Combinations of thermoplastic polymers with polyhydroxyalkanoates and fumaric acid

Abstract

Compositions of polymeric blends of thermoplastic polymers with polyhydroxyalkanoate (hereinafter referred to as PHA) are described. When blended, these combinations can produce an undesirable odor. This odor is reduced or eliminated by adding fumaric acid to the odorous combination. Methods of making the compositions of the invention and resulting products are also described.

Description

95610.12016COMBINATIONS OF THERMOPLASTIC POLYMERS WITH POL YHYDROXYALKANO ATES AND FUMARIC ACIDCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to United States Provisional Patent Application No. 63 / 788,537, filed April 14, 2025, the entire contents of which is incorporated by reference herein.BACKGROUND OF THE INVENTION1, Field of the Invention:

[0002] The present disclosure describes compositions of polymeric blends of thermoplastic polymers with polyhydroxyalkanoate (hereinafter referred to as PHA). When blended, these combinations can produce undesirable odors. Such odors can be reduced or eliminated by adding fumaric acid, or another suitable odor-reducing additive to the odorous combination. Methods of making the compositions of the invention are also described.2, Description of the State of the Art:

[0003] In the first decade of this century, more plastic was produced than all the plastic in history up to the year 2000. The use of plastic materials on a large scale has represented a mark in the history of technological development; however, the increasing utilization of these materials is resulting in serious environmental problems. In the case of petrochemical-derived plastic resins, approximately 900 billion pounds worldwide are produced annually, and it is estimated that this number will continue to increase each year by approximately four percent.

[0004] Greenhouse gas emissions have been increasing globally at an alarming rate. Global anthropogenic emissions of CO2 and CH4 have almost hit 43.1 billion tons and 9,390 mmtC02e, respectively (Global Carbon Project Budget-2019, Global Methane Initiative Report-2018). The overall global atmospheric concentrations of CO2 and CH4 have increased by 12.07 and 5.9%, respectively, in the last two decades (NOAA-ESRL, 2020). Moreover, the global warming potential of CH4 is 28-36 times higher than CO2 (US-EPA).

[0005] The use of microorganisms as biocatalysts for the sequestration of CO2 and CH4 require mild operating conditions and do not release any toxic by-products resulting in an attractive means to produce value-added products having very low negative carbon95610.12016footprints. Naturally occurring methane-oxi dizing microorganisms are known as methanotrophs. Owing to their ability to utilize methane as the source of carbon and energy, methanotrophs serve as excellent candidates for methane sequestration.

[0006] Some methanotrophs possess an added advantage of sequestering CH4 as a substrate for enzymatic hydrogenation into methanol and thereby qualify as suitable candidates for CH4 sequestration. Besides their ability to harness noxious Cl compounds, methanotrophs can also serve as potential cell-factories for a wide-range of high-value products, e g., methanol, ectoine / hydroxyectoine, poly-P-hydroxybutyrate (PHB), single cell protein, extracellular polysaccharide, lipids etc.

[0007] The PHA polymer class and more specifically poly-P-hydroxybutyrate (PHB) produced using methane as a substrate is of particular interest. PHB is one of the simplest and most important polymers in the polyhydroxyalkanoates (PHAs) biopolymer family, an important family of biodegradable biopolymers, which are polyesters naturally synthesized by over 300 different microorganisms, serving as natural energy reserves for the microbe.

[0008] The commercial interest in PHBs is directly related to the biodegradability and biocompatibility characteristics, their thermo-mechanical properties and production costs, and also their ability to serve as a carbon sequestration vehicle, which in turn can be used to lower the carbon footprint of polymers that it may be blended with. Unfortunately, blends of PHA's with certain common resins, additives, and fillers can often emit an undesirable odor when processed at higher temperatures.BRIEF SUMMARY OF THE INVENTION

[0009] A composition comprising a polymer combination of at least one thermoplastic polymer, at least one polyhydroxyalkanoate, and fumaric acid is disclosed, wherein the composition has reduced odor compared to a corresponding composition that does not include fumaric acid.

[0010] The present invention includes several advantages, not all of which are incorporated in a single embodiment.

[0011] In general, the present invention describes a composition that is useful for the manufacture of articles containing polyhydroxyalkanoate. In particular, the invention pertains to95610.12016an article of manufacture having a composition comprising a blend of polymeric material, such as a polyolefin (e.g., polypropylene) with a PHA that, when blended, has reduced odor (in some cases a low odor, or in still additional cases, no odor).

[0012] The present invention further addresses a need for improving the carbon footprint of petrochemical-derived plastic resins, such as but not limited to polypropylene.

[0013] The present invention further identifies thermoplastic polymer materials (including, in particular embodiments, polypropylene materials) that when blended with PHA, most specifically PHB, to produce a PHA-containing polymer alloy, and can reduce or eliminate noxious odors and can also maintain and / or improve the desired physical and mechanical properties of the base polymeric material, while lowering the overall carbon footprint of the base polymeric material.

[0014] The novel PHB -containing polymer compositions can be made by any suitable method, using any suitable order of processing.

[0015] Thus, a need exists for improving the carbon footprint of the approximately 900 billion pounds of petrochemical-derived plastic resins that are produced worldwide on an annual basis and lower or eliminate odors associated with polymeric combinations with PHA. Through the incorporation of methane based PHA or PHB into these petrochemical-derived plastic resins thereby creating a PHA-containing polymer, the carbon footprint of the resulting PHA-containing polymer may be reduced by a range of amounts, including an amount of CO2e equivalent to the full physical weight of that PHB-containing polymer. In addition to providing an enormous opportunity to sequester carbon, vis-a-vis PHA-containing polymers, the present invention seeks to minimize the undesirable odor that is typical when blends of PH As are processed with synthetic polymers and formulation components which are common in the thermoplastics industry.

[0016] Processing of the combination of thermoplastic polymer with PHA, especially PHB, is known to produce noxious odors. Processing these combinations in the presence of fumaric acid has been found to eliminate these odors.

[0017] There is provided herein, in several embodiments, a composition comprising a polymer combination comprising fumaric acid and having a reduced odor profde. There is95610.12016provided herein, in several embodiments, a composition comprising a polymer combination of at least one thermoplastic polymer, at least one polyhydroxyalkanoate, and fumaric acid.

[0018] In several embodiments, the thermoplastic polymer is a polyolefin. In several embodiments, the polyolefin is selected from polypropylene, polyethylene, a polyolefin elastomer, a thermoplastic polyolefin, or a combination thereof. In several embodiments, the polyolefin is polypropylene.

[0019] In several embodiments, the polyhydroxyalkanoate comprises PHB, PHBV, PHB4HV, PHBHHx, or a mixture thereof. In several embodiments, the polyhydroxyalkanoate is PHB.

[0020] In several embodiments, the thermoplastic polymer comprises a polyolefin and the polyolefin is present in an amount ranging from about 50% to about 99.9% of the composition by weight, the polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight, and the fumaric acid is present in an amount ranging from about 0.01 % to about 10% of the composition by weight.

[0021] In several embodiments, the particle size for fumaric acid is 150 mesh or higher. In several embodiments, the particle size for fumaric acid is 100-120 mesh, 120-130 mesh, 130-140 mesh, 140-150 mesh, 150-180 mesh or 180-200 mesh (or any size within those ranges).

[0022] In several embodiments, the thermoplastic polymer is polystyrene, acrylonitrile butadiene styrene, polycarbonate / acrylonitrile, butadiene styrene, polycarbonate, polyamide, acrylic and methacrylic polymer and / or copolymer, cellulose ester, polyvinyl chloride, thermoplastic polyurethanes, thermoplastic elastomers, polyethylene terephthalate, or a combination thereof.

[0023] There is also provided herein a composition comprising a combination of polymers having reduced odor emission, the composition comprising at least one thermoplastic polymer, at least one polyhydroxyalkanoate, and an odor-reducing additive.

[0024] In several embodiments, the at least one thermoplastic polymer is present in an amount ranging from about 50% to about 99.9% of the composition by weight. In several embodiments, the at least one polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight. In several embodiments, the odor-reducing95610.12016additive is present in an amount ranging from about 0.01 % to about 10% of the composition by weight. In several embodiments, the composition exhibits a reduced odor as compared to combinations of polymers that do not comprise an odor-reducing additive.

[0025] In several embodiments, the odor-reducing additive comprises fumaric acid.

[0026] In several embodiments, the odor emission is reduced by at least about 20% as compared to compositions not comprising an odor reducing additive.

[0027] In several embodiments, the odor emission is reduced by at least about 30% as compared to compositions not comprising an odor reducing additive.

[0028] In several embodiments, the odor-reducing additive is selected from the group consisting of sebacic acid, stearic acid, palmitic acid, dimer acid (Pripol 1027), citric acid, pectin, green tea polyphenols, fumaric acid, adipic acid, and itaconic acid.

[0029] In several embodiments, the odor-reducing additive is present in an amount between about 0.01% and about 5% of the composition by weight. In several embodiments, the odor-reducing additive is present in an amount between about 0.03% and about 3% of the composition by weight.

[0030] Additionally provided for herein is a composition comprising a combination of polymers having reduced odor emission, the composition comprising at least one thermoplastic polymer, at least one polyhydroxyalkanoate, and an odor-reducing additive comprising fumaric acid.

[0031] In several embodiments, the at least one thermoplastic polymer is present in an amount ranging from about 50% to about 99.9% of the composition by weight. In several embodiments, the at least one polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight. In several embodiments, the fumaric acid is present in an amount ranging from about 0.01 % to about 10% of the composition by weight, and wherein the composition exhibits a reduced odor as compared to combinations of polymers that comprise a non-fumaric acid odor-reducing additive.

[0032] In several embodiments, the fumaric acid is present in an amount ranging from about 0.05% to about 3% of the composition and the composition exhibits odor emission that is95610.12016reduced by at least about 30% as compared to a combination of polymers that comprise a non-fumaric acid odor-reducing additive.BRIEF DESCRIPTION OF THE DRAWINGS

[0033] A further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings. All drawings are not to scale.

[0034] FIG. l is a bar chart showing the results of an analysis of odor emitted by various compounds provided for herein.DETAILED DESCRIPTION OF THE INVENTION

[0035] This specification describes a composition comprising a polymer combination of at least one thermoplastic polymer, a polyhydroxyalkanoate (PHA), and fumaric acid and methods for making the same, wherein the composition has reduced odor compared to a corresponding composition that does not include fumaric acid. One preferred thermoplastic polymer is polypropylene, which belongs to the group of polyolefins. If the PHA component is produced from a methane emissions-derived substrate, the carbon footprint of the thermoplastic polymer resin can be reduced.

[0036] The present invention relates to a blend of two polymeric materials wherein the thermoplastic polymer component, preferably polypropylene, is between about 50% - 99.9% of the total PHA-containing blend. The PHA, which is preferably PHB, is between about 0.1% to about 50% of the total PHA-containing blend. The two most preferred polymers, polypropylene and PHB, may include homopolymers, copolymers, and blends thereof.Thermoplastic polymer

[0037] The composition contains at least one thermoplastic polymer. The most preferred thermoplastic polymer is the polyolefin polypropylene. Petrochemical-derived thermoplastic polymer resin can also include all other polymers used in the plastics manufacturing industry, including, but not limited to, polystyrene, polyethylene (PE), acrylonitrile butadiene styrene (ABS), polycarbonate / acrylonitrile butadiene styrene (PC-ABS), polycarbonate (PC), polyamides including polyamide 6 (PA-6) (also known as Nylon 6 or polycaprolactam), acrylic and methacrylic polymers and copolymers, such as PMMA, cellulose esters, polyvinyl chloride (PVC), thermoplastic polyurethanes (TPU) and other thermoplastic elastomers (TPE), or polyesters (such95610.12016as polyethylene terephthalate, or PET) in combination with a PHA component. In one embodiment, blending of PHB is preferred with polyolefins. A polyolefin is a type of polymer with the general formula (CH2CHR)n where R is an alkyl group. They are usually derived from a small set of simple olefins (alkenes). They include polypropylene homopolymers and copolymers, impact polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), poly-I-butene, 1,2-polybutadiene, hydrogenated material thereof, polyolefin elastomers, thermoplastic polyolefins, EPDM rubber and polyisobutylene. A preferred polyolefin is the polypropylene class which includes polypropylene homopolymers, copolymers, and impact polypropylenes. Specific polypropylenes, include such brand names Sumitomo YIOI, Flint Hills PP4, Lyondel Bassel Profax 6523, Exxon 5341E1, Braskem FT200WV, and Pinnacle 1120H.PHA

[0038] The present specification generally relates to a PHA-containing polymer composition for the manufacture of durable articles having lower odor, and, optionally, a lower carbon footprint. Polyhydroxyalkanoate polymers can be generated by many known means, but can include manufacture using microorganisms or microorganism enzymes; by bacterial fermentation of sugars, lipids, starches, agricultural biomass or gases; or by chemical reaction not inside of microbial cell walls. PHAs include, but are not limited to, polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-covalerate (PHBV), polyhydroxyhexanoate (PHHx) and blends thereof as discussed in detail below, as well as both short chain length (SCL), medium chain length (MCL), and long chain length (LCL) PHAs. While the term PHB, as the most preferred component, will be used throughout this application one skilled in the art will understand that the breadth of this invention would apply to the family of PHAs.

[0039] The PHA can be a homopolymer (all monomer units are the same). Examples of PHA homopolymers include poly 3 -hydroxy alkanoates (e.g., poly 3 -hydroxypropionate (hereinafter referred to as P3HP), poly 3-hydroxybutyrate (hereinafter referred to as PHB) and poly 3 -hydroxy valerate), poly 4-hydroxyalkanoates (e.g., poly 4-hydroxybutyrate (hereinafter referred to as P4HB), or poly 4-hydroxyvalerate (hereinafter referred to as P4HV)) and poly 5-hydroxyalkanoates (e.g., poly 5-hydroxyvalerate (hereinafter referred to as PSHV)).95610.12016

[0040] In certain embodiments, the starting PHA is a copolymer (containing two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. Examples of PHA copolymers include poly 3-hydroxybutyrate-co-3-hydroxypropionate (hereinafter referred to as PHB3HP), poly 3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as PHB4HB), poly 3-hydroxybutyrate-co-4-hydroxyvalerate (hereinafter referred to as PHB4HV), poly 3-hydroxybutyrate-co-3-hydroxyvalerate (hereinafter referred to as PHB3HV), poly 3-hydroxybutyrate-co-3-hydroxyhexanoate (hereinafter referred to as PHB3HH) poly 3-hydroxybutyrate-co-5-hydroxyvalerate (hereinafter referred to as PHBSHV)and Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx).

[0041] 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. Although examples of PHA copolymers having two different monomer units have been provided, 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 orPHB-co-3-HO-co-3HD-co-3HDd (these types of PHA copolymers are hereinafter referred to asPHB3HX). Typically, where the PHB3HX has 3 or more monomer units the 3HB monomer is at least 70% by weight of the total monomers, preferably 85% by weight of the total monomers, most preferably greater than 90% by weight of the total monomers for example 92%, 93%, 94%, 95%, 96% by weight of the copolymer and the HX comprises one or more monomers selected from 3HH, 3HO, 3RD, 3HDd.

[0042] The homopolymer (where all monomer units are identical) PHB and 3-hydroxybutyrate copolymers (PHB3HP, PHB4HB, PHB3HV, PHB4HV, PHBSHV, PHB3HHP, hereinafter referred to as PHB copolymers) containing 3-hydroxybutyrate and at least one other monomer are of particular interest for commercial production and applications. It is useful to describe these copolymers by reference to their material properties as follows. Type I PHB copolymers typically have a glass transition temperature (Tg) in the range of 6°C to -10°C, and a melting temperature Tm of between 80°C to 180°C. Type 2 PHB copolymers typically have a Tg of -20°C to -50°C and Tm of 55°C to 90°C and are based on PHB4HB, PHBSHV polymers95610.12016with more than 15% 4HB, SHV, 6HH content or blends thereof. In particular embodiments, the Type 2 copolymers have a phase component with a Tg of -1 5°C to -45°C and no Tm.

[0043] The molecular weight of PHA ranges between about 5,000,000 and about 2,500,000 Daltons, between about 2,500,000 and about 1,000,000 Daltons, between about 1,000,000 and about 750,000 Daltons, between about 750,000 and about 500,000 Daltons, between about 500,000 and about 250,000 Daltons, between about 250,000 and about 100,000 Daltons, between about 100,000 and about 50,000 Daltons, between about 50,000 and about 10,000 Daltons, and overlapping ranges thereof.

[0044] In determining the molecular weight, techniques such as gel permeation chromatography (GPC) can be used. The PHA can have a 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 certain embodiments, preferably, the PHAs generally have a weight-average molecular weight in the range of 100,000 to 700,000. For example, the molecular weight range for PHB and Type I PHB copolymers for use in this application are in the range of 20,000 Daltons to 1.5 million Daltons as determined by GPC method and the molecular weight range for Type 2 PHB copolymers for use in the application 20,000 to 1.5 million Daltons.

[0045] As discussed above, the novel blended polyolefin / polyhydroxyalkanoate composition of the present invention comprise, in one embodiment, blends of polypropylene and PHB. Optionally additives such as those disclosed below may be used to further change the desired properties of the blended composition of the present invention.

[0046] The functional characteristics of the PHA include, but are not limited to, molecular weight, polydispersity and / or polydispersity index, melt flow and / or melt index, monomer composition, co-polymer structure, melt index, non-PHB material concentration, purity, impact strength, density, specific viscosity, viscosity resistance, acid resistance, mechanical shear strength, flexural modulus, elongation at break, freeze-thaw stability, processing conditions tolerance, shelf. -life / stability, hygroscopicity, and color. As used herein, the term "poly dispersity index" (or PDI), shall be given its ordinary meaning and shall be considered a measure of the distribution of molecular mass of a given polymer sample (calculated as the weight average molecular weight divided by the number average molecular weight).95610.12016Branched Polyhydroxyalkanoates

[0047] The term "branched PHA" refers to a PHA with branching of the chain and / or coupling of two or more chains. Branching on side chains is also contemplated.Branching can be accomplished by various methods. The PHAs described previously can be branched by branching agents by free-radical-induced coupling of the polymer. In certain embodiment, the PHA is branched prior to combination in the method. In other embodiments, the PHA is reacted with peroxide in the methods of the invention. The branching increases the melt strength of the polymer and can impart greater compatibility of the polymeric components of the formulation. PHA can be branched in any of the ways described in U.S. Pat. Nos. 6,620,869, 7,208,535, 6,201,083, 6,156,852, 6,248,862, 6,201,083 and 6,096,810 all of which are incorporated herein by reference in their entirety.

[0048] The polymers of the invention can also be branched according to any of the methods disclosed in International Publication No. WO 2010 / 008447, titled "Methods For Branching PHA Using Thermolysis" or International Publication No. WO 2010 / 008445, titled "Branched PHA Compositions, Methods for Their Production, and Use in Applications, " both of which were published in English on Jan. 21, 2010, and designated the United States. These applications are incorporated by reference herein in their entirety.Branching Agents

[0049] The branching agents, also referred to as a free radical initiator, for use in the compositions and methods described herein include organic peroxides. Peroxides are reactive molecules and can react with linear PHA molecules or previously branched PHA by removing a hydrogen atom from the polymer backbone, leaving behind a radical. PHA molecules having such radicals on their backbone are free to combine with each other, creating branched PHA molecules. Branching agents are selected from any suitable initiator known in the art, such as peroxides, azoderivatives (e.g., azo-nitriles), peresters, and peroxycarbonates. Suitable peroxides for use in the present invention include, but are not limited to, organic peroxides, for example dialkyl organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane (available from Akzo Nobel as TRIGANOX 101), 2,5-dimethyl-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, di-t-amyl peroxide, t-amylperoxy-2-ethylhexylcarbonate (TAEC), t-butyl cumyl peroxide, n-butyl-4,4-bis(t-butylperoxy)valerate, 1, l-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1, l-bis(t-butylperoxy)-95610.120163,3,5-trimethylcyclohexane (CPK), 1, I -di(t-butylperoxy)cyclohexane, 1, T-di(t-amylperoxy)-cyclohexane, 2,2-di(t-butyl peroxy )butane, ethyl -3, 3 -di(t-butyl peroxy )butyrate, 2,2-di(t-amylperoxy)propane, ethyl-3,3-di(t-amylperoxy)butyrate, t-butylperoxy-acetate, t-amylperoxyacetate, t-butylperoxybenzoate, t-amylperoxybenzoate, di-t-butyldiperoxyphthalate, di-(tert-butylperoxyisopropyl)benzene (VulCup®) and the like. Combinations and mixtures of peroxides can also be used. Examples of free radical initiators include those mentioned herein, as well as those described in, e.g., Polymer Handbook, 3rd Ed., J. Brandrup & E. H. Immergut, John Wiley and Sons, 1989, Ch. 2. Eradiation (e.g., e-beam or gamma irradiation) can also be used to generate PHA branching.

[0050] The efficiency of branching and coupling of the polymer(s) can also be significantly enhanced by the dispersion of organic peroxides in a coupling agent, such as a polymerizable (i.e., reactive) plasticizers. The polymerizable plasticizer should contain a reactive functionality, such as a reactive unsaturated double bond, which increases the overall branching and coupling efficiency.Coupling Agents

[0051] Coupling agents, also referred to as co-agents, used in the methods and compositions of the invention are coupling agents comprising two or more reactive functional groups such as epoxides or double bonds. These coupling agents modify the properties of the polymer. These properties include, but are not limited to, melt strength or toughness. One type of coupling agent is an "epoxy functional compound." As used herein, "epoxy functional compound" is meant to include compounds with two or more epoxide groups capable of increasing the melt strength of polyhydroxyalkanoate polymers by branching, e.g., end branching as described above.

[0052] When an epoxy functional compound is used as the coupling agent in the disclosed methods, a branching agent is optional. As such one embodiment of the invention is a method of branching a starting PHA, comprising reacting a starting PHA with an epoxy functional compound and then further blending this PHA with polypropylene. Alternatively, the invention is a method of branching a starting polyhydroxyalkanoate polymer, by reacting a starting PHA, a branching agent and an epoxy functional compound and then further blending this PHA with polypropylene. Alternatively, the invention is a method of branching a starting95610.12016polyhydroxyalkanoate polymer, comprising reacting a starting PHA, and an epoxy functional compound in the absence of a branching agent and then further blending this PHA with polypropylene. Such epoxy functional compounds can include epoxy-functional, styrene-acrylic polymers (such as, but not limited to, e.g., MP -40 (Kaneka)), acrylic and / or polyolefin copolymers and oligomers containing glycidyl groups incorporated as side chains (poly(ethylene-glycidyl methacrylate-co-methacrylate)), and epoxidized oils (such as, but not limited to, e.g., epoxidized soybean, olive, linseed, palm, peanut, coconut, seaweed, cod liver oils, or mixtures thereof, e.g., Merginat® ESBO (Hobum, Hamburg, Germany) and EDENOL® B 316 (Cognis, Dusseldorf, Germany)).

[0053] For example, reactive acrylics or functional acrylics coupling agents are used to increase the molecular weight of the polymer in the branched polymer compositions described herein. Such coupling agents are sold commercially. One such compound is MP-40 (Kaneka) and still another is Petra line from Honeywell, see for example, U.S. Pat. No. 5,723,730. Such polymers are often used in plastic recycling (e.g., in recycling of polyethylene terephthalate) to increase the molecular weight (or to mimic the increase of molecular weight) of the polymer being recycled.

[0054] Fatty acid esters or naturally occurring oils containing epoxy groups (epoxidized) and / or chemical unsaturation can also be used. Examples of naturally occurring oils are olive oil, linseed oil, soybean oil, palm oil, peanut oil, coconut oil, seaweed oil, cod liver oil, or a mixture of these compounds. Particular preference is given to epoxidized soybean oil (e.g., Merginat® ESBO from Hobum, Hamburg, or EDENOL® B 316 from Cognis, Dusseldorf), but others may also be used.

[0055] Another type of coupling agent are agents with two or more double bonds. Coupling agents with two or more double bond coupling PHAs by after reacting at the double bonds. Examples of these include: diallyl phthalate, pentaerythritol urethane acrylate, tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, diethylene glycol dimethacrylate, bis(2-methacryloxyethyl)phosphate.

[0056] In general, it appears that compounds with terminal epoxides may perform better than those with epoxide groups located elsewhere on the molecule.95610.12016

[0057] Compounds having a relatively high number of end groups are the most desirable. Molecular weight may also play a role in this regard, and compounds with higher numbers of end groups relative to their molecular weight (e.g., the Joncryl® resins are in the 3000-4000 g / mol range) are likely to perform better than compounds with fewer end groups relative to their molecular weight (e.g., the Omnova products have molecular weights in the 100,000-800,000 g / mol range).Nucleating Agents

[0058] A nucleating agent can be added to the blended composition to aid in its crystallization. Nucleating agents for various polymers are simple substances, metal compounds including composite oxides, for example, carbon black, calcium carbonate, synthesized silicic acid and salts, silica, zinc white, clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, metal salts of organophosphates, and boron nitride; low-molecular organic compounds having a metal carboxylate group, for example, metal salts of such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, and isophthalic acid monomethyl ester; high-molecular organic compounds having a metal carboxylate group, for example, metal salts of such as: carboxyl-group-containing polyethylene obtained by oxidation of polyethylene; carboxyl-group-containing polypropylene obtained by oxidation of polypropylene; copolymers of olefins, such as ethylene, propylene and butene-I, with acrylic or methacrylic acid; copolymers of styrene with acrylic or methacrylic acid; copolymers of olefins with maleic anhydride; and copolymers of styrene with maleic anhydride; high-molecular organic compounds, for example: alpha-olefins branched at their 3-position carbon atom and having no fewer than 5 carbon atoms, such as 3,3 dimethylbutene-1,3-methylbutene-l,3-methylpentene-l,3-methylhexene-l, and 3,5,5-trimethylhexene-l; polymers ofvinylcycloalkanes such as vinylcyclopentane, vinylcyclohexane, and vinylnorbomane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; poly(glycolic acid); cellulose; cellulose esters; and cellulose ethers; phosphoric or phosphorous acid and its metal salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis(4-tert-butylphenyl) phosphate, and methylene bis-(2,4-tert-butylphenyl)phosphate; sorbitol derivatives such as bis(p-95610.12016methylbenzylidene)sorbitol and bis(p-ethylbenzylidene)sorbitol; and thioglycolic anhydride, p-toluenesulfonic acid and its metal salts. The above nucleating agents may be used either alone or in combinations with each other. In particular embodiments, the nucleating agent is cyanuric acid. In certain embodiments, the nucleating agent can also be another polymer

[0059] The nucleating agent can be selected from: cyanuric acid, carbon black, mica talc, silica, boron nitride, clay, calcium carbonate, synthesized silicic acid and salts, metal salts of organophosphates, and kaolin. In particular embodiments, the nucleating agent is cyanuric acid.

[0060] The nucleating agent can be dispersed in a liquid carrier, the liquid carrier is a plasticizer, e.g., a citric compound or an adipic compound, e.g., acetylcitrate tributyrate ((CITROFLEX® A4) plasticizer, Vertellus, Inc., High Point, N.C.), or DBEEA (dibutoxy ethoxy ethyl adipate), a surfactant, e.g., Triton X- 100 surfactant, TWEEN-20 surfactant, TWEEN-65 surfactant, Span-40 surfactant or Span 85 surfactant, a lubricant, a volatile liquid, e.g., chloroform, heptane, or pentane, an organic liquid or water.

[0061] The nucleating agent can be aluminum hydroxy diphosphate or a compound comprising a nitrogen-containing heteroaromatic core. The nitrogen-containing heteroaromatic core is pyridine, pyrimidine, pyrazine, pyridazine, triazine, or imidazole.

[0062] In particular embodiments, the nucleating agent can include aluminum hydroxy diphosphate or a compound comprising a nitrogen-containing heteroaromatic core. The nitrogencontaining heteroaromatic core is pyridine, pyrimidine, pyrazine, pyridazine, triazine, or imidazole. The nucleating agent can be a nucleating agent as described in U.S. Pat. App. Pub.2005 / 0209377, by Allen Padwa, which is herein incorporated by reference in its entirety.

[0063] Another nucleating agent for use in the blended compositions and methods described herein are milled as described in WO 2009 / 129499 titled "Nucleating Agents for Polyhydroxy alkanoates," which was published in English and designated the United States, which is herein incorporated by reference in its entirety. Briefly, the nucleating agent is milled in a liquid carrier until at least 5% of the cumulative solid volume of the nucleating agent exists as particles with a particle size of 5 microns or less. The liquid carrier allows the nucleating agent to be wet milled. In other embodiments, the nucleating agent is milled in liquid carrier until at least 10% of the cumulative solid volume, at least 20% of the cumulative solid volume, at least95610.1201630% or at least 40%-50% of the nucleating agent can exist as particles with a particle size of 5 microns or less, 2 microns or less or I micron or less. In alternative embodiments, the nucleating agents is milled by other methods, such as jet milling and the like. Additionally, other methods are utilized that reduce the particle size.

[0064] The cumulative solid volume of particles is the combined volume of the particles in dry form in the absence of any other substance. The cumulative solid volume of the particles is determined by determining the volume of the particles before dispersing them in a polymer or liquid carrier by, for example, pouring them dry into a graduated cylinder or other suitable device for measuring volume. Alternatively, cumulative solid volume is determined by light scattering.Additives

[0065] Additives may be added to the novel blended composition. Such additives may be mixed at a suitable time during the processing of the components for forming the blend PHA-containing polymer composition. One or more additives are included in the blended compositions to impart one or more selected functional characteristics to the blended PHA-containing polymer compositions and any molded article made therefrom. Examples of additives that may be included in the present invention include, but are not limited to, heat stabilizers, process stabilizers, light stabilizers, antioxidants, slip / antiblock agents, pigments, UV absorbers, fillers, lubricants, pigments, dyes, colorants, compatibilizers, antistats, flow promoters plasticizers, processing aids, branching agents, strengthening agents, nucleating agents (discussed in further detail below), talc, wax, calcium carbonate, radical scavengers or a combination of one or more of the foregoing functional additives.

[0066] The branching agent and / or coupling agent is added to one or more of these for easier incorporation into the polymer. For instance, the branching agent and / or coupling agent is mixed with a plasticizer, e.g., a non-reactive plasticizer, e.g., a citric acid ester, and then compounded with the polymer under conditions to induce branching.

[0067] Optionally, additives are included in the blended compositions of the present invention at a concentration of about 0.05 to about 20% by weight of the total composition. For example, the range in certain embodiments is about 0.05 to about 5% of the total composition. The additive is any compound known to those skilled in the art to be useful in the production of thermoplastics.95610.120161. Fillers

[0068] Examples of suitable fillers include but are not limited to glass fibers and minerals such as precipitated calcium carbonate, ground calcium carbonate, talc, wollastonite, alumina trihydrate, wood flour, ground walnut shells, coconut shells, and rice husk shells and the like.2. Antioxidants

[0069] Antioxidants are a known class of stabilizers which includes, for example, hindered phenols, triaryl phosphites, aromatic amines, hydroxylamines, and the like. Irganox 1010 and 168 mixture is the most classic phenolic antioxidants package in polyolefin industry. Consequently, it may be beneficial to add compounds to help stabilize the PHB against oxidation and ultraviolet light.

[0070] Suitable antioxidants include, for example, organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3, 5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or the like; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, or combinations including at least one of the foregoing antioxidants. Antioxidants are generally used in amounts of from 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.3. Compatibilizers

[0071] Compatibilizers are more commonly used in polypropylene compounding to enhance the bonding of different raw materials in the system. The more commonly used compatibilizers are the maleic anhydride grafted polypropylene (MAH-g-PP). It is abundantly used in a glass fiber reinforced polypropylene system to enhance the physical property of such95610.12016product by chemically binding the glass fiber and polypropylene. Glass fibers for such purposes are surface treated to be more apt in such systems. It is a well-known fact that when the peroxide and MAH are added into the system at the same time, the expected effects are lowered.

[0072] Calcium stearate (CaSt) and Zinc stearate (ZnSt) are the most commonly used processing aids that are used in manufacturing and compounding of polypropylene based products. These are some of the worst chemicals that degrade PHB. Again, different polypropylene manufacturers will choose to use different amounts and types, or even whether or not to use such based on their order of production of products and expected final outcomes, etc.4. Plasticizers

[0073] In compositions wherein the PHA is poly-3-hydroxybutyrate, for example, plasticizers are often used to change the glass transition temperature and modulus of the composition, but surfactants may also be used.

[0074] The blend can include one or more plasticizers. Examples of plasticizers include phthalic compounds (including, but not limited to, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n-decyl phthalate, n-octyl phthalate, and n-decyl phthalate), phosphoric compounds (including, but not limited to, tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, and tri chloroethyl phosphate), adipic compounds (including, but not limited to, dibutoxy ethoxy ethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, diisodecyl adipate, n-octyl n-decyl adipate, n-heptyl adipate, and n-nonyl adipate), sebacic compounds (including, but not limited to, dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, and butyl benzyl sebacate), azelaic compounds, citric compounds (including, but not limited to, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate), glycolic compounds (including, but not limited to, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl ethyl glycolate), trimellitic compounds (including, but not limited to, tri octyl trimellitate and tri-n-octyl n-decyl trimellitate), phthalic isomer compounds (including, but not limited to, dioctyl95610.12016isophthalate and dioctyl terephthalate), ricinoleic compounds (including, but not limited to, methyl acetyl, recinoleate and butyl acetyl recinoleate), polyester compounds (including, but not limited to reaction products of diols selected from butane diol, ethylene glycol, propane 1,2 diol, propane 1,3 diol, polyethylene glycol, glycerol, diacids selected from adipic acid, succinic acid, succinic anhydride and hydroxyacids such as hydroxystearic acid, epoxidized soy bean oil, chlorinated paraffins, chlorinated fatty acid esters, fatty acid compounds, plant oils, pigments, and acrylic compounds. The plasticizers may be used either alone, respectively, or in combinations with each other.5. Surfactants

[0075] The composition, preferably blended polypropylene / PHB compositions, of the present invention can 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 surfactant, available from Penreco (Dickinson, Tex., USA). MAXSPERSE® W-6000 surfactant and W-3000 solid surfactant are available from Chemax Polymer Additives (Piedmont, S.C., USA). Non-ionic surfactants with HLB values ranging from about 2 to about 16 can be used, examples being TWEEN-20 surfactant, TWEEN-65 surfactant, Span-40 surfactant and Span 85 surfactant.

[0076] 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 saltformalin polycondensation products, dialkylsulfosuccinic acid ester salts, alkyl sulfosuccinate di salts, polyoxyethylene alkyl sulfosuccinic 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 ethoxysulfates, 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 phosphoric95610.12016acid salts, sodium alkylamine oxide bi stridecyl sulfosuccinates, sodium di octyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium diamylsulfosuccinate, sodium diisobutyl sulfosuccinate, alkylamine guanidine polyoxyethanol, disodium sulfosuccinate ethoxylated alcohol half esters, disodium sulfosuccinate ethoxylated nonylphenol half esters, disodium isodecyl sulfosuccinate, disodium N-octadecylsulfosuccinamide, tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinamide, disodium mono- or didodecyldiphenyl oxide disulfonates, sodium diisopropylnaphthalenesulfonate, and neutralized condensed products from sodium naphthalenesulfonate.6. Lubricants

[0077] 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 metal surfaces during processing and can include polyethylene, paraffin oils, and paraffin waxes in combination with metal stearates (e.g., zinc stearate). Other lubricants include stearic acid, amide waxes, ester waxes, metal carboxylates, and carboxylic acids. Lubricants are normally added to polymers in the range of about 0.1 percent to about 5 percent by weight, generally from about 0.7 percent to about 0.1 percent by weight of the compound. Solid lubricants is warmed and melted before or during processing of the blend.7. Antimicrobial Agents

[0078] One or more anti-microbial agents can also be added to the compositions and methods of the invention. A wide range of chemical and natural compounds are used as antimicrobials, including but not limited to: organic acids, essential oils, cations and elements (e.g., colloidal silver). Commercial examples include but are not limited to PolySept® Z microbial, UDA and AGION®.

[0079] PolySept® Z microbial (available from PolyChem Alloy) is an organic salt based, non-migratory antimicrobial. "UDA" is Urtica dioica gglutinin. AGION® antimicrobial is a silver compound. AMICAL® 48 silver is diiodomethyl p-tolyl sulfone.8. Heat Stabilizers

[0080] Suitable heat stabilizers include, for example, organo phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- and di-nonylphenyl)phosphite or the like; phosphonates such as dimethyl benzene phosphonate or the like, phosphates such as trimethyl phosphate or the like, or combinations including at least one of the foregoing heat95610.12016stabilizers. Heat stabilizers are generally used in amounts of from 0.01 to 0.5 parts by weight based on 100 parts by weight of the total composition, excluding any fdler.9. Light Stabilizers

[0081] Suitable light stabilizers include, for example, benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxy benzophenone or the like or combinations including at least one of the foregoing light stabilizers. Light stabilizers are generally used in amounts of from 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.10. Antistatic Agents

[0082] Suitable antistatic agents include, for example, glycerol monostearate, sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, or combinations of the foregoing antistatic agents. In one embodiment, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or any combination of the foregoing may be used in a polymeric resin containing chemical antistatic agents to render the composition electrostatically dissipative.11. Mold Releasing Agents

[0083] Suitable mold releasing agents include for example, metal stearate, stearyl stearate, pentaerythritol tetrastearate, beeswax, montan wax, paraffin wax, or the like, or combinations including at least one of the foregoing mold release agents. Mold releasing agents are generally used in amounts of from 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.12. UV Absorbers

[0084] Suitable UV absorbers include for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; 2-(2H-benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)-phenol (CYASORB® 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB. TM. 531); 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl]-5-(octyloxy)-phenol (CYASORB. TM. 1164); 2,2'-(l,4-phenylene)bis(4H-3,Lbenzoxazin-4-one) (CYASORB. TM. UV-3638); l,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-acryloyl )oxy]methyl]propane (UVINUL® 3030); 2,2'-(l,4-phenylene)bis(4H-3,l-benzoxazin-4-one); l,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-di phenyl- acryloyl)oxy ]methyl]propane; nano-size inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all with particle size less than 100 nanometers; or the like, or95610.12016combinations including at least one of the foregoing UV absorbers. UV absorbers are generally used in amounts of from 0.01 to 3.0 parts by weight, based on 100 parts by weight based on 100 parts by weight of the total composition, excluding any filler.13. Pigments

[0085] Suitable pigments can include inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates; sulfates and chromates; carbon blacks; zinc ferrites; ultramarine blue; Pigment Brown 24; Pigment Red 101; Pigment Yellow 119; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, anthanthrones, di oxazines, phthalocyanines, and azo lakes; Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green 7, Pigment Yellow 147 and Pigment Yellow 150, or combinations including at least one of the foregoing pigments. Pigments are generally used in amounts of from 1 to 10 parts by weight, based on 100 parts by weight based on 100 parts by weight of the total composition, excluding any fdler.14. Dyes

[0086] Suitable dyes include organic dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbons; scintillation dyes (preferably oxazoles and oxadiazoles); aryl-or heteroaryl-substituted poly (2-8 olefins); carbocyanine dyes; phthalocyanine dyes and pigments; oxazine dyes; carbostyryl dyes; porphyrin dyes; acridine dyes; anthraquinone dyes; arylmethane dyes; azo dyes; diazonium dyes; nitro dyes; quinone imine dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); and xanthene dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 5-amino-9-diethyliminobenzo(a)phenoxazoni um perchlorate; 7-amino-4-m ethyl carbostyryl; 7-amino-4-methylcoumarin; 3-(2'-benzimidazolyl)-7-N,N-di ethylaminocoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenyl)-5-(4-t-butylphenyl)- 1 ,3,4-oxadiazole; 2-(4-biphenyl)-6-phenylbenzoxazole-l,3; 2,5-Bis-(4-biphenyl)-l )-l,3,4-oxadiazole; 2,5-bis-(4-biphenyl)-oxazole; 4,4'-bis-(2-butyloctyloxy)-p-quaterphenyl, p-bis(o-methylstyryl)-benzene; 5,9-95610.12016diaminobenzo( a)phenoxazonium perchlorate; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; 1,1' -diethyl-2, 2' -carbocyanine iodide; 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7-diethylamino-4-methyl coumarin; 7-diethylamino-4-trifluorom ethyl coumarin; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 7-ethylamino-6-methy 1 -4-trifluoromethylcoumarin; 7-ethylamino-4-trifluoromethy 1 coumarin; nile red; rhodamine 700; oxazine 750; rhodamine 800; IR 125; IR 144; IR 140; IR 132; IR 26; IRS; diphenylhexatri ene; diphenylbutadiene; tetraphenylbutadiene; naphthalene; anthracene; 9,10-diphenylanthracene; pyrene; chrysene; rubrene; coronene; phenanthrene or the like, or combinations including at least one of the foregoing dyes. Dyes are generally used in amounts of from 0.1 to 5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.15. Colorants

[0087] Suitable colorants can include titanium dioxide, anthraquinones, perylenes, perinones, indanthrones, quinacridones, xanthenes, oxazines, oxazolines, thioxanthenes, indigoids, thioindigoids, naphthalimides, cyanines, xanthenes, methines, lactones, coumarins, bis-benzoxazolylthiophene (BBOT), naphthalenetetracarboxylic derivatives, monoazo and diazo pigments, triarylmethanes, aminoketones, bis(styryl)biphenyl derivatives, and the like, as well as combinations including at least one of the foregoing colorants. Colorants are generally used in amounts of from 0.1 to S parts by weight, based on 100 parts by weight of the total composition, excluding any filler.16. Blowing Agents

[0088] Suitable blowing agents include for example, low boiling halohydrocarbons and those that generate carbon dioxide; blowing agents that are solid at room temperature and when heated to temperatures higher than their decomposition temperature, generate gases such as nitrogen, carbon dioxide, ammonia gas, such as azodicarbonamide, metal salts of azodicarbonamide, 4,4' oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium carbonate, or the like, or combinations including at least one of the foregoing blowing agents. Blowing agents are generally used in amounts of from I to 20 parts by weight, based on 100 parts by weight of the total composition, excluding any fdler.17. Other

[0089] Additional materials can be used to improve flow and other properties may be95610.12016added to the composition, such as low molecular weight hydrocarbon resins. Particularly useful classes of low molecular weight hydrocarbon resins are those derived from petroleum CS to C9 feedstock that are derived from unsaturated CS to C9 monomers obtained from petroleum cracking. Non-limiting examples include olefins, e.g. pentenes, hexenes, heptenes and the like; diolefins, e.g. pentadienes, hexadienes and the like; cyclic olefins and diolefins, e.g. cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, methyl cyclopentadiene and the like; cyclic diolefin dienes, e.g., dicyclopentadiene, methylcyclopentadiene dimer and the like; and aromatic hydrocarbons, e.g. vinyltoluenes, indenes, methylindenes and the like. The resins can additionally be partially or fully hydrogenated.Method

[0090] The novel PHA-containing polymer compositions can be made by any suitable method, using any suitable order of processing. In certain embodiments, a preferred particle size for fumaric acid is 150 mesh or higher and the fumaric acid is added as a dry powder. For example, the method can comprise the steps of: (a) mixing, in a molten state, the PHA polymers in combination with a polymeric material and fumaric acid to form a blend; and (b) cooling the blend to form a solid PHA-containing polymer composition, which can then be shaped into an article. In another embodiment, the PHA-containing polymers are in the form of a fine particle size powder and blended by dry-blending the components at a pre-determined ratio, mixed and processed. The novel PHA-containing polymer compositions of this invention can be fabricated into commercially useful articles. Any suitable mixing device can be used such as, for example, an extruder (e g., single screw or twin screw). The methods can additionally comprise other steps, such as the step of pelletizing the blend.

[0091] The method includes mixing: a thermoplastic polymer (e.g., polypropylene) and the PHA, under conditions sufficient to form a blended composition that is capable of forming articles of manufacture having the desired physical and mechanical properties.

[0092] In one embodiment, a method is provided for improving the odor and functional characteristics of the PHA-containing polymer blend comprising the steps of: (a) providing a thermoplastic polymer, PHA, and fumaric acid; (b) blending the thermoplastic polymer, PHA, and fumaric acid to form a mixture; (c) heating said mixture to between 50°C and 250°C; and (d) resulting in the thermoplastic polymer and PHA being miscible and effecting functional95610.12016modifications of the thermoplastic polymer and PHA wherein the functional modification increases the impact strength, toughness and elongation of the final product.

[0093] Additionally, provided herein is a method for forming a blended polymer resin pellet, where the method includes combining: the a thermoplastic polymer, the PHA, and fumaric acid components, where the composition is melted and formed under suitable conditions to form a blended resin pellet.

[0094] The novel compositions of this invention can be fabricated into commercially useful articles, such as blow-molded articles, injection molded articles, films, fibers, sheets (including multilayer sheets), molding, cutlery, fiber, nonwovens, filament, monofilaments, rod, tube, bottle, pellet or foam. The articles can be formed by commercial mixing, molding, extruding, thermoforming or blowing of the polypropylene / PHA blended composition.

[0095] In any of the compositions, methods, processes or articles described herein, the polypropylene and PHA components can be in the form of a fine particle size powder, pellet, or granule and combined by mixing or blending.

[0096] For the fabrication of useful articles, the compositions 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, nonwovens, monofilaments, film, sheet, rod, tube, bottle, or other shape. Such processing is performed using any art-known technique, such as, but not limited to, extrusion, injection 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.

[0097] The compositions are used to create, without limitation, a wide variety of useful products, e.g., automotive, consumer durable, construction, electrical, medical, and packaging products. For instance, the polymeric compositions is used to make, without limitation, films (e.g., packaging films, agricultural film, mulch film, erosion control, hay bale wrap, slit film, food wrap, pallet wrap, protective automobile and appliance wrap, etc.), golf tees, caps and closures,95610.12016agricultural supports and stakes, paper and board coatings (e.g., for cups, plates, boxes, etc.), thermoformed products (e.g., trays, containers, lids, yoghurt pots, cup lids, plant pots, noodle bowls, moldings, etc.), housings (e.g., for electronics items, e.g., cell phones, PDA cases, music player cases, computer cases and the like), bags (e.g., trash bags, grocery bags, food bags, compost bags, etc.), hygiene articles injection molded articles (writing instruments, cutlery, such as forks, spoons and knifes, aquarium decorations, disk cases, etc.), solution and spun fibers and melt blown fabrics and non-wovens (threads, yams, wipes, wadding, disposable absorbent articles), blow moldings (deep containers, bottles, etc.) and foamed articles (cups, bowls, plates, packaging, etc.).

[0098] 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 in an oven and heated. When soft enough to be formed, it is transferred to a mold and formed into a shape.

[0099] During thermoforming, when the softening point of a semi-crystalline polymer is reached, the polymer sheet begins to sag. The window between softening and droop is usually narrow. It can therefore be difficult to move the softened polymer sheet to the mold quickly enough. Branching the polymer can be used to increase the melt strength of the polymer so that the sheet is more readily processed and maintains its structural integrity. Measuring the sag of a sample piece of polymer when it is heated is therefore a way to measure the relative size of this processing window for thermoforming.

[0100] Blow molding, which is similar to thermoforming and is used to produce deep draw products such as bottles and similar products with deep interiors, also benefits from the increased elasticity and melt strength and reduced sag of the polymer compositions described herein.Blends / Masterbatch

[0101] The composition can also be prepared as a masterbatch for example, by incorporating any additive(s) in a PHA-containing polymer combination and producing pellets of the resultant composition for addition to subsequent processing. In a masterbatch the concentration of the additive(s) is (are) higher than the final amount for the product to allow for proportionate mixing of the additive in the final composition.

[0102] Masterbatches are solid, concentrated plastic additives that are designed to be easily95610.12016incorporated into a base polymer during the manufacturing process. The masterbatch is typically supplied in pellet or granular form, and it's mixed with the raw polymer during extrusion, injection molding, or other plastic processing techniques. Masterbatches make it easier to add pigments and additives to the polymer, reducing the need for precise dosing equipment and minimizing dust pollution. The reduced odor polyolefin / PHA blends can be produced by first preparing a masterbatch with a high concentration of fumaric acid in either the polyolefin or the PHA and adding this masterbatch during processing to a greater amount of the desired polyolefin.

[0103] This invention allows for the production of PHA-containing polymer blends having a reduced odor, a low carbon footprint, and with an advantageous balance of desirable physical properties.EXAMPLESExample 1

[0104] The following raw ingredients were dry blended together at the weight percentages defined in Table 1. The formulations all consisted of the following weight percentages at 400g total scale: 5% PHB, an additive at the percentage specified in Table 1, and the balance being Braskem 2000WV polypropylene. The dry blend was compounded into pellets using an 18 mm co-rotating twin screw extruder operating at a speed of 300 RPM with barrel temperatures of 150-190°C. All additives were chosen as examples of acidic additives across varying chemical classes.

[0105] The odor was determined as follows. A 4-hole 0.04" Teflon press out die was used so that four sample discs can be pressed at once. Position #1 always being the control, with no additive. 2 g of pellets were placed and used for each press out. A Carver heated manual hydraulic press was set at 230 °C and 20 lbs. pressure and compression time was 10 minutes. Aluminum foil was used on both sides of the discs for release. The sample discs were smelled by 3-5 participants within 5 min of removal from the press.Scale 1 - 31. No odor2. Observable unpleasant odor3. Strong odor which produces an involuntary response, such as a cringe.Table I95610.12016Formulation Additive PHB Braskem FT2OOWV Numbertype % wt (g) % wt(g) % Wt (g) 1 None N / A N / A 5% 20.0 95% 380.0 2 sebacic acid 1.0% 4.0 5% 20.0 94.0% 376.0 3 stearic acid 1.0% 4.0 5% 20.0 94.0% 376.0 4 palmitic acid 1.0% 4.0 5% 20.0 94.0% 376.0dimer acid5 (Pripol 1027) 1.0% 4.0 5% 20.0 94.0% 376.0 6 citric acid 0.1% 0.4 5% 20.0 94.9% 379.6 7 citric acid 1.0% 4.0 5% 20.0 94.0% 376.0 8 pectin 1.0% 4.0 5% 20.0 94.0% 376.0green tea 1.0% 4.0 5%9 polyphenols 20.0 94.0% 376.0 10 fumaric acid 0.1% 0.4 5% 20.0 94.9% 379.6 11 fumaric acid 1.0% 4.0 5% 20.0 94.0% 376.0 12 adipic acid 0.1% 0.4 5% 20.0 94.9% 379.6 13 adipic acid 0.2% 0.8 5% 20.0 94.8% 379.2 14 adipic acid 0.3% 1.2 5% 20.0 94.7% 378.8 15 itaconic acid 0.1% 0.4 5% 20.0 94.9% 379.616 itaconic acid 1.0% 4.0 5% 20.0 94.0% 376.0

[0106] The control, containing PHB and the polypropylene with no additives, had an intense, unpleasant odor with a value of 3. Dimer acid, sebacic acid, green tea polyphenols, and adipic gave no improvement or only a modest improvement in odor. Several additives (stearic acid, palmitic acid, and citric acid) gave observable improvements in the odor, but produced fumes during compounding which limits their practical utility. Pectin and green tea polyphenols gave a brown color, which also limits their utility. Itaconic acid gave an observable suppression of the unpleasant odor of the control but gave a cheese-like odor which was also unacceptable. Of the additives tested, only fumaric acid gave odor suppression with none of these other disadvantages. See the resulting odor chart included as Fig. 1. Bars in the graph marked with represent those that exhibited emission of fumes during compounding. Bars in the graph marked with “B” represent those that turned brown during compounding. Bars in the graph marked with "C” represent those that emitted a cheese-like odor during compounding (which is a known odor profile associated with the thermal degradation of PHB, as it can produce short-chain fatty acids (such as crotonic acid) that have a pungent, cheese-like smell). Thus, in several embodiments fumaric acid is used when odor reduction is a key goal. Other additives can be used in some95610.12016embodiments, where higher odor tolerance may be tolerated.

[0107] The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

[0108] In the detailed description, references to “various embodiments”, "one embodiment", "an embodiment", "an example embodiment", etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described. After reading the description, it will be apparent to one skilled in the relevant art(s) how to implement the disclosure in alternative embodiments.

[0109] Steps recited in any of the method or process descriptions may be executed in any order and are not necessarily limited to the order presented. Furthermore, any reference to singular includes plural embodiments, and any reference to more than one component or step may include a singular embodiment or step. Also, any reference to attached, fixed, connected, coupled or the like may include permanent (e.g., integral), removable, temporary, partial, full, and / or any other possible attachment option. Any of the components may be coupled to each other via friction, snap, sleeves, brackets, clips or other means now known in the art or hereinafter developed. Additionally, any reference to without contact (or similar phrases) may also include reduced contact or minimal contact.

[0110] With respect to ingredients that are grouped by function or characterized herein, unless otherwise expressly stated herein, it is not precluded that such an ingredient could be grouped with or characterized by another function. For example, an ingredient discussed herein as a solubilizer could also function as a surfactant and vice versa. The ranges disclosed herein also encompass any and all overlap, sub-ranges, and combinations thereof. Language such as “up to,” “at least,” “greater than,” “less than,” “between,” and the like includes the number recited. Numbers preceded by a term such as “about” or “approximately” include the recited numbers. For95610.12016example, “about 90%” includes “90%. ” Language such as “at least 95% (S)-nicotine in the form of a free base alkaloid includes 96%, 97%, 98%, 99%, and 100% (S)-nicotine in the form of a free base alkaloid. Any titles or subheadings used herein are for organization purposes and should not be used to limit the scope of embodiments disclosed herein.[OlH] Benefits, other advantages, and solutions to problems have been described herein with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any elements that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as critical, required, or essential features or elements of the disclosure. The scope of the disclosure is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean "one and only one" unless explicitly so stated, but rather "one or more." Moreover, where a phrase similar to 'at least one of A, B, and C or 'at least one of A, B, or C is used in the claims or specification, it is intended that the phrase be interpreted to mean that A alone may be present in an embodiment, B alone may be present in an embodiment, C alone may be present in an embodiment, or that any combination of the elements A, B and C may be present in a single embodiment; for example, A and B, A and C, B and C, or A and B and C.

[0112] All structural, chemical, and functional equivalents to the elements of the abovedescribed various embodiments that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for an apparatus or component of an apparatus, or method in using an apparatus to address each and every problem sought to be solved by the present disclosure, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element is intended to invoke 35 U.S.C. 112(f) unless the element is expressly recited using the phrase “means for.” As used herein, the terms “comprises”, “comprising”, or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a chemical, chemical composition, process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such chemical, chemical composition, process, method, article, or apparatus.95610.12016

Claims

95610.12016WHAT IS CLAIMED IS:1) A composition comprising a polymer combination of at least one thermoplastic polymer, at least one polyhydroxyalkanoate, and fumaric acid.2) The composition of claim 1, wherein the thermoplastic polymer is a polyolefin.3) The composition of claim 2, wherein said polyolefin is polypropylene, polyethylene, a polyolefin elastomer, or a thermoplastic polyolefin.4) The composition of claim 2, wherein said polyolefin is polypropylene.5) The composition of claim 1, wherein the polyhydroxyalkanoate is PHB, PHBV, PHB4HV or PHBHHx.6) The composition of claim 1, wherein the polyhydroxyalkanoate is PHB.7) The composition of claim 1, wherein thermoplastic polymer comprises a polyolefin and the polyolefin is present in an amount ranging from about 50% to about 99.9% of the composition by weight, wherein the polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight, and the fumaric acid is present in an amount ranging from about 0.01 % to about 10% of the composition by weight.8) The composition of claim 1, wherein a particle size for fumaric acid is 150 mesh or higher.9) The composition of claim 1, wherein said thermoplastic polymer is polystyrene, acrylonitrile butadiene styrene, polycarbonate / acrylonitrile, butadiene styrene, polycarbonate, polyamide, acrylic and methacrylic polymer and / or copolymer, cellulose ester, polyvinyl chloride, thermoplastic polyurethanes, thermoplastic elastomers, or95610.12016polyethylene terephthalate.10) A composition comprising a combination of polymers having reduced odor emission, the composition comprising:at least one thermoplastic polymer,wherein the at least one thermoplastic polymer is present in an amount ranging from about 50% to about 99.9% of the composition by weight; at least one polyhydroxyalkanoate,wherein the at least one polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight; and an odor-reducing additive,wherein the odor-reducing additive is present in an amount ranging from about 0.01 % to about 10% of the composition by weight, and wherein the composition exhibits a reduced odor as compared to combinations of polymers that do not comprise an odor-reducing additive.11) The composition of Claim 10, wherein the odor-reducing additive comprises fumaric acid.12) The composition of Claim 10 or 11, wherein the odor emission is reduced by at least about 20% as compared to compositions not comprising an odor reducing additive.13) The composition of Claim 10, 11, or 12, wherein the odor emission is reduced by at least about 30% as compared to compositions not comprising an odor reducing additive.14) The composition of Claim 10, wherein the odor-reducing additive is selected from the group consisting of sebacic acid, stearic acid, palmitic acid, dimer acid (Pripol 1027), citric acid, pectin, green tea polyphenols, fumaric acid, adipic acid, and itaconic acid.15) The composition of any one of claims 10-14, wherein the odor-reducing additive is present in an amount between about 0.01% and about 5% of the composition by95610.12016weight.16) The composition of any one of claims 10-15, wherein the odor-reducing additive is present in an amount between about 0.03% and about 3% of the composition by weight.17) A composition comprising a combination of polymers having reduced odor emission, the composition comprising:at least one thermoplastic polymer,wherein the at least one thermoplastic polymer is present in an amount ranging from about 50% to about 99.9% of the composition by weight; at least one polyhydroxyalkanoate,wherein the at least one polyhydroxyalkanoate is present in an amount ranging from about 0.1 % to about 50% of the composition by weight; and an odor-reducing additive comprising fumaric acid,wherein the fumaric acid is present in an amount ranging from about 0.01 % to about 10% of the composition by weight, andwherein the composition exhibits a reduced odor as compared to combinations of polymers that comprise a non-fumaric acid odor-reducing additive.18) The composition of Claim 17, wherein the fumaric acid is present in an amount ranging from about 0.05% to about 3% of the composition and the composition exhibits odor emission that is reduced by at least about 30% as compared to a combination of polymers that comprise a non-fumaric acid odor-reducing additive.19) The composition of Claim 17, wherein the non-fumaric acid odor-reducing additive is selected from the group consisting of sebacic acid, stearic acid, palmitic acid, dimer acid (Pripol 1027), citric acid, pectin, green tea polyphenols, fumaric acid, adipic acid, and itaconic acid.

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