15% 3-hydroxyhexanoate and b a blend of poly(3-hydroxybutyrate·co-4-hydroxybutyrate) having a content of 20% to 50% 4-hydroxybutyrate, and the weight of the polymer a) is the polymer a) 5% to 95% by weight of the combined weight of the polymer b); a) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate having a content of 3% to 15% 3-hydroxyhexanoate And b) a blend of poly(3-hydroxybutyrate-co-5-hydroxyvalerate) having from 20% to 50% of 5-hydroxyvalerate, and the weight of the polymer a) Gather 5% to 95% by weight of the combination of &) and polymer b); or a) poly(3-hydroxybutyrate-co-3-hydroxyl group having a content of 3% to 15% 3-hydroxyhexanoate a hexanoate) and b) a blend of poly(3-hydroxybutyrate-co-3_hydroxyhexanoate) having a 5% to 50% 3-hydroxyhexanoate content and the polymer a) The weight is from 5% to 95% by weight of the combined weight of the polymer a) and the polymer b). 18. The fiber of claim 16 or 17, wherein the polymer a) comprises from 20% to 60% by weight of the combined weight of the polymer a) and the polymer b) and the polymer b The weight of the polymer a) is from 4% to 8〇0/〇 of the combined weight of the polymer a) and the polymer b). 19. The fiber 80 201042103 dimension of any one of claims 12 to 18, wherein the polyhydroxyalkanoate further has a 20% to 50% 4-hydroxybutyrate content with the polymer C). Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blending. The fiber according to any one of claims 12 to 18, wherein the polyhydroxyalkanoate is further polymerized with c) having a hydroxyvalerate content of 20% to 50%. Butyrate-co--5-hydroxyvalerate) blending. The fibrination dimension according to any one of claims 12 to 18, wherein the polyhydroxyalkanoate further has a concentration of 5% to 50% 3 _ hexanoate content with c) (3 - butylbutyrate-co--3-p-hexanoate) blending. 22. The fiber of claim 19, 20 or 21, wherein the weight of the polymer c) comprises the combined polymer weight of the polymer a), the polymer b) and the polymer c) 5% to 95%. The fiber according to claim 21, wherein the polymer c has a weight of 5% to 40% by weight of the polymer of the polymer a), the polymer b) and the polymer c). 24. A non-woven mesh comprising fibers as claimed in clauses 2-3 to 23. 25. A disposable article comprising the fibers of items 1 through 23 of the scope of the patent application. 26. An extruded meltblown fiber comprising between about 85 wt% and about % wt% of bio-produced polyhydroxybutyrate, between about 5% and about 15% of ethidium lemon Tri-n-butyl acid sate wherein the fiber has a weight average molecular weight of at least about 2〇〇81 201042103 kg/mol. 27. An extruded fiber comprising a bio-produced polyhydroxyalkanoate, a plasticizer, and a wet-milled nucleating agent' wherein the fiber has a weight average molecular weight of at least about 15 〇 kg/mol. 28 · a fiber comprising a polymer, a plasticizer and a nucleating agent, wherein the nucleating agent is dispersed in the polymer at least 5 degrees of the cumulative solid volume of the nucleating agent, or less than 5 Micron particles exist. Eight, the pattern: (such as the next page) 82