Thermoplastic blends for injection molding

Abstract

This disclosure provides formulations and processes that reduce the injection molding cycle times for poly(hydroxyalkanoate) blends which may contain a succinate polymer such as poly(butylene succinate), a filler such as lignocellulosic biomass and other additives. Blending of PHA with the second polymer may increase biodegradability and compostability.

Description

THERMOPLASTIC BLENDS FOR INJECTION MOLDINGCROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to and the benefit of U.S. App. No. 63 / 662,887, filed June 21, 2024, the contents of which are hereby incorporated by reference in their entirety.FIELD OF DISCLOSURE

[0002] The present disclosure is related to articles comprising a polyhydroxyalkanoate (PHA) blend suitable for injection molding. These injection molded articles may be used to create a variety of products including articles such as utensils and packaging containers including food or beverage containers such as bottles and containers. The PHA blend typically comprises a polyhydroxyalkanoate and a second biodegradable polymer such as a succinate polymer (e.g., succinate copolymer including polybutylene succinate) and optionally a filler such as lignocellulosic biomass (or the biomass produced from an extract thereof).BACKGROUND

[0003] Biodegradable resins attracted attention as environmentally friendly resins because the resins turn into substances that originally exist in nature due to actions such as hydrolysis under the environment and microbial metabolism. Polyhydroxyalkanoates are biological polyesters synthesized by a broad range of natural and genetically engineered bacteria as well as genetically engineered plant crops. These polymers are biodegradable thermoplastic materials, produced from renewable resources, with the potential for use in a broad range of industrial applications.

[0004] However, polyhydroxyalkanoate (PHA) typically been brittle with poor flexibility, resulting in a slower pace of industrial adoption until sufficient mechanical properties can be achieved. PHAs can have slow crystallization, poor processibility and thermal degradation at processing temperatures. The degradation temperature is close to melting temperature which causes polymer chain scission. Slow crystallization presents a major hurdle for injection molding because of lack of sufficient stiffness to eject the part from the mold. PHAs also have higher brittleness and rigidness than other thermoplastics which limits their application.

[0005] For example, thermoplastic resins using polyhydroxyalkanoates (PHA) and other biodegradable polymers such as polybutylene succinate (PBS) are often difficult tomanufacture into articles. These resins may have strength comparable to general-purpose plastics but often have processing problems such as slow cycle times during injection molding.

[0006] It is therefore an object of this disclosure to provide PHA based blends that allow for injection molding of a wider array of articles such as food utensils and packaging. Processes for the production of these articles are also provided using the thermoplastic resins of the present disclosure.SUMMARY

[0007] In accordance with the foregoing objectives and others, the present disclosure provides blends of PHA suitable for creation of biodegradable articles (e.g., food utensils such as forks, knives, and spoons, containers such as food containers) through, for example, molding processes which include injection molding processes involving compositions comprising these PHA blends. The articles may be used in a wide variety of industries such as the food and beverage industry or consumer packaged goods (e.g., beauty, personal care, haircare, skincare, cleaning, pharmaceutical, nutraceutical, household) product. In some embodiments, the thermoplastic PHA blends of the present disclosure may be characterized as having an injection molding cycle time of less than 30 s (e.g., less than 20 s, less than 15 s).

[0008] Without wishing to be bound by theory, the relative ratio of the PHA polymer to the immiscible polymer in the blend may be directly related to the ability7to form articles through the molding processes described herein (and, possibly, with the characteristic processing ability and / or biodegradability7and / or compostability). For example, in some embodiments, the immiscible polymer (e.g., succinate polymer such as polybutylene succinate) is present in the continuous phase of the blend of polyhydroxyalkanoate (PHA) and immiscible polymer and, for example, the composition has less than 50% PHA by weight of the composition. In some embodiments, the immiscible polymer is a biodegradable aromatic / aliphatic polyester such as a succinate polymer (e.g., polyalkylene succinate) terephthalate polymer (e.g., polyalkylene terephthalate). For example, the second optionally immiscible polymer may be polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate, polybutylene succinate terephthalate, polyethylene succinate terephthalate. In some embodiments, the polyalkylene succinate and / or polyalky lene terephthalate monomeric units are present in a co-polymer, such as copolymer with an ether and / or amide and / or aliphatic monomeric unit. Some polhydroxyalkanoates and / or second polymers are described in U.S. Pat. No. 8,822,584, whichis hereby incorporated by reference in its entirety and particularly in relation to polyhydroxyalkanoates and aromatic / aliphatic polyesters.

[0009] In some embodiments, the composition may comprise: a) polyhydroxy alkanoate (PHA), and b) a second polymer (e.g., a biodegradable aromatic / aliphatic polyester such as a succinate polymer (e.g., poly alkylene succinate) terephthalate polymer (e.g., polyalkylene terephthalate)); wherein the composition is characterized as having an injection molding cycle time of less than 30 s (e.g., less than 20 s, less than 15 s). For example, the succinate polymer may be a succinate polymer (e.g., polybutylene succinate) including copolymers thereof. In some embodiments, the second polymer (e.g., a biodegradable aromatic / aliphatic polyester such as a succinate polymer (e.g., polyalkylene succinate) terephthalate polymer (e.g.. poly alkylene terephthalate)) is biodegradable. For example, the succinate polymer may be polyalkylene succinate (e.g., polybutylene succinate). In various implementations, the polyhydroxyalkanoate is a polyhydroxy valerate polymer (e.g., polyhydroxy valerate copolymer such as a polyhydroxybutyratehydroxyvalerate (PHBV) including poly(3-hydroxybutyrate-co-3- hydroxyvalerate) (P3HB3HV), poly(3-hydroxybutyrate-co-4-hydroxyvalerate) (P3HB4HV)). The weight ratio of polyhydroxy alkanoate to succinate polymer is less than (or from 0.01 to) 1 (e.g., less than 2:3, 1: 100 to 1: 1, 1:100 to 2:3, l: 10 to 1 : 1, l : 10 to 2:3, l :4 to 1: 1, I:4 to 5:6, 3:7 to 2:3). In particular embodiments, the PHA and / or second polymer (e.g., aromatic / aliphatic polyester) is independently crystalline or semi-crystalline.

[0010] Compositions are provided which may comprise a thermoplastic resin (e.g., the PHA blends described herein) and a filler such as a lignocellulosic biomass. The present disclosure is partially premised on the characteristics afforded to compositions, such as processing ability and / or compostability and / or biodegradability, when combining fillers such as lignocellulosic biomasses with PHA blends. Lignocellulosic biomass is obtained from plants and typically has a complex structure containing cellulose, hemicellulose, lignin, and other polysaccharides. Rice husks (hulls), bamboo fiber, wheat straw, industrial hemp and fruit peels are some examples of lignocellulosic biomass sources. In various implementations, the composition comprises a filler. For example, the filler may comprise, consist essentially of, or be a lignocellulosic biomass. In various implementations, more than 90% (e.g., more than 95%, more than 98%, more than 99%) of the filler is lignocellulosic biomass by weight of the filler.The lignocellulosic biomass may be milled (e.g., milled rice husk) or the biomass of an extract thereof. For example, the lignocellulosic biomass is the biomass of an extract (e.g., the biomass remaining following extraction of milled rice husk such as alcoholic (e.g., ethanolic) extraction, aqueous, hot water extraction, or supercritical carbon dioxide extraction, or combinations thereof). In certain embodiments, the alcoholic extract is an ethanolic extract (e.g., 200 proof denatured ethanol comprising an alkane such as heptane). The lignocellulosic biomass may have a D90 particle size (e.g., as measured by dynamic light scattering) of less than 1000 pm (e.g., less than 750 pm, less than 500 pm). In various implementations, the low extractive biomass (the solid biomass remaining after extraction) is formed from a mixture having a weight ratio of solids to liquids of less than (or from 0.01 to) 1 (e.g., from 1 : 100 to 1 : 1, from 1: 10 to 1 : 1, from 1:5 to 1 : 1, from 1 :2 to 1 : 1. from 1:4 to 1:2). In various implementations, the lignocelluosic biomass has a moisture content of less than (or from 0.01 to) 5% by weight (e.g., less than 1% by weight). In some embodiments, the filler has a D90 particle size (e.g., as measured by dynamic light scattering) of less than 1000 pm (e.g., less than 750 pm, less than 500 pm). In various implementations, the weight ratio of thermoplastic resin (e.g., weight sum of the polyhydroxyalkanoate and the succinate polymer) to filler is from 1 : 10 to 10: 1 (e.g. , 1: 1 to 10: 1 :, 1: 1 to 1 :5, 1 : 1 to 1 :3, 1:1 to 1:2).

[0011] Compositions are provided which may comprise a thermoplastic resin (e.g., the PHA blends described herein) and a filler such as a lignocellulosic biomass, along with additives like glycerol, diatomaceous earth, or tocopherol acetate.

[0012] For example, the composition may comprise: a) from 60% to 70% thermoplastic resin by weight of the composition; and b) from 25% to 50% (e.g., 30% to 40%) lignocellulosic biomass by weight of the composition; wherein the sum of components a), and b) is less than 95% or less than 99% or less than less than 100%. or from 90% to 100% or from 95%-100%.

[0013] Articles (or a portion thereof) formed from these compositions are also provided. The article may be a food utensil (e.g., knife, fork, spoon) or package.

[0014] The compositions (or articles) of the present disclosure may have higher filler weights than ty pically encountered in similar articles. For example, the composition may comprise more than 20% filler by weight of the composition (e.g., more than 25% filler by weight of the composition, from 20%-50% filler by weight, from 25%-50% filler by weight of the composition, from 30%-40% filler by weight of the composition). Without wishing to bebound by theory, using high volume ratios of filler in the composition, a range of different blends can be used to formation of articles (e.g.. potentially with the mechancial properties for article creation and / or decreased cycle times and / or compostability and / or biodegradability). For example, in some embodiments, the composition comprises 30% filler by volume of the composition (e.g., more than 40% filler by volume of the composition, from 30% to 60% filler by volume of the composition, from 30% to 50% filler by volume of the composition, from 40% to 60% filler by volume of the composition, from 40% to 50% filler by volume of the composition). The composition may have a density of from 1.1 to 1.4 g / cm3. In some embodiments, the filler is a higher density filler (e.g., having a density of greater than 2.5 g / cm3) such as talc which has a density of from 2.7 g / cm3-2.8 g / cm3. In other embodiments, the filler may be a lower density filler with a density of from 0.5-1.5 g / cm3such as lignocellulosic biomass.

[0015] Methods for producing the articles are provided. The methods may involve forming an article comprising molding (e.g., injection molding) the compositions of the present disclosure (e.g., PHA / second polymer blends, thermoplastic resins comprising a lignocellulosic biomass filler). Methods of forming an article (e.g.. food utensil, container) may comprise: extruding and / or molding (e.g., extrusion blow molding, injection blow molding, injection stretch blow molding, and / or injection molding) a composition of the present disclosure.The method may further comprise surface treating the extruded and / or molded composition.

[0016] The article may be a molded article formed from mixing a first thermoplastic resin composition (e.g., a composition comprising PHA or succinate polymer) and a second thermoplastic resin composition (e.g., a composition comprising the other of PHA or succinate polymer), wherein the first thermoplastic resin composition and the second thermoplastic resin compositions have different degrees of crystallinity, extruded, and surface treated. For example, the first thermoplastic resin may have a tensile modulus greater than (or up to 5000 MPa) 1000 MPa (e.g., greater than 1500 MPa, greater than 1800 MPa, from 1000 MPa to 2500 MPa from 1000 MPa to 2000 MPa, from 1500 MPa to 2000 MPa, from 1700 to 1900 MPa, from 1800 to 1850 MPa) and the second thermoplastic resin has a tensile modulus less than 1000 MPa (e.g., less than 800 MPa, less than 600 MPa, less than 500 MPa, from 100 to 1000 MPa, from 200 to 600 MPa, from 200 MPa to 500 MPa, from 400 MPa to 500 MPa, from 450MPa to 490 MPa) as measured by ISO527. In some embodiments, the first thermoplastic resin has a melting point greater than 150°C (e.g., 150°C to 160°C) and the second thermoplastic resin has a melting point less than 150°C (e.g., 40°C to 120°C) as measured by differential scanning calorimetry run from 30°C to 200°C by 10°C / min. In various implementations, the weight ratio of the first thermoplastic resin to the second thermoplastic resin is from 10: 1 to 1: 10 (e.g., 9: 1 to 1:9, 5: 1 to 1:5, 4: 1 to 1:4. 3: 1 to 1 :3, 2: 1 to 1 :2, 3:2 to 2:3, 2: 1 to 5: 1). In particular embodiments, the weight ratio of polyhydroxyalkanoate to second polymer (e.g.. succinate polymer such as poly (butylene succinate)) is from 10: 1 to 1: 1 (e g., 5: 1 to 1 : 1, 3: 1 to 1: 1). The article may be a kitchen utensil (e.g., fork, knife, spoon) or a container such as container for housing a food or beverage or consumer packaged good product.BRIEF DESCRIPTION OF THE FIGURES

[0017] FIG. 1 plots the injection molding cycle time as a function of the polyhydroxyalkanoate (PHA) weight percentage in the thennoplastic fraction (the remaining portion of the thermoplastic fraction being poly(butylene succinate)) of composites comprising 60% thermoplastic (PHA / PBS) and 40% lignocellulosic biomass (black line) or composites comprising 100% thermoplastic (PHA / PBS) at various fractions (dotted line).

[0018] FIG. 2 provides a comparison of illustrating the effect of various fillers on the thermoplastic resin composition. Second heating DSC scan (@ 5 °C / min) of (a) 75% thermoplastic (50% PHA:50% PBS) (dark grey) and 25% Diatomaceous Earth (DE) (b) 75% thermoplastic (50% PHA:50% PBS) and 25% milled rice hull biomass (light grey).

[0019] FIG. 3 compares the biodegradability (under industrial anerobic conditions) after 17 days for cellulose (control), PHA / Rice Husk resin (Resin A), and PHA / PBS / Rice Husk resin (Resin B).

[0020] FIG. 4 compares the biodegradability (under home anerobic conditions) after 18 days for cellulose (control), PHA / Rice Husk resin (Resin A), and PHA / PBS / Rice Husk resin (Resin B).

[0021] FIG. 5 compares the marine biodegradability after 28 days for cellulose (control) and PHA / Rice Husk resin (Resin A).

[0022] FIG. 6 is an image illustrating the compostability of spoons following 8 weeks in composting inoculum.

[0023] FIG. 7 is an image of the composting inoculum and spoon mixture after 8 weeks of measurement.DETAILED DESCRIPTION

[0024] Detailed embodiments of the present disclosure are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the disclosure that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the disclosure is intended to be illustrative, and not restrictive.

[0025] All terms used herein are intended to have their ordinary7meaning in the art unless otherwise provided. All concentrations are in terms of percentage by weight of the specified component relative to the entire w eight of the topical composition, unless otherwise defined.

[0026] As used herein, “a” or “an” shall mean one or more. As used herein when used in conjunction with the word “comprising,” the words “a” or “an” mean one or more than one. As used herein “another” means at least a second or more.

[0027] As used herein, all ranges of numeric values include the endpoints and all possible values disclosed between the disclosed values. The exact values of all half-integral numeric values are also contemplated as specifically7disclosed and as limits for all subsets of the disclosed range. For example, a range of from 0.1% to 3% specifically discloses a percentage of 0.1%, 1%. 1.5%, 2.0%, 2.5%, and 3%. Additionally, a range of 0.1 to 3% includes subsets of the original range including from 0.5% to 2.5%, from 1% to 3%, from 0. 1% to 2.5%, etc. It will be understood that the sum of all weight or mol percentages of individual components will not exceed 100%.

[0028] By “consist essentially” it is meant that the ingredients include only the listed components along with the normal impurities present in commercial materials and with any other additives present at levels which do not affect the operation of the embodiments disclosed herein, for instance at levels less than 5% by weight or less than 1% or even 0.5% by weight.

[0029] The amounts of these various ingredients range individually or collectively ty pically from about 0.001 wt % to about 20 wt % by weight of the composition. The nature of these ingredients and their amounts may be compatible w ith the function of the compositions of the disclosure. The identification of a particular agent as having a certain function is not limiting, unless otherwise indicated, and does not preclude the same agent from having additional activities.

[0030] The present disclosure provides articles such as cutlery for a product formed from a blend of polymers blend suitable for forming articles and compositions which may be molded and / or extruded to form these articles. The blended polymers may be a polyhydroxyalkanoate (PHA) and a second polymer such as an aromatic / aliphatic polyester. The PHA and / or second polymer may be semi-crystalline. For example, the polymer may have a crystallinity' of more than 20% (and less than 100% or less than 90% or less than 80% or less than 70%). Semi crystalline polymers (particularly when the second polymer is semi crystalline) may afford decreased cycle times. Amorphous polymers may have a crystallinity of less than 5% as determined by differential scanning calorimetry' (DSC). Melting point (Tm), peak crystallization temperature (Tc), heat of fusion (Hf) and percent cry stallinity may be determined using the procedure according to ASTM E 794-85, which is hereby incorporated by reference in its entirety. Differential scanning calorimetric (DSC) data may be obtained using a TA Instruments Discovery' DSC machine or a Perkin-Elmer DSC 7 machine. Generally, to obtain these measurements, samples weighing approximately 5-10 mg are sealed in aluminum sample pans. The DSC data are recorded by heat-cool-heat cycles which may comprise first heating the sample to 25° C to 180° C at 5° C / min, then cooling the sample from 180° C. to -50° C. at 5° C / min and then gradually heating it to 180° C. at a rate of 5° C. / minute. Areas under the melting curves are measured and used to determine the heat of fusion and the degree of crystallinity. The percent cr stallinity (X %) may be calculated using the formula, X %=[area under the curve (Joules / gram) / B (Joules / gram)]*100, where B is the heat of fusion for the homopolymer of the major monomer component. These values for B may be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, which is hereby incorporated by reference in its entirety and particularly in relation to B values. For the semi-crystalline polymers, having appreciable crystallinity, the melting temperature is ty pically measured and reported during the second heating cycle (or second melt). For the amorphous polymers, having comparatively low levels of crystallinity, the melting temperature is typically measured and reported during the first heating cycle. Prior to the DSC measurement, the sample may be aged (typically by holding it at ambient temperature for a period up to about 2 days) or annealed to maximize the level of crystallinity.Thermoplastic Resin

[0031] In general, the thermoplastic resin of the present disclosure is a composition comprising a polyhydroxy alkanoate blend with a second polymer (biodegradable polymer) that may be immiscible with the polyhydroxyalkanoate. These resins may be used to producearticles through various manufacturing processes such as molding and / or extrusion. These blends have unexpectedly superior cycle times (which is further enhanced by the addition of other components such as specific fillers including lignocellulosic biomass and extracts the biomass remains following extraction thereof or other fillers such as diatomaceous earth (DE)). For example, the composition may comprise an immiscible blend of polyhydroxyalkanoate and the second polymer, where the second polymer is present in the continuous phase. In some embodiments, the second polymer is present in the continuous phase and the composition comprises more than 30% or more than 40% or more than 50% or more than 60% or more than 70% polyhydroxyalkanoate by weight of the composition.

[0032] The polyhydroxyalkanoate may have one or more monomeric units having the structure:wherein x 1, 2, 3, 4, 5, 6, 7, 8; andR is hydrogen or alkyl (e.g., C1-C12 alkyl, Ci-Cs alkyl, C1-C4 alkyl, C1-C2 alkyl). The polyhydroxy alkanoate (or PHA or poly(hydroxyalkanoate)) of the polymeric composition used to form the substrate in the article may comprise a variety’ of monomer contents, homopolymers or copolymers, including terpolymers, or mixtures thereof. In certain embodiments, the polyhydroxyalkanoate (or PHA or poly(hydroxyalkanoate)), may be a copolymer made up of from 75 to 99.9 mole percent monomer residues of 3-hydroxy butyrate and from 0.1 to 25 mole percent monomer residues of a valerate polymer. In certain embodiments, the poly(hydroxyalkanoates) of the polymeric composition preferably have a weight average molecular weight from 50,000 Daltons to 7.5 million Daltons, and more preferably have a weight average molecular weight from 300,000 Daltons to 3.0 million Daltons. The weight average molecular weight of the PHA may range between 600,000 to 2,000,000 Daltons as measured by light scattering and GPC with polystyrene standards. In particular embodiments the molecular weight is 500,000 to 750,000 or 700,000 to 1,500,000 Daltons.

[0033] In certain embodiments, the starting PHA used in the blend can be a copolymer (containing two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. For example, in some embodiments, the polyhydroxyalkanoate may be a short chain polyhydroxyalkanoate copolymer. In someembodiments, the PHA polymers are block polymers. Examples of PHA copolymers include poly 3-hydroxybutyrate-co-4-hydroxyvalerate, poly 3-hydroxybutyrate-co-3-hydroxyvalerate and poly 3-hydroxybutyrate-co-5-hydroxyvalerate.

[0034] By selecting the monomer types and controlling the ratios of the monomer units in a given PHA copolymer, a wide range of material properties can be achieved. The PHA can have more than two different monomer units (e.g., three different monomer units, four different monomer units, five different monomer units, six different monomer units). An example of a PHA having 4 different monomer units would be PHB-co-3HH-co-3HO-co-3HD or PHB-co- 3-HO-co-3HD-co-3HDd (these types of PHA copolymers may be referred to as PHB3HX).

[0035] In specific embodiments. the 3HBV copolymer is polyhydroxybutyratehydroxyvalerate such as poly-3-hydroxybutyrate-co-3-hydroxyvalerate. For example, the content of 3-hydroxybutyrate in the 3HB copolymer is 35% to 99% by weight of the 3HB copolymer, 45% to 99% by weight of the 3HB copolymer, or 75% to 1% by weight of the 3HB copolymer. In certain embodiments, the 3-hydroxy butyrate polymer (e.g., PHBV, PHB) and / or hydroxyoctanoate polymer (e.g., PHO) has a molecular weight of 500,000 to 1,500,000 Daltons as measured by gel permeation chromatography, and a glass transition temperature as measured by differential scanning calorimetry of from -5 to -50 °C. In other example embodiments, the 3-hydroxybutyrate polymer or hydroxy octanoate polymer has a molecular weight of 550.000 to 750,000 Daltons as measured by gel permeation chromatography, and a glass transition temperature as measured by differential scanning cal on mein of -10 to -30 °C.

[0036] The PHA and / or second polymer (e.g., succinate polymer such as PBS) may be independently synthesized from renewable sources such as extraction from organisms or petroleum based sources such as transesterification processes involving petro-based monomers. For example. PHAs and / or the second polymer can be extracted from sources including, but not limited to, single-celled organisms, such as bacteria or fungi, and higher organisms, such as plants. These sources, together with the PHAs that are biosynthesized, are generally referred to as biomass. While biomass can comprise wild-type organisms, they also can comprise genetically engineered species specifically designed for the production of particular PHAs of interest to the grower.

[0037] In some embodiments, the blend of PHA polymers is a blend of PHA polymers having a weight ratio of crystalline: amorphous of greater than 1 : 1 (e.g., from 1 : 1 to 10: 1, from 1 : 1 to5: 1, from 2: 1 to 10: 1, from 1 : 1 to 2: 1, from 2: 1 to 5: 1, from 50:50 to 70:30). In some embodiments, the blend comprises a mixture of PHA polymers having a weight ratio of crystalline:amorphous of greater than 50:50 (e.g., between 50:50 and 70:30). In some embodiments, the PHA (e.g., PHBV is crystalline, semi -crystalline, or amorphous). Powder form of these components may be compounded into individual pellets in the indicated ratio for subsequent mixing a delivery’ to a blow and / or extrusion machine.

[0038] The polyhydroxy alkanoate (e.g., PHBV) may have a valerate content of less than 25 mol % (e.g, from l%-25%, from 5%-25%, from 10%-25%, from 12%-25%. from 12%-20%, from 13%-20%, from 14%-20%, from 15%-20%, from 14%-16%).

[0039] The thermoplastic resin blends of the present disclosure (e.g., for use in forming an article through a molding process such as injection molding), which may comprise a blend of polyhydroxy alkanoate and a biodegradable (or compostable) polymer (e.g., a biodegradable polymer having one or more monomeric units such as monomers and co-polymers) independently having the structure -[C(O)-RI-C(O)-O-R.2-O]- wherein Ri is C2-C6 alkylene (e.g., ethylene, propylene, butylene, pentylene) or arylene (e.g., phenylene) and R2 is C2-C6 alkylene (e.g., ethylene, propylene, buty lene, pentyd ene), a succinate polymer, a terephthalate polymer, an adipate polymer, a poly(ethylene succinate), poly(butylene succinate), polypropylene succinate), poly(ethylene adipate), poly(butylene adipate), polypropylene adipate), poly(butylene terephthalate), polypropylene terephthalate). poly(ethylene succinate- co-adipate), polypropylene succinate-co-adipate), poly(butylene succinate-co-adipate), polypropylene succinate-co-adipate), poly(ethylene succinate-co-terephthalate), polypropylene succinate-co-terephthalate). poly(butylene succinate-co-terephthalate), polypropylene succinate-co-terephthalate), polyputylene adipate-co- terephthalate) (PBAT), poly(caprolactone), poly(lactic acid) (PLA), cellulose esters (such as cellulose acetate), polyvinyl alcohol (PVOH), thermoplastic starch, and mixtures thereof).

[0040] The biodegradable polymer blend thermoplastic composition may include compositions of polybutylene-succinate (PBS) or polybutylene-succinate-adipate (PBSA) and a bio based copolymer of 3-hydroxybutyrate (3HB) incorporating one or more comonomers selected from 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH) and 3-hydroxyoctanoate (3HO).

[0041] In some embodiments, the PHA (e.g., PHBV) is crystalline, semi-crystalline, or amorphous. In some embodiments, the second polymer (e.g., succinate polymer) is crystalline, semi-crystalline, or amorphous.

[0042] Physical properties and rheological properties of polymeric materials depend on the molecular weight and distribution of the polymer. ‘'Molecular weight” is calculated in a number of different ways. Unless otherwise indicated, “molecular weight” refers to weight average molecular weight. For example, a number average molecular weight (Mn) represents the arithmetic mean of the distribution and is the sum of the products of the molecular weights of each fraction, multiplied by its mole fraction. The weight average molecular weight (Mw) is the sum of the products of the molecular weight of each fraction, multiplied by its weight fraction. Mwis generally greater than or equal to Mn.

[0043] Forming the article may occur through the combination of various biodegradable and / or compostable compositions as described herein. In various implementations, the article is made from a first polymeric material (or thermoplastic resin composition such as a composition comprising PHA or a succinate polymer) and an additional material including one or more excipients such as a nucleating agent and / or a filler, which are mixed to form a first mixture. This first polymeric material may have a degree of cry stallinity of greater than 30% or greater than 40% or greater than 50% or greater than 60% or greater than 70% or greater than 80% or greater than 90%. The first mixture and a second compostable polymeric material (e.g., the other of PHA or succinate polymer if one is present in the first composition) may then be mixed to form a second mixture. The second polymeric material may have a degree of crystallinity' of from 15% to 45%. The second mixture may be melted and extruded to form an extrudate. The extrudate may be cooled to form the biodegradable substrate for formation of the article. The degree of crystallinity calculated for the compositions of the invention can be determined by various methods, for example, density calculations, x-ray diffraction (XRD), electron diffraction, neutron scattering, nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry, infrared absorption (FTIR). or Raman spectroscopy.

[0044] The material properties of the thermoplastic blend may be altered by incorporating an additional agent such as a filler and / or nucleating agent and / or deodorant into one of more thermoplastic blend compositions used to create the substrate for subsequent article molding. These components may be impregnated within the thermoplastic resin blend resulting in subsequent impregnation of the hardened resin used for the articles. Any additional component (e.g., filler, nucleating agent, deodorant, plasticizer, surfactant) may be independently presentin the composition in an amount of less than 40% or less than 30% or less than 20% or less than 10% or less than 5% or less than 3% by weight of the composition). In particular embodiments, the composition comprises less than 30% or less than 20% or less than 10% or less than 5% or than 3% nucleating agents (e.g., talc, boron nitride, or combinations thereof) and be characterized as having an injection molding cycle time of less than 30 s (e.g., less than 20 s, less than 15 s).

[0045] For example, the composition may comprise a nucleating agent selected from the group consisting of erythritols, pentaerythritol, dipentaerythritols, artificial sweeteners, stearates, polysaccharides, sorbitols, mannitols, inositols, polyester waxes, nanoclays, behenamide, erucamide, stearamide, oleamide, polyhydroxybutyrate, thymine, cyanuric acid, cytosine, adenine, uracil, guanine, boron nitride and mixtures thereof.

[0046] In some embodiments, the polymeric composition includes a plasticizer (e.g., less than (or from 0.1% to) 15% plasticizer by weight. This plasticizer may be selected from the group consisting of sebacates, citrates, fatty esters of adipic, succinic, and glucaric acids, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight from 200-10,000 g / mol, poly(ethylene glycols) having a number average molecular weight of 400-10,000 g / mol, esters of vegetable oils, long chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, polymeric plasticizers, poly(hydroxy alkanoates) copolymers comprising at least 18 mole percent monomer residues of hydroxyalkanoates other than hydroxybutyrate, and mixtures thereof. In certain implementations, the polymeric composition includes from 5 weight percent to 15 weight percent of the plasticizer.

[0047] According to some embodiments, the polymeric composition preferably also includes up to 20 weight percent of an impact modifier. This impact modifier may be selected from the group consisting of acrylic-based resins and emulsions, isosorbide derivatives, natural rubbers, aliphatic polyesters, or mixtures thereof. In various implementations, the polymeric composition may include from 5 weight percent to 15 weight percent of the impact modifier. In some embodiments, the PHA renders the presence of an additional impact modifier unnecessary. In certain aspects, further additives may also be included in the polymeric composition.

[0048] In some instances, the composition also includes up to 50 weight percent of one or more additives selected from the group consisting of poly(vinyl alcohols), poly(vinyl acetate),poly(vinyl laurate), poly(ethylene vinyl acetate), poly(glycolic acid), furandicarboxylic acidbased polyesters, cellulose, nanocellulose, glucans, and mixtures thereof. Some additives may be biodegradable such as cellulose, nanocellulose, glucans and mixtures thereof. However, some additives may inhibit the biodegradability of the films. The use of these materials may be limited such that the biodegradable of the resultant article would be considered biodegradable, for example, as measured be the various ASTM protocols described herein.

[0049] In certain embodiments, the compositions include one or more surfactants. Surfactants are generally used to de-dust, lubricate, reduce surface tension, and / or densify. Examples of surfactants include, but are not limited to mineral oil, castor oil, and soybean oil. One mineral oil surfactant is Drakeol 34, available from Penreco (Dickinson, Tex., USA). Maxsperse W-6000 and W-3000 solid surfactants are available from Chemax Polymer Additives (Piedmont, S.C., USA). Non-ionic surfactants with HLB values ranging from 2 to 16 can be used, examples being TWEEN-20, TWEEN-65, Span-40 and Span 85.

[0050] Anionic surfactants include: aliphatic carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid; fatty acid soaps such as sodium salts or potassium salts of the above aliphatic carboxylic acids; N-acyl-N-methylglycine salts, N-acyl- N-methyl-beta-alanine salts, N-acylglutamic acid salts, polyoxyethylene alkyl ether carboxylic acid salts, acylated peptides, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, naphthalenesulfonic acid salt-formalin polycondensation products, melaminesulfonic acid salt-formalin polycondensation products, dialkylsulfosuccinic acid ester salts, alkyl sulfosuccinate disalts, polyoxyethylene alkylsulfosuccinic acid disalts, alkylsulfoacetic acid salts, (alpha-olefinsulfonic acid salts, N-acylmethyltaurine salts, sodium dimethyl 5- sulfoisophthalate, sulfated oil. higher alcohol sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid salts, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkyl phenyl ether sulfuric acid salts, monoglysulfate, sulfuric acid ester salts of fatty' acid alkylolamides, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkyl phenyl ether phosphoric acid salts, alkyl phosphoric acid salts, sodium alkylamine oxide bistridecylsulfosuccinates, sodium dioctylsulfosuccinate, sodium dihexylsulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium diamylsulfosuccinate, sodium diisobutylsulfosuccinate, alkydamine guanidine polyoxyethanol, disodium sulfosuccinate ethoxylated alcohol half esters, disodium sulfosuccinate ethoxylated nonylphenol half esters, disodium isodecylsulfosuccinate, disodium N-octadecylsulfosuccinami de, tetrasodiumN-(l,2- dicarboxyethyl)-N-octadecylsulfosuccinamide, disodium mono- or didodecyldiphenyl oxidedisulfonates, sodium diisopropylnaphthalenesulfonate, and neutralized condensed products from sodium naphthalenesulfonate.

[0051] One or more lubricants can also be added to the compositions and methods of the invention. Lubricants are normally used to reduce sticking to hot processing metal surfaces and can include polyethylene, paraffin oils, and paraffin waxes in combination with metal stearates. Other lubricants include stearic acid, amide waxes, ester waxes, metal carboxylates, and carboxylic acids. Lubricants are normally added to polymers in the range of 0.1 percent to 1 percent by weight, generally from 0.7 percent to 0.8 percent by weight of the compound. Solid lubricants may be warmed and melted before or during processing of the blend.

[0052] Antioxidants can include, but are not limited to. sterically hindered phenols, aryl amines, thioureas, thiocarbamates, phosphites, thioether esters, and combinations of the foregoing. Suitable examples of antioxidants include, but are not limited to, alkylated monophenols, including but not limited to, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- di-methylphenol. 2.6-di-tert-butyl-4-ethylphenol, 2.6-di-tert-butyl-4-n-bulylphenol. 2,6-di- tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(?-methylcyclohexyl)-4,6- dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2, 4, 6-tri cyclohexylphenol, 2.6-di-tert-butyl- 4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(l '-methylundec- l'-yl)phenol, 2,4- dimethy l-6-( 1 '-methylheptadec- 1 '-y 1 )phenol, 2,4-dimethy l-6-( 1 '-methyltri dec- 1 -yl)phenol and mixtures thereof, alkylthiomethylphenols, including but not limited to, 2,4-dioctylthiomethyl- 6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2.4-dioctylthiomethyl-6- ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, hydroquinones and alky lated hydroquinones, including but not limited to. 2,6-di-tert-butyl-4-methoxyphenol, 2.5 di-tert- butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6- di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3.5-di-terl-butyl-4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4- hydroxyphenyl) adipate, tocopherols, including but not limited to, a-tocopherol, P-tocopherol, y-tocopheroL 6-tocopherol and mixtures thereof (e.g., vitamin E), hydroxylated thiodiphenyl ethers, including but not limited to, 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4- octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol). 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide. alkylidenebisphenols, including but not limited to, 2,2'-methylenebis(6-tert-butyl-4- methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(?-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol). 2,2'- methylenebis(6-nonyl-4-methylphenol). 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'- ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'- methylenebis[6-(?-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(?,?-dimethylbenzyl)- 4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2- methylphenol). l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5- methyl-2-hydroxybenzyl)-4-methylphenol, 1 , 1 ,3-tris(5-tert-butyl-4-hy droxy-2- methylphenyl)butane, l,l-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n- dodecylmercaptobutane, ethylene glycol bis|3.3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate|. bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)di cyclopentadiene, bis[2-(3'-tert-butyl-2'- hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, l,l-bis-(3,5-dimethyl- 2-hydroxyphenyl)butane, 2.2-bis(3.5-di-terl-butyl-4-hydroxyphenyl)propane. 2,2-bis(5-tert- butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, l,l,5,5-tetra-(5-tert-butyl-4- hydroxy-2-methylphenyl)pentane, O-, N- and S-benzyl compounds, including but not limited to, 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5- dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3.5-di-tert-butylbenzylmercaptoacetate. tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydro\y-2.6- dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl- 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, hydroxybenzylated malonates, including but not limited to, dioctadecyl-2, 2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl -2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, aromatic hydroxybenzyl compounds, including but not limited to, l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- trimethylbenzene, 1.4-bis(3.5-di-tert-butyl-4-hydroxy benz l J-2.3.5.6-tetramethylbenzene.2.4.6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, triazine compounds, including but not limited to, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-l,3,5-triazine, 2- octylmercapto-4.6-bis(3.5-di-tert-butyl-4-hydroxyanilino)-l,3,5-triazine, 2-octylmercapto-4.6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,3,5-triazine. 2,4,6-tris-(3.5-di-tert-butyl-4- hydroxyphenoxy)-l,2,3-triazine, l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, l,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris-(3,5-di-tert- butyl-4-hydroxyphenylethyl)-l,3,5-triazine, l,3.5-tris(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)-hexahydro-l,3,5-triazine, l,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate, benzylphosphonates, including but not limited to, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4- hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert- butyl-4-hydroxybenzylphosphonic acid, acylaminophenols, including but not limited to, 4- hydroxylauranilide, 4-hydroxystearanilide, octy l N-(3,5-di-tert-butyl-4- hydroxyphenyl)carbamate, esters of ?-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol. octadecanol. 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2.6.7-trioxabicyclo[2.2.2]octane. esters of 0- (5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2- {3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy } - 1 , 1 -dimethylethyl] -2,4,8, 10- tetraoxaspiro[5.5] -undecane, esters of 6-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide. 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane, esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol.. 1,2- propanediol, neopentyl glycal, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3- thiaundecanol. 3-thiapentadecanol, trimethylhexanediol. trimethylolpropane, 4- hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane, amides of 6-(3,5-di-tert-butyl-4- hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-buty-4- hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3 ,5 -di-tert-buty 1-4- hydroxyphenylpropionyl)trimethylenedi amide, N,N'-bis(3.5 -di-tert-buty 1-4- hydroxyphenylpropionyl)hy dr azide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard?XL-l, supplied by Uniroyal), ascorbic acid (vitamin C), aminic antioxidants, including but not limited to, N,N'-di-isopropyl-p- phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, dimethylpentyl)-p- phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(l- methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl- p-phenylenediamine. N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p- phenylenediamine. N-( 1 ,3-dimethylbutyl)-V -phenyl-p-phenylenediamine. N-( 1- methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N.N'-dimethyl-N.N'-di-sec-butyl-p-phenylenediamme. diphenylamine, N-allyldiphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1- naphthyl amine, N-(4-tert-octylphenyl)-l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, including but not limited to, p,p'-di-tert-octyldiphenylamine, 4-n- butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4- dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine 2,6-di- tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane. 4,4'- diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1 ,2-bis [(2- methylphenyl)amino] ethane, l,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(l',3'- dimethylbutyl)phenyl] amine, tert-octyl ated N-phenyl-1 -naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated teak-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-l ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated Cert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'- tetraphenyl-l,4-diaminobut-2-ene, and combinations of the foregoing. The composition may comprise less than (or from 0.01% to) 2% antioxidant by weight or less than 1% by weight or less than 0.5% by weight or from 0.05% to 2% by weight or from 0.05% to 1% by weight or from 0.05% to 0.5% by weight.

[0053] The present application is partially premised on the discovery' that the use of the thermoplastic resins and / or the biomass of the present disclosure may be added without affecting the cycle time. For example, the composition may have less than 10% or less than 5% or less than 2% additive (e.g., plasticizer, antioxidant, combination thereof) by weight of the composition.Filler

[0054] In some embodiments, the composition comprises a filler. The polymeric composition may also include up to 60% (or from 0.1% to) a filler by weight of the composition. This filler may be selected from the group consisting of calcium carbonate, talc, nano clays, nanocellulose, hemp fibers, kaolin, carbon black, wollastonite, glass fibers, carbon fibers, graphite fibers, mica, silica, dolomite, barium sulfate, magnetite, halloysite, zinc oxide, titanium dioxide, montmorillonite, feldspar, boron, steel, carbon nanotubes, cellulose fibers, flax, cotton, starch, polysaccharides, aluminum hydroxide, magnesium hydroxide, modified starches, chitins and chitosans, alginates, gluten, zein, casein, collagen, gelatin, polysaccharides, guar gum, xanthan gum, succinoglycan, natural rubbers; rosinic acid, lignins, natural fibers, jute, kenaf, hemp, ground nut shells, wood flour, and mixtures thereof, and mixtures thereof. In some embodiments, the polymeric composition includes from 5 weight percent to 60 weight percent of the filler. In various implementations, the filler comprises less than 5% or less than 1% or less than 0.5% talc by weight of the filler. Without wishing to be bound by theory, the present compositions may incorporate higher filler amounts (particularly with lignocellulosic biomass based fillers) affording the thermoplastic blends capable of having improved manufacturing capabilities such as reduced cycle times and product characteristics such as biodegradability and / or compostability. The filler may comprise without limitation materials like cellulose, talc, calcium carbonate, starch, or a combination thereof. In particular embodiments, the filler comprises a lignocellulosic biomass (e.g. , a mass derived from plant matter comprising lignin and cellulose and / or hemicellulose). In some embodiments, the lignocellulosic biomass has had certain components removed therefrom, for example, by applying an extraction to the lignocellulosic biomass and collecting the solid content for use as a filler.

[0055] For example, the filler may be formed from:(a) contacting a lignocellulosic feedstock with a fluid (e.g., water, an alcohol such as ethanol, a combination thereof), to form a slurry' of lignocellulosic material in the fluid (e.g., at a temperature in the range of between about 150° C. to about 250° C , and a pressure in the range of between about 200 psi to about 1000 psi, or between about 200 psi to about 1500 psi) for a time period (e.g., more than 1 minute, more than 5 minutes, more than an hour, more than a day from 1 minute to 1 week, from 12 hours to 48 hours, from 12 hours to 36 hours); and(b) recovering the solid material, the reaction slurry' to be used as the filler (for optional further processing such as moisture removal).In some embodiments, the solid material is further washed with the fluid one or more times. In some embodiments, the solid material may be filtered (e.g., passed through a first mesh and optionally collected on a second mesh). For example, the first and second mesh independently may be a mesh of from 20-100 (e.g., from 40-80, from 45-75).

[0056] In some embodiments, the slurry is formed in a reaction vessel, digester, or digestion reactor. The ratio of solid lignocellulosic material: liquid extraction solvent in the reaction vessel, digester or digestion reactor may be less than (or from 0.01 to) 1 (e.g., from 1: 100 to 1: 1, from 1: 10 to 1: 1, from 1:5 to 1 : 1, from 1:2 to 1 : 1, from 1:4 to 1:2). In some embodiments, the slurry is not heated. In some embodiments, the slurry is heated, e.g., to a temperature of from 25°C to 100°C.

[0057] Alcohols that can be used in the extraction include or comprise: ethanol, methanol, isopropanol, butanol, polyols, propylene glycol, ethylene glycol or combinations thereof. In certain aspects, the extraction fluid can comprise: carbon dioxide, ammonia, ethane, ethylene, acetone, propane, propylene, nitrous oxide and butane and combination thereof; or. carbon dioxide and one or more co-solvents (e.g., alcohol, water).

[0058] The lignocellulosic feedstock may comprise: a wood, optionally a hardwood or a softwood; a cotton fiber; a grass or any plant of the genus Miscanthus a straw; a cane; an agricultural residue, optionally a com cob or a com husk, or a sugar cane bagasse; a residue generated in an oil palm production process, or a palm tree (or any plant of the family Arecaceae) harvesting or production process, and optionally a palm mesocarp fiber; a palm frond or a palm trunk; fruit peels; a rice husk; a rice bran; or, any combination thereof. The lignocellulosic feedstock may be ground and / or milled and / or spheronized prior to addition to the extraction liquid.Article Formation

[0059] The present disclosure provides an article such as a kitchen utensil or packaging for a consumer goods product, wherein the article includes at least one biodegradable portion which comprising the aforementioned polymeric composition (or the composition having been processed by, for example, molding and / or extrusion). In certain embodiments, the biodegradable portion (or entire article) is formed a method selected from the group consisting of injection molding, compression molding, thermoforming, cast and blown film formation,extrusion coating, extrusion blow molding, injection blow molding, injection stretch blow molding, and extrusion profiling. In particular embodiments, the article (or a portion thereof) is formed from a blow molding process such as injection blow molding or injection stretch blow molding or extrusion blow molding.

[0060] A compostable material for use as the substrate in the articles described herein may comprise a polymeric PHA material, the second polymer (e.g., succinate polymer) and a nucleating agent. In some embodiments, the material has a degree of crystallinity of greater than 50%. The degree of crystallinity of the material may affect the thermal and mechanical properties of the material.

[0061] The degree of crystallinity of the article can be roughly characterized by the portion of the material in which the compostable polymeric material has crystallized in comparison to the entire material. The compostable polymeric material can in some cases crystallize on its own during cooling, so some of the cry stal li zed portions are in regions of the material without the nucleating agent. The presence of the nucleating agent can accelerate crystallization, so some of the crystallized portions may be localized near nucleating agent dispersals in the polymeric material. The crystallized portions of the material may include spherulite structures, which can be formed by a controlled crystallization (cooling) process.

[0062] As described above, the degree of crystallinity of the material 100 can be calculated as % crystallinity by dividing the amount of the crystalline phase by the total amount of the material and multiplying by 100 as determined by differential scanning calorimetry (DSC). For the fabrication of useful articles, the compositions described herein are processed preferably at a temperature above the crystalline melting point of the polymers but below the decomposition point of any of the ingredients (e g, the additives described above, with the exception of some branching agents) of the polymeric composition. While in heat plasticized condition, the polymeric composition is processed into a desired shape, and subsequently cooled to set the shape and induce crystallization. Such shapes can include, but are not limited to, a fiber, filament, film, sheet, rod, tube, bottle, or other shape. Such processing may be performed using any technique, such as, but not limited to, extrusion, injection molding, injection stretch molding, extrusion blow molding, compression molding, blowing or blow molding (e.g, blown film, blowing of foam), calendaring, rotational molding, casting (e.g, cast sheet, cast film), or thermoforming. Thermoforming is a process that uses films or sheets of thermoplastic. The polymeric composition is processed into a film or sheet. The sheet of polymer is then placed inan oven and heated. When soft enough to be formed it is typically transferred to a mold and formed into a shape.

[0063] In some embodiments, the article may be a food utensil such a fork, spoon, knife, spork, or straw. In some embodiments, the article may be used for food packaging, beverage packaging, or consumer packaged goods packaging. The packaging may provide physical protection for a product (<?.g., including but not limited to food, beverage such as wine, beer, hard seltzer, spirits, ready to drink cocktail, carbonated soft drinks, seltzerjuices water: beauty product, personal care product, haircare product, pharmaceutical product, cleaning product, natural and dietary supplement products); the product in the package may require protection from, among other things, shock, vibration, compression, temperature, moisture content fluctuation, CO2, oxygen content fluctuation, ultraviolet light, and / or bacteria. The packaging may take the form of trays, bags, boxes, cans, cartons, pallets, or bottles.

[0064] Articles made from the compositions described herein such as those produced by combining multiple PHA compositions with different cry stallinities or those produced by combining a PHA composition with another biodegradable polymer may exhibit greater tensile toughness and elongation while exhibiting an increased biodegradability. Without wishing to be bound by theory', the combination of PHA with a second polymer (particularly those that are immiscible with the PHA such as succinate polymers) and / or the use of low-extractive lignocellulosic biomass with thermoplastic resins such as PHA blends is suitable for the preparation of articles having the appropriate impact strength and / or tensile strength.

[0065] As explained above, the article may be molded such as blow molded, injection molded, extrusion molded, injection blow molded, extrusion blow molded, injection stretch blow molded, or combinations thereof. Molded articles can additionally be made from the blend compositions described herein. Polymers (or composites comprising the PHA with the second polymer (e.g., succinate polymer such as polybutylene succinate) and / or lignoceullosic biomass such as low-extractive lignocellulosic biomass) used for injection molded parts are first fed into a heated barrel and melted. As is typical in extrusion blow molding, these polymers may be extruded into a mold cavity such as a tube, sealed within the cavity , inflated with air expand to the shape of the cavity, and cooled to form an extrusion blow molded article. In some embodiments, the polymer (or composite) may be mixed and forced into a closed mold cavity under pressure to create the part (e.g., through injection, through extrusion). The part may be cooled and so hardens to the configuration of the cavity. After cooling, the moldgenerally opens, and the part may then be ejected and sometimes subjected to further finishing steps (e.g., the surface treatment).

[0066] Whether the article-making process such as utensil making process is an injection stretch blow molding process where the injected preliminary products are typically referred to as ‘'preforms” or an injection blow molding or extrusion blow molding process where the injected products are typically called “parisons,” the hot melt generally begins to cool the instant it enters an injection cavity because such cavities are relatively much colder than the distribution manifolds and injection nozzles through which the melt travels on its way to the injection cavities. If melt enters some of the cavities of a set of multiple cavities at a slightly different time than others and / or at a different rate, the melt in some cavities will cool at different rates than others, and some will not have as much time to cool down as others before the preforms are pulled out of the injection mold for the next stage in the process. This can affect the quality and consistency of the finished products. Balancing the relative temperature of the melt and mold (particularly within an appropriate tolerance for mass production) can result in increased and more consistent articles. In some embodiments, the polymer (or polymer blend) may be heated to a temperature of from 115°C to 220°C (e.g., from 120°C- 205°C, from 135°C to 150°C, from 150°C to 185°C, from 185°C to 220°C) in order to form a melt to place in the mold cavity. The mold cavity may be kept at a temperature of from 30°C- 50°C (e.g., with water). The dryer temperature may be kept at, for example, 75°C to 100°C. Leveraging the properties of the PHA polymer blends of the present disclosure, the extruder RPM may be, for example from 3-10 RPM (e.g., 5-7 RPM). In various implementations, these blends may be molded with an extruder load of from 35%-40%, an RPM of from 5-7 RPM, a melt pressure of from 950 psi to 2000 psi (e.g., from 1000 psi to 1200 psi).

[0067] The subject matter described in this disclosure can be implemented in particular embodiments so as to realize certain product characteristics. For example, the compostable material can have a suitable degree of crystallinity that allows for the material (for example, in sheet form) to be quickly thermoformed (or another forming, manufacturing, or conversion process). The compostable material can have a heat deflection temperature (HDT) that is higher than the HDT of traditional utensils. The compostable material can be microwavable, such that the compostable material can be exposed to microwave energy and retain its thermal and mechanical properties and without deforming. A microwavable material can have a high heat resistance and adequate stiffness at elevated temperatures. Optionally, the outer surface of an article made of a microwaveable material remains sufficiently cool such that the article can besafely handled. In some embodiments, the compostable material is substantially free of impact modifier (for example, does not include an impact modifier) but still has suitable ductility and / or strength. In some embodiments, the compostable material is visually transparent or translucent.Biodegradable and / or Compostable

[0068] This disclosure describes articles that may be generally compostable. Articles comprising compostable or biodegradable material may include an organic or inorganic material configured to chemically or physically break down or decompose under aerobic and / or anaerobic conditions, such as in a municipal or industrial composting or digesting facility. In some embodiments, the article may be configured to chemically or physically break down or compose in marine or freshwater environments. For example, in some embodiments, an article of the present disclosure may contain 90% to 100% or 99% to 100% compostable and / or biodegradable material(s). The article may, for example, have aerobic (e.g., compost) biodegradability characterized by more than 70% or more than 80% or more than 90% after 28 days as measured at 58°C according to ISO14855 (compost). In some embodiments, the article may have aerobic compostability of more than 60% or more than 70% at 25°C according to ISO 14851 (activated sludge). In some embodiments, the article may have anaerobic compostability (e.g., biogas) of more than 60% or more than 70% or more than 80% or more than 90% or more than 95% or more than 99% at 35°C according to 1SO14853 (aqueous phase). In some embodiments, the article may have anaerobic compostability (e g., biogas) of more than 60% or more than 70% at 52°C according to ISO15985 (solid phase). In various implementations, the article may be biodegraded in sea water to form H2O and CO2 (e.g., as characterized by a biochemical oxygen demand (BOD) test and / or a chemical oxygen demand (COD) test at, for example, 27°C, and with a, for example freeze grinded pow der of the article, having a BOD / COD result greater than 50% after 10 days or after 15 days or after 20 days or after 25 days or after 30 days or after 35 days or after 40 days or after 45 days or after 50 days).

[0069] Typically, the articles of the present disclosure are compostable and / or biodegradable as described herein. Although not preferred, an article of the present disclosure (e.g., food utensil, food container, beverage container, consumer packaged good container) may include one or more generally non-compostable or non-biodegradable materials. However, in most embodiments, if present, the non-compostable or non-biodegradable materials are present in small amounts such as less than 1% by weight or less than 0.1% by weight of the article. In some embodiments, the article is formed from a unitary piece of material (which may beoptionally surface treated). In some embodiments, the sheet material may be extruded, coextruded. or laminated. In some embodiments, the sheet material may be extruded, co-extruded, or laminated using a single screw extruder or a multi-screw extruder (e.g., twin screw extruder). By providing compostable materials as articles for particular products, consumers of such products may produce that is less harmful to the environment, degrades quicker than non- compostable products in landfills and / or natural environments (e.g., the ocean).

[0070] Biodegradable compositions generally undergo biodegradation by living organisms (microbes) in anaerobic and aerobic environments (as determined by ASTM D5511). in soil environments (as determined by ASTM 5988), in freshwater environments (as determined by ASTM D5271 (EN 29408)), or in marine environments (as determined by ASTM D6691). The biodegradability of biodegradable plastics can also be determined using ASTM D6868 and European EN 13432. In some embodiments, the articles of the present disclosure are also “compostable”, as determined by ASTM D6400 for industrial (typically at 58°C) or home compostability (typically at 28°C). For example, a composition may be characterized as biodegradable if more than 90% carbon to CO2 occurs in one year under anerobic conditions. Each of the protocols are incorporated herein by reference in their entirety and in particular to how to identify biodegradable and compostable materials. In some embodiments, the compositions of the present disclosure are industrially compostable, home compostable, or a combination thereof. In some embodiments, the compositions of the present disclosure are industrially compostable but not home compostable.

[0071] In embodiments, the renewable carbon content of the polymer composition of the invention as measured by ASTM D6866 is at least 1% by weight of the composition, at least 20% by weight of the composition, at least 40% by weight of the composition, at least 80% by w eight of the composition, at least 95% by weight of the composition, at least 99% by w eight of the composition, or is 100% by w eight of the composition.

[0072] The biodegradation rate by gravimetric methods. In this case, a polymer film is buried in soil or other media containing active aerobic microorganisms and water. The w eight loss of the polymer film over time is then measured and used to determine the disintegration rate. Several organizations certify the biodegradability of polymers under different standards and conditions. These include Vincotte, DIN-CERTCO and European Bioplastics. These are all European-based certifications for industrial composting, home composting, soil, fresh water and sea water biodegradation. The requirements standard utilized for composting, soil and water biodegradation is EN 13432 while the test method utilized is EN 14995. For sea waterbiodegradation, the requirement standard is ASTM D7081 and the test method is ASTM D6691. In the US, Biodegradable Products Institute (BPI) certifies for industrial composting using the standards ASTM D6400 (plastics) and D6868 (paper coatings). The Australian Bioplastics Association has also set up biodegradation certificates for home and industrial compositing following the standards AS4736-2006 and AS5810-2010.EXAMPLES

[0073] Example 1

[0074] Rice husks were milled to produce lignocellulosic biomass with particle size distribution with 90% of particles passing below 450 pm as measured through a particle size analyzer. Milled biomass powders were dried at 105 °C to reduce the moisture content below 1% by weight. The milled biomass powder was combined with polybutylene succinate (PBS) and polyhydroxyalkanoate (PHA). The PBS had a density of 1.27 g / cm3, melt flow rate (MFR) of 22 g per 10 min (tested at 190 °C with 2.16 kg test mass) using ASTM DI 238 method, melting temperature peak at 114 °C, and glass transition temperature (Tg) at 89 °C. The PHA was poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB) and had a melting temperature peak at 150 °C, Tgat -15 °C, and MFR of 11 g / 10 min (tested at 190 °C with 2. 16 kg test mass). The MFR of PHA / PBS blends between ratios 40 / 60 to 30 / 70 ranged between 14.2 to 19.4 g per 10 min (at 190 °C with 2.16 kg test mass).

[0075] Compounding of thermoplastics and lignocellulosic biomass was carried out on a Leistritz twin-screw extruder with temperature zones from 118°C to 205°C to provide compounded resins. Injection molding of 60% by weight PBS / PHA (thermoplastic) and 40% by weight lignocellulosic biomass extrusion-compounded resin. Injection molding was carried out at 160-165°C temperature. These compositions were prepared at various ratios of PHA:PBS to examine the injection molding cycle time for the thermoplastic resin blends. Table 1 provides the corresponding injection molding times for each blend of thermoplastic resin.Table 1

[0076] As can be seen, the cycle times of compositions comprising thermoplastic resin and lignocellulosic biomass filler responded non-linearly with respect to the PHA:PBS weight ratio with all blends illustrating a faster cycle time in relation to the pure PHA. A marked and unexpectedly steep reduction in cycle times was observed with PHA: PBS weight ratios of less than 60:40 and PHA:PBS blends having as much as 40% PHA showed almost identical cycle times to pure PBS / filler compositions.

[0077] Thermoplastic resins with variations of the content of filler (e.g., biomass as prepared above, diatomaceous earth (DE)), identity of polyhydroxyalkanoate (semi-cry stalline (scPHA) or amorphous), and the relative ratio of succinate polymer (PBS) to polyhydroxy alkanoate (PH3B4HB). The resins were then injection molded. Table 2 provides the corresponding cycle times and injection pressures applied during the processing.Table 2

[0078] FIG. 1 plots the injection molding cycle time as a function of PHA weight percentage of the thermoplastic resin fraction. In FIG. 1 , each data point is labelled with the relative weight ratio of PHA:PBS in the thermoplastic fraction comprising the filler. As can be seen, the filler decreases the cycle times at ratios of PHA:PBS of greater than 30:70. Additionally, rice hulls provided a statistically significant decrease in cycle times as compared to diatomaceous earth filler. For example, in the 50:50 blend of PBS:scPHA with 25% filler by weight of the composition, diatomaceous earth provided a cycle time of 80 s while rice hulls provided a cycle time of 55 s.

[0079] Tensile properties of the injection molded finished product were assessed for several of these blends. The injection molded finished product was a disposable knife. Table 3 provides the measured tensile properties for each disposable knife as a relative change in relation to the 100% PBS product. Percentages are based on the percentages present in the composition used to form the disposable knife.Table 3

[0080] As can be seen in Table 3, DE does not provide the tensile strength or modulus (stiffness) that biomass can provide at the same weight percentages in the composition. Cutlery containing DE instead of biomass (at the same filler loading) broke easily and had low mechanical properties. Addition of PHA and / or biomass increases the strength and stiffness compared to neat PBS providing unexpected advantages. For example, a 75% thermoplastic resin (50% PBS:50% PHA) composition having 25% diatomaceous earth (DE) could not prepare knife cutlery because the parts were sticking in the mold and were bent when pulled out (however a similar result was not seen when using biomass).

[0081] Additional prep

[0082] Measurements on the crystallinity and the heating curve were also measured for several formulations. Table 4 provides the crystallinity of formulations as measured from the 2ndheating curve in DSC measurements.Table 4Calculation of crystallinity from melting enthalpy, enthalpy values for 100% crystalline polymer were taken as 1 10 J / g for PBS and 146 J / g for PHA, based on Saeng-on J, Aht-Ong D., Journal of Applied Polymer Science. 135.43 (2018): 46836 and Wellen RM, et al. Polymer testing. 32.2 (2013): 215-20, each of which are hereby incorporated by reference in their entirety and particularly in relation to crystallinity’ calculations and enthalpy values of polymers.

[0083] FIG. 2 compares the effect of filler on the second heating DSC scan (5°C / min) of 75% Thermoplastic (50% PHA: 50% PBS)and 25% filler. The filler was either milled rice hullbiomass or diatomaceous earth. As can be seen, there is no crystallization when diatomaceous earth is used as filler. However, when lignocellulosic biomass was used, PHA crystallization was observed. Without wishing to be bound by theory, it is believed that the unexpectedly increased crystallinity (particularly PHA crystallinity) induced through the use of certain fillers such as lignocellulosic biomass results in the decreased injection molding cycles times.

[0084] Example 2

[0085] Milled rice husk biomass was prepared similar to milling technique described in Example 1. Milled biomass was soaked in 200 proof ethanol denatured with heptane at 40% solid to liquid ratio for 24 hours to solubilize the specific extractives from milled rice husk. This biomass-ethanol slurry was washed with 2 times the volume of total slurry with fresh ethanol to remove compounds extracted from the biomass. The washed slurry was filtered through 60 mesh and then air-dried for several days with turning of biomass with spatula to remove the ethanol. The solid low-extractives biomass was then dried in a conventional oven at 105 °C for 6 h.

[0086] The biomass of the extract was compounded at 35% concentration with 65% PBS thermoplastic by extrusion at 120-205 °C temperature to make a composite resin. This composite resin had significantly reduced odor of agricultural grain, as measured by qualitative smell test by several people. A reduction in odor was also noticed during extrusion (compounding) of thermoplastics with biomass.

[0087] Example 3

[0088] Thermoplastic resins of the present disclosure underwent industrial biodegradability (ASTM 6400). home biodegradability (tests were performed covering all international and national standards such as AS 5810. NF T 51-800), and marine biodegradability tests (ASTM D6691). With regard to the home composting measurements, the standards are directly based on those for industrial biodegradability, since the two processes mainly differ in temperature and duration. The home biodegradability' testing occurs at ambient temperature (while industrial biodegradability occurs at 58°C), and the certification requirement requires 90% carbon to CO2 conversion at 28°C in one year.

[0089] For the biodegradability studies, blends of PHA with rice hulls and blends of PHA / PBS with rice hulls were measured and compared to cellulose.

[0090] FIG. 3 shows the biodegradation percentage for Cellulose, 60 wt% scPHA / 40 wt% milled Rice Hulls (Resin A), and 18 wt% PHA / 42 wt% PBS / 40 wt % milled Rice Hulls (ResinB) as measured by the industrial composting (aerobic biodegradation at 58°C) for the first 17 days of the biodegradation test using cellulose as a reference. The data in FIG. 3 is the average values determined from three replicate runs of each sample (and control). Table 5 provides the Total Organic Carbon (TOC) measurement, net CO2 production, and parameters relating to the biodegradation percentage for the tests after 17 days of experiment. Table 5

[0091] Neat PBS typically has a biodegradation rate in controlled compost at aerobic biodegradation conditions and 58°C of 5.8% release as shown in Kunioka M, et al. Int J Mol Sci 10.10 (2009): 4267-4283, which is hereby incorporated by reference in its entirety. For example, at 16 days, PBS of industrial composting conditions, neat PBS had a biodegradation of 5.8% (CO2 release). However, as can be seen, PBS incorporation into compositions with PHA (e.g., scPHA) and / or fillers, particularly at high amounts of filler, unexpectedly did not inhibit the biodegradability of the resultant material sufficiently to prevent meeting biodegradability standards of the compositions and articles formed therefrom.

[0092] FIG. 4 shows the biodegradation percentage for Cellulose, PHA / Rice Hulls (Resin A), and PHA / PBS / Rice Hulls (Resin B) as measured by the home composting (aerobic biodegradation at 28°C) for the first 18 days of the biodegradation test using cellulose as a reference. The data in FIG. 4 is the average values determined from three replicate runs of each sample (and control). Table 6 provides the Total Organic Carbon (TOC) measurement, net CO2 production, and parameters relating to the biodegradation percentage for the tests after 18 days of experiment.Table 6

[0093] FIG. 5 shows the biodegradation percentage for Cellulose, PHA / Rice Hulls (Resin A) as measured by the marine aerobic biodegradation tests in seawater (ASTM D661) for the first18 days of the biodegradation test using cellulose as a reference. The data in FIG. 5 is theaverage values determined from three replicate runs of Resin A (and control). Table 7 provides the Total Organic Carbon (TOC) measurement, net CO2 production, and parameters relating to the biodegradation percentage for the tests after 18 days of experiment.Table 7

[0094] As can be seen the compositions of the present disclosure are trending towards biodegradable as identified by, for example, ASTM 6400 (and similar home biodegradability testing at 28°C) and ASTM D6691.

[0095] Example 4

[0096] Compostability tests were performed on spoons formed from extrusion of Resin A (PHA / Rice Hulls). Spoons were mixed in a 1 wt% concentration (5 spoons, each cut into 3 pieces) with compost inoculum. The obtained mixtures were incubated in the dark at ambient temperature (28°C ± 2°C). Two replicates are performed per test item and qualitatively evaluated during the time period of evaluation.

[0097] FIG. 6 provides an overview of the visual observations of a spoon at the beginning of the compostability study and after 8 weeks in compost inoculum. The width of each box at the bottom of the figure represents 1 cm. As can be seen, after 8 weeks of composting, the sppon has transformed into small fragments. These small fragments crumble easily, are soft, and fragile. FIG. 7 provides an image of the compost inoculum after 8 weeks of testing. As can be seen, the spoon fragments are not visually obvious in the compost.

[0098] As various changes can be made in the above-described subject matter without departing from the scope and spirit of the present disclosure, it is intended that all subject matter contained in the above description, or defined in the appended claims, be interpreted as descriptive and illustrative of the present disclosure. Many modifications and variations of the present disclosure are possible in light of the above teachings. Accordingly, the present description is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims.

[0099] All documents cited or referenced herein and all documents cited or referenced in the herein cited documents, together with any manufacturer’s instructions, descriptions, productspecifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated by reference, and may be employed in the practice of the disclosure.

Claims

CLAIMS1. A composition comprising: a) polyhydroxyalkanoate (PHA), and b) a succinate polymer; wherein the composition is characterized as having an injection molding cycle time of less than 30 s (e.g., less than 20 s, less than 15 s).

2. The composition according to claim 1. wherein said succinate polymer is a succinate copolymer (e.g., polybutylene succinate).

3. The composition according to any one of claims 1-2, wherein said succinate polymer is biodegradable.

4. The composition according any one of claims 1-3, wherein said succinate polymer is polyalkylene succinate (e.g., poly butylene succinate).

5. The composition according to any one of claims 1-4, wherein the polyhydroxyalkanoate is a polyhydroxyvalerate polymer (e.g., polyhydroxyvalerate copolymer such as a polyhydroxybutyratehydroxy valerate (PHBV) including poly(3- hydroxybutyrate-co-3-hydroxy valerate) (P3HB3HV). poly(3-hydroxybutyrate-co-4- hydroxyvalerate) (P3HB4HV)).

6. The composition according to any one of claims 1-5, wherein the weight ratio of polyhydroxyalkanoate to succinate polymer is less than (or from 0.01 to) 1 (e.g., less than 2:3, 1 : 100 to 1 :1, 1: 100 to 2:3, 1: 10 to 1: 1, 1 : 10 to 2:3, 1 :4 to 1 :1, 1:4 to 5:6, 3:7 to 2:3).

7. The composition according to any one of claims 1-6, wherein the composition further comprises a fdler.

8. The composition according to claim 7, wherein the filler comprises lignocellulosic biomass.

9. The composition according to claim 8, wherein the lignocellulosic biomass comprises or is milled (e.g.. milled rice husk) or the biomass of an extract thereof.

10. The composition according to claim 8 or 9, wherein the lignocellulosic biomass is the biomass of an extract (e.g., the biomass remaining following alcoholic extraction of milled rice husk such as ethanolic extraction).

11. The composition according to any one of claims 8-10. wherein the lignocelluosicbiomass has a moisture content of less than (or from 0.01 to) 5% by weight (e.g., less than 1% by weight).

12. The composition according to any one of claims 7-11. wherein the filler has a D90 particle size (e.g., as measured by dynamic light scattering) of less than 1000 pm (e.g.. less than 750 pm, less than 500 pm).

13. The composition according to any one of claims 7-12, wherein the weight ratio of thermoplastic resin (e.g., weight sum of the polyhydroxyalanoate and the succinate polymer) to filler is from 1: 10 to 10:1 (e.g., 1: 1 to 10: 1 :, 1 : 1 to 1 :5, 1 :1 to 1:3, 1: 1 to 1:2).

14. The composition according to any one of claims 7-13, wherein the composition comprises more than 20% filler by weight of the composition (e.g., more than 25% filler byweight of the composition, from 20%-50% filler by weight, from 25%-50% filler by weight of the composition, from 30%-40% filler by weight of the composition).

15. The composition according to any one of claims 7-14, wherein the composition comprises more than 30% filler by volume of the composition (e.g., more than 40% filler by volume of the composition, from 30% to 60% filler by volume of the composition, from 30% to 50% filler by volume of the composition, from 40% to 60% filler by volume of the composition, from 40% to 50% filler by volume of the composition).

16. A composition comprising a thermoplastic resin and a lignocellulosic biomass; wherein the lignocellulosic biomass is the solid biomass remaining following an alcoholic extraction of rice husk.

17. The composition according to claim 16, wherein the rice husk is milled.

18. The composition according to any one of claims 16-17, wherein the lignocellulosic biomass has a D90 particle size (e.g., as measured by dynamic light scattering) of less than 1000 pm (e.g.. less than 750 pm, less than 500 pm).

19. The composition according to any one of claims 16-18, wherein the extract is formed from a mixture having a weight ratio of solids to liquids of less than (or from 0.01 to) 1 (e.g., from 1:100 to 1 : 1, from 1: 10 to 1 : 1, from 1 :5 to 1 :1, from 1:2 to 1: 1, from 1:4 to 1:2).

20. The composition according to any one of claims 16-19, wherein the lignocelluosic biomass has a moisture content of less than (or from 0.01 to) 5% by weight (e.g., less than 1% by weight).

21. The composition according to any one of claims 16-20, wherein the thermoplastic resin is a blend of polyhydroxyalkanoate and a succinate polymer.

22. The composition according to claim 21, wherein said succinate polymer is a succinate copolymer.

23. The composition according to claim 21 or 22, wherein said succinate polymer is biodegradable.

24. The composition according any one of claims 21-23, wherein said succinate polymer is polyalkylene succinate (e.g., polybutylene succinate).

25. The composition according to any one of claims 21-24, wherein the polyhydroxyalkanoate is a polyhydroxyvalerate copolymer (e.g., poly(3-hydroxybutyrate-co- 3-hydroxy valerate) (P3HB3HB), poly(3-hydroxybutyrate-co-4-hydroxy valerate) (P3HB4HB)).

26. The composition according to any one of claims 21-25, wherein the weight ratio of polyhydroxy alkanoate to succinate polymer is less than (or from 0.01 to) 1 (e.g., less than 2:3, 1 : 100 to 1 : 1, 1: 100 to 2:3, l: 10 to 1 : 1, l : 10 to 2:3, l:4 to 1 : 1, 1:4 to 5:6, 3:7 to 2:3).

27. A composition comprising: a) from 60% to 70% thermoplastic resin by weight of the composition; and b) from 30% to 40% lignocellulosic biomass or an extract thereof by weight of the composition; wherein the sum of components a) and b) is less than 95% or less than 99% or less than less than 100%. or from 90% to 100% or from 95%-100%.

28. The composition according to any one of claims 1-27, wherein the composition comprises less than 2% additives (e.g., plasticizers such as glycerol, antioxidants such as tocopherols, combinations thereof) by weight of the composition.

29. An article (or a portion thereof) formed from the composition according to any one of claims 1-28.

30. The article according to claim 29, wherein the article is a food utensil (e.g., knife, fork, spoon) or package.

31. A method of forming an article comprising molding (e.g., injection molding) the composition according to any one of claims 1-28.

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