Biodegradable and compostable materials for semi-rigid packaging and products, and processes for preparing the same

Abstract

A biodegradable bioplastic composition includes a mixture of polyhydroxyalkanoate (PHA) polymers, an organic biomass dispersed within the polymer, a clay, and a flow agent. The mixture of PHA polymers includes poly 3-hydroxybutyrate 4-hydroxybutyrate (P34HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). The P34HB and PHBV are each 100% biobased, plant-derived, and biodegradable. Articles formed from the biodegradable bioplastic composition and methods of making the biodegradable bioplastic composition are also disclosed.

Description

BIODEGRADABLE AND COMPOSTABLE MATERIALS FOR SEMI-RIGID PACKAGING AND PRODUCTS, AND PROCESSES FOR PREPARING THE SAMECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent App. No. 63 / 529,250, filed July 27, 2023, the content of which is incorporated by reference in its entirety.FIELD

[0002] The present technology is generally related to non-petrochemically-derived compositions for semi-rigid packaging.BACKGROUND

[0003] There is a growing interest in eco-friendly packaging as an alternative to petroleum-based plastic or other heavier packaging materials such as glass, which incur a larger carbon footprint when shipping. Plastic packaging is the main contributor to overall plastic production and disposal. Conventional petroleum-based plastic packaging options are unsustainable because they generate tons of waste by accumulating in landfills and polluting the environment when improperly disposed, and they also consume a nonrenewable oil resource and pollute the environment during the crude oil refinement process. The accumulation of plastic waste and pollution is a particularly acute problem for single-use, disposable plastic products or small objects that are too small to be recycled regardless of the material. And not all plastics are recyclable, and for even those that are recyclable they may not make it to the recycling facility or may only be recycled a limited number of times.

[0004] Conventional compostable plastics like polybutylene succinate (PBS), poly(butyl- ene succinate-co-butylene adipate) (PBSA), poly caprolactone (PCL), polybutyrate adipate terephthalate (PBAT), and aliphatic-aromatic copolyesters (AACs), are biodegradable but rely on fossil fuel sources and are therefore not fully sustainable and may biodegrade to toxic components.

[0005] Conventional biodegradable fermentation-derived polymers such as pure polylactic acid (PLA) or polyhydroxyalkanoates (PHA) are synthesized cleanly via bacterial fermentation of a carbohydrate source without the need for fossil fuels, but products made purelywith these materials are typically only used to make single-use thin films, and are often incompatible with hot-filled consumer products (e.g. PLA is fragile in the 55-65°C temperature range). Furthermore, PLA can take months to decompose under industrial composting conditions and can generate acidic byproducts that decrease the pH of soil or compost.SUMMARY

[0006] The packaging disclosed herein is fully biodegradable, sustainable, non-toxic, and not made using fossil fuel sources. The packaging is monolithic, semi-flexible, thin-walled, liquid compatible, and suitable for multiple uses with a years-long shelf life. Further, the packaging compositions disclosed herein include materials that can utilize blow molding manufacturing methods, such as extrusion blow molding enabling the manufacture of plastic- free containers with a small neck opening & a large chassis, which was previously not possible with injection molding.

[0007] Non-petrochemically-derived compositions for semi-rigid packaging are formed from a mixture of bioplastic polymers, organic matter, and flow agents. In particular, the present disclosure relates to compositions including various non-petrochemically derived polyhydroxyalkanoates (PHA), organics, and flow agents to form a composite material that is eco-friendly, biodegradable, industrially compostable, free of petrochemicals, compatible with blow molding and thermoforming manufacturing techniques, and comprise suitable mechanical properties for packaging, such as flexibility, liquid-compatibility, and durability across multiple uses.

[0008] In one aspect disclosed herein, a biodegradable bioplastic composition is provided. In some aspects, the biodegradable bioplastic composition comprises, consists of, or consists essentially of a mixture of polyhydroxyalkanoate (PHA) polymers comprising poly 3 -hydroxybutyrate 4-hydroxybutyrate (P34HB) and poly(3-hydroxybutyrate-co-3 -hydroxyvalerate) (PHBV). In some aspects, the composition comprises, consists of, or consists essentially of an organic biomass dispersed within the polymer, and at least one flow agent.

[0009] In some aspects, the at least one flow agent comprises, consists of, or consists essentially of a non-petrochemically derived flow agent. In some aspects, the P34HB and the PHBV are each independently 100% plant derived, 100% biobased, and 100% biodegradable. In some aspects, the P34HB and the PHBV are each independently 50%, or 60%, or 70%, or 80%, or 90%, or 95% plant derived, biobased, and biodegradable. In some aspects, the P34HB and the PHBV each independently have a molecular weight of about 250,000 Da toabout 1,050,000 Da. In some aspects, the P34HB and the PHBV each independently have an average molecular weight of about 650,000 Da.

[0010] In some aspects, the biodegradable bioplastic composition comprises, consists of, or consists essentially of about 70 wt.% to about 90 wt.% of the mixture of PHA polymers. In some aspects, the composition comprises, consists of, or consists essentially of about 5 wt.% to about 45 wt.% of the P34HB; about 40 wt.% to about 80 wt.% of the PHBV; about 1 wt.% to about 30 wt.% of the organic biomass; and about 0.1 wt.% to about 15 wt.% of the flow agent. In some aspects, the composition comprise, consists of, or consists essentially of about 15 wt.% to about 95 wt.% PHA; about 5 wt.% to about 20 wt.% of the organic biomass; and about 0.5 wt.% to about 15 wt.% of the flow agent. In some aspects, the composition comprises, consists of, or consists essentially of about 82% PHA; about 10 wt.% organic biomass; and about 8 wt.% non-petrochemically derived flow agent.

[0011] In some aspects, the biodegradable bioplastic composition is 100% biodegradable. In some aspects, the biodegradable bioplastic composition is free of petrochemically derived components.

[0012] In some aspects, the organic biomass comprises, consists of, or consists essentially of one or more of bamboo powder, bamboo fiber, hemp fiber, castor plant fiber, wool, charcoal powder, nutshell powder, pulp, or a combination of two or more thereof.

[0013] In some aspects, the flow agent comprises, consists of, or consists essentially of calcium carbonate (CaCO3). In some aspects, the flow agent comprises, consists of, or consists essentially of calcium carbonate (CaCO3) and montmorillonite. In some aspects, the montmorillonite has an average particle diameter of about 20 nm to about 2500 nm. In some aspects, the calcium carbonate has an average particle diameter of 5 nm to 100 nm. In some aspects, the calcium carbonate has an average particle diameter of about 20 nm to about 50 nm.

[0014] In some aspects, the flow agent comprises, consists of, or consists essentially of glycerol monostearate, mono- and di-glycerides, polyglycerol esters, or combinations thereof.

[0015] In some aspects, the biodegradable bioplastic composition has an average tensile strength of about 25 MPa to about 80 MPa as determined by ASTM D638-22.

[0016] In some aspects, the biodegradable bioplastic composition is chemically compatible with one or more solvents selected from water, dimethicone, glycerin, coconut oil, or combinations thereof.

[0017] In yet another aspect disclosed herein, an article comprising, consisting of, or consisting essentially of the biodegradable bioplastic composition. In some aspects, the article has a tensile strength of about 25 MPa to about 80 MPa at 20 °C or at room temperature. In some aspects, the article has a wall thickness of about 0.01 mm to about 10.0 mm. In some aspects, the article is a packaging container or packaging closure. In some aspects, the article is a pellet having a diameter of about 0.01 mm to about 10.0 mm. In some aspects, the article has a shelf life of greater than 12 months. In some aspects, the article has a shelf life of greater than 36 months. In some aspects, the article is non-toxic to the environment when disposed at end of life cycle, and wherein the article has a decomposition rate greater than that of 100% PHA.

[0018] In yet another aspect, a method of making a biodegradable bioplastic composition is disclosed. In some aspects, the method comprises, consists of, or consists essentially of homogenizing a mixture of a poly 3 -hydroxybutyrate 4-hydroxybutyrate (P34HB), a poly(3-hy- droxybutyrate-co-3 -hydroxy valerate) (PHBV), an organic biomass, a clay, and a flow agent, cooling the mixture in water at a temperature of 0 °C to 100 °C, or 30 °C to 80 °C, and resting the mixture for a period of about 24 hours to 72 hours to form a compound.

[0019] In some aspects, the P34HB is biobased. In some aspects, the method further comprises, consists of, or consists essentially of synthesizing the P34HB by fermenting plant biomass chosen from sugars, starches, and lipids. In some aspects, the method further comprises, consists of, or consists essentially of pelletizing the compound to form pellets. In some aspects, the method further comprises, consists of, or consists essentially of forming a biodegradable bioplastic article from the pellets. In some aspects, step of forming comprises, consists of, or consists essentially of blow molding or thermoforming. In some aspects, the step of forming comprises, consists of, or consists essentially of blow molding and blow molding comprises drying the pellets at a temperature of about 45 °C to 85 °C; and blow molding the pellets at a temperature ranging from 130 °C to 185 °C, or from about 140 °C to 175 °C, or from about 150 °C to 170 °C.

[0020] In some aspects, the biodegradable bioplastic composition is devoid of petrochem- ically derived components.

[0021] In some aspects, homogenizing is conducted at a temperature of about 120 °C to about 160 °C. In some aspects, the flow agent is non-petrochemically derived.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1 is a flow chart of a process of forming the compositions for biodegradable compostable packaging.

[0023] FIG. 2A is an article made according to the process in FIG. 1, in cross-sectional view; and FIG. 2B is a perspective view for the same article as shown in FIG. 2A.DETAILED DESCRIPTION

[0024] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0025] Provided herein are non-petrochemically derived, biodegradable, bioplastic compositions for use as monolithic, semi-flexible, thin-walled, liquid compatible containers suitable for multiple uses with a years-long shelf life. As provided herein, the bioplastic compositions surprisingly exhibit physical and performance-based measurements similar to, and in some cases exceeding, conventional plastics. Specifically, the bioplastic compositions demonstrate comparable density, as well as superior water vapor and oxygen transmission, while also retaining greater tensile strength and elasticity compared to conventional plastics utilized for flexible containers. Moreover, the claimed compositions have the added advantage of being biodegradable, thus drastically limiting their environmental impact as a suitable replacement to conventional plastic packaging.Definitions

[0026] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0027] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0028] The phrase “and / or” as used in the present disclosure will be understood to mean any one of the recited members individually or a combination of any two or more thereof - for example, “A, B, and / or C” would mean “A, B, C, A and B, A and C, B and C, or the combination of A, B, and C ”

[0029] As used herein, “greater than” and “less than” limits may also include the number associated therewith. Stated another way, “greater than” and “less than” may be interpreted as “greater than or equal to” and “less than or equal to.” It is contemplated that this language may be subsequently modified in the claims to include “or equal to.” For example, “greater than 4.0” may be interpreted as, and subsequently modified in the claims as “greater than or equal to 4.0.”

[0030] The term “biobased” as used herein refers to a material derived from biological resources such as plants, animals, or microorganisms.

[0031] The term “biodegradable” as used herein refers to the capability of being decomposed by natural biological processes, typically microorganisms, into simpler substances such as water, carbon dioxide, and biomass.

[0032] The term “biomass” or “organic biomass” as used herein refers to organic matter derived from plants and / or animals. Preferably, biomass is derived from renewable plants and / or animals. Biomass may be used as a material for forming biobased products.

[0033] The term “bioplastic” as used herein refers to a type of plastic derived from renewable biomass sources rather than fossil fuels.

[0034] The term “chemically compatible” as used herein refers to the capability of coexisting or interacting without adverse chemical reactions or incompatibilities. Adverse chemical reactions may produce products that are toxic to humans, animals, or the environment. Incompatibilities may result in degraded mechanical properties.

[0035] The term “clay” as used herein refers to a naturally-occurring mineral composed of hydrous aluminum phyllosilicates (e.g. kaolin, A12Si2Os(OH)4), sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations found on or near some planetary surfaces. For example, the clay may be montmorillonite, (Na,Ca)o.33(Al,Mg)2(Si40io)(OH)2 nH20.

[0036] The term “compostable” as used herein refers to the capability of undergoing biological decomposition in a compost environment, leaving no toxic residues.

[0037] Consumer safe” means suitable for use as packaging for a variety of liquid, solid, and powder materials without danger of leeching potentially toxic or irritating additives present in other materials such as plasticizers (phthalates), hardeners (bisphenol A or BP A), and non-stick agents (per- and polyfluoroalkyl substances or PF AS).

[0038] The term “decomposition rate” as used herein refers to the speed at which a material breaks down or decomposes under specific environmental conditions, preferably measured by weight loss over time.

[0039] The term “eco-friendly” means having little or no harmful impact on the environment, considering its entire lifecycle from production to disposal.

[0040] The term “flow agent” as used herein refers to a substance added to materials to improve their flow properties during processing or degradation, such as reducing viscosity.

[0041] The term “non-toxic” means not harmful or poisonous to living organisms or the environment. “Non-toxic to the environment” refers to not harmful or poisonous to the environment.

[0042] The term “petrochemically derived” as used herein refers to materials produced from chemicals derived from petroleum or natural gas. Also referred to herein as “fossil fuel- derived.” Materials that are not petrochemically derived are not produced from chemicals derived from petroleum or natural gas.

[0043] The term “renewable” as used herein refers to resources that are naturally replenished on a human timescale, either continuously or cyclically.

[0044] As used herein, “semi-rigid” means a flexible container that compresses when squeezed by human hand, as characterized by a 1) Young’s modulus (elasticity) value of 0.10-3.0 GPa (compared to rigid containers with a higher Young’s modulus of around >3.0-4.0 GPa) and 2) a high tensile strength of 25-80 MPa (compared to rigid containers with a lower tensile strength of around 10-24 MPa).

[0045] The term “shelf life” as used herein refers to the length of time a product can be stored before it deteriorates beyond acceptable performance standards for its intended use. “Shelf-life” may also refer to the length of time a product remains suitable for consumption and sale.

[0046] The term “sustainable” as used herein refers to processes that can be maintained or continued over the long term without significantly depleting natural resources or causingsevere environmental degradation. Sustainable starting materials, reaction products, compositions, and / or formulations are derived from renewable sources. The term “sustainable” therefore is in contrast to “non-sustainable” starting materials, reaction products, compositions, and / or formulations that contain carbon from a limited natural resource, such as fossil fuel (e.g., petroleum or coal), natural gas, and the like.

[0047] Generally, reference to a certain element such as hydrogen or H is meant to include all isotopes of that element. For example, if an R group is defined to include hydrogen or H, it also includes deuterium and tritium. Compounds comprising radioisotopes such as tritium, C14, P32and S35are thus within the scope of the present technology. Procedures for inserting such labels into the compounds of the present technology will be readily apparent to those skilled in the art based on the disclosure herein.

[0048] In general, “substituted” refers to an organic group as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituted group is substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (z.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, het- erocyclyl, heterocyclylalkyl, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxylates; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxy- amines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; pentafluorosulfanyl (z.e., SFs), sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; and nitriles (z.e., CN).

[0049] Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups also include rings and ring systems in which a bond to a hydrogen atom is replaced with a bond to a carbon atom. Therefore, substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

[0050] Alkyl groups include straight chain and branched chain alkyl groups having from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or, in some embodiments, from 1 to8, 1 to 6, or 1 to 4 carbon atoms. Alkyl groups may be substituted or unsubstituted. Examples of straight chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pen- tyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dime- thylpropyl groups. Representative substituted alkyl groups may be substituted one or more times with substituents such as those listed above, and include without limitation haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, carboxyalkyl, and the like.

[0051] Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups having from 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to 10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. Exemplary monocyclic cycloalkyl groups include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[2.1.1]hexane, adamantyl, decalinyl, and the like. Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2, 6-di substituted cyclohexyl groups, which may be substituted with substituents such as those listed above.

[0052] Cycloalkylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a cycloalkyl group as defined above. Cycloalkylalkyl groups may be substituted or unsubstituted. In some embodiments, cycloalkylalkyl groups have from 4 to 16 carbon atoms, 4 to 12 carbon atoms, and typically 4 to 10 carbon atoms. Substituted cycloalkylalkyl groups may be substituted at the alkyl, the cycloalkyl or both the alkyl and cycloalkyl portions of the group. Representative substituted cycloalkylalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, mono-, di- or tri-substituted with substituents such as those listed above.

[0053] Alkenyl groups include straight and branched chain alkyl groups as defined above, except that at least one double bond exists between two carbon atoms. Alkenyl groups may be substituted or unsubstituted. Alkenyl groups have from 2 to 12 carbon atoms, and typicallyfrom 2 to 10 carbons or, in some embodiments, from 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In some embodiments, the alkenyl group has one, two, or three carbon-carbon double bonds. Examples include, but are not limited to vinyl, allyl, -CH=CH(CH3),-CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, among others. Representative substituted alkenyl groups may be mono-substituted or substituted more than once, such as, but not limited to, mono-, di- or tri-substituted with substituents such as those listed above.

[0054] Cycloalkenyl groups include cycloalkyl groups as defined above, having at least one double bond between two carbon atoms. Cycloalkenyl groups may be substituted or unsubstituted. In some embodiments the cycloalkenyl group may have one, two or three double bonds but does not include aromatic compounds. Cycloalkenyl groups have from 4 to 14 carbon atoms, or, in some embodiments, 5 to 14 carbon atoms, 5 to 10 carbon atoms, or even 5, 6, 7, or 8 carbon atoms. Examples of cycloalkenyl groups include cyclohexenyl, cyclopentenyl, cyclohexadienyl, cyclobutadienyl, and cyclopentadienyl.

[0055] Cycloalkenylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to a cycloalkenyl group as defined above. Cycloalkenylalkyl groups may be substituted or unsubstituted. Substituted cycloalkenylalkyl groups may be substituted at the alkyl, the cycloalkenyl or both the alkyl and cycloalkenyl portions of the group. Representative substituted cycloalkenylalkyl groups may be substituted one or more times with substituents such as those listed above.

[0056] Alkynyl groups include straight and branched chain alkyl groups as defined above, except that at least one triple bond exists between two carbon atoms. Alkynyl groups may be substituted or unsubstituted. Alkynyl groups have from 2 to 12 carbon atoms, and typically from 2 to 10 carbons or, in some embodiments, from 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In some embodiments, the alkynyl group has one, two, or three carbon-carbon triple bonds. Examples include, but are not limited to -C=CH, -C=CCH3, -CH2C=CCH3, and -C=CCH2CH(CH2CH3)2, among others. Representative substituted alkynyl groups may be mono-substituted or substituted more than once, such as, but not limited to, mono-, di- or tri-substituted with substituents such as those listed above.

[0057] Aryl groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups herein include monocyclic, bicyclic, and tricyclic ring systems. Aryl groups maybe substituted or unsubstituted. Thus, aryl groups include, but are not limited to, phenyl, az- ulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pen- talenyl, and naphthyl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. In some embodiments, the aryl groups are phenyl or naphthyl. The phrase “aryl groups” includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like). Representative substituted aryl groups may be mono-substituted (e.g., tolyl) or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl groups, which may be substituted with substituents such as those listed above.

[0058] Aralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined above. Aralkyl groups may be substituted or unsubstituted. In some embodiments, aralkyl groups contain 7 to 16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substituted aralkyl groups may be substituted at the alkyl, the aryl or both the alkyl and aryl portions of the group. Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-indanylethyl. Representative substituted aralkyl groups may be substituted one or more times with substituents such as those listed above.

[0059] Heterocyclyl groups include aromatic (also referred to as heteroaryl) and non-aro- matic ring compounds containing 3 or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S. Heterocyclyl groups may be substituted or unsubstituted. In some embodiments, the heterocyclyl group contains 1, 2, 3 or 4 heteroatoms. In some embodiments, heterocyclyl groups include mono-, bi- and tricyclic rings having 3 to 16 ring members, whereas other such groups have 3 to 6, 3 to 10, 3 to 12, or 3 to 14 ring members. Heterocyclyl groups encompass aromatic, partially unsaturated, and saturated ring systems, such as, for example, imidazolyl, imidazolinyl and imidazolidinyl groups. The phrase “heterocyclyl group” includes fused ring species including those comprising fused aromatic and non-aromatic groups, such as, for example, benzotriazolyl, 2,3-dihydro- benzo[l,4]dioxinyl, and benzo[l,3]dioxolyl. The phrase also includes bridged polycyclic ring systems containing a heteroatom such as, but not limited to, quinuclidyl. The phrase includes heterocyclyl groups that have other groups, such as alkyl, oxo or halo groups, bonded to one of the ring members, referred to as “substituted heterocyclyl groups.” Heterocyclyl groupsinclude, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazoli- dinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrrolyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl, ox- azolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidyl, pi- perazinyl, morpholinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxathi- ane, dioxyl, dithianyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, dihydropyridyl, dihydrodithiinyl, dihydrodithionyl, homopiperazinyl, quinuclidyl, indolyl, in- dolinyl, isoindolyl,azaindolyl (pyrrolopyridyl), indazolyl, indolizinyl, benzotri azolyl, benzimidazolyl, benzofuranyl, benzothiophenyl, benzthiazolyl, benzoxadi azolyl, benzoxazinyl, ben- zodithiinyl, benzoxathiinyl, benzothiazinyl, benzoxazolyl, benzothiazolyl, benzothiadi azolyl, benzo [1,3] dioxolyl, pyrazolopyridyl, imidazopyridyl (azabenzimidazolyl), triazolopyridyl, isoxazolopyridyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, quinoliz- inyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl, pteridinyl, thianaphthyl, dihydrobenzothiazinyl, dihydrobenzofuranyl, dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl, tetrahydroindazolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotria- zolyl, tetrahydropyrrolopyridyl, tetrahydropyrazolopyridyl, tetrahydroimidazopyridyl, tetra- hydrotriazolopyridyl, and tetrahydroquinolinyl groups. Representative substituted heterocy- clyl groups may be mono-substituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl groups, which are 2-, 3-, 4-, 5-, or 6-substituted, or disubstituted with various substituents such as those listed above.

[0060] Heteroaryl groups are aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S. Heteroaryl groups may be substituted or unsubstituted. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidaz- opyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadi azolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups include fused ring compounds in which all rings are aromatic such as indolyl groups and include fused ring compounds in which only one of the rings is aromatic, such as 2,3-dihydro indolyl groups. Representativesubstituted heteroaryl groups may be substituted one or more times with various substituents such as those listed above.

[0061] Heterocyclylalkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heterocyclyl group as defined above. Heterocyclylalkyl groups may be substituted or unsubstituted. Substituted heterocyclylalkyl groups may be substituted at the alkyl, the heterocyclyl or both the alkyl and heterocyclyl portions of the group. Representative heterocyclyl alkyl groups include, but are not limited to, morpholin-4-yl-ethyl, furan-2-yl-methyl, imidazol-4-yl-methyl, pyri din-3 -yl-me- thyl, tetrahydrofuran-2-yl-ethyl, and indol-2-yl-propyl. Representative substituted heterocyclylalkyl groups may be substituted one or more times with substituents such as those listed above.

[0062] Heteroaralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined above. Heteroaralkyl groups may be substituted or unsubstituted. Substituted heteroaralkyl groups may be substituted at the alkyl, the heteroaryl or both the alkyl and heteroaryl portions of the group. Representative substituted heteroaralkyl groups may be substituted one or more times with substituents such as those listed above.

[0063] Groups described herein having two or more points of attachment (i.e., divalent, trivalent, or polyvalent) within the compound of the present technology are designated by use of the suffix, “ene.” For example, divalent alkyl groups are alkylene groups, divalent aryl groups are arylene groups, divalent heteroaryl groups are divalent heteroarylene groups, and so forth. Substituted groups having a single point of attachment to the compound of the present technology are not referred to using the “ene” designation. Thus, e.g., chloroethyl is not referred to herein as chloroethylene.

[0064] Alkoxy groups are hydroxyl groups (-OH) in which the bond to the hydrogen atom is replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Alkoxy groups may be substituted or unsubstituted. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxy groups include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, isohexoxy, and the like. Examples of cycloalkoxygroups include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above.

[0065] The terms “alkyloyl” and “alkyloyloxy” as used herein can refer, respectively, to - C(O)-alkyl groups and -O-C(O)-alkyl groups. Similarly, “aryloyl” and “aryloyloxy” refer to -C(O)-aryl groups and -O-C(O)-aryl groups.

[0066] The terms "aryloxy" and “arylalkoxy” refer to, respectively, a substituted or unsubstituted aryl group bonded to an oxygen atom and a substituted or unsubstituted aralkyl group bonded to the oxygen atom at the alkyl. Examples include but are not limited to phenoxy, naphthyloxy, and benzyloxy. Representative substituted aryloxy and arylalkoxy groups may be substituted one or more times with substituents such as those listed above.

[0067] The term “carboxylate” as used herein refers to a -COOH group.

[0068] The term “ester” as used herein refers to -COOR70and -C(O)O-G groups. R70is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl- alkyl or heterocyclyl group as defined herein. G is a carboxylate protecting group. Carboxylate protecting groups are well known to one of ordinary skill in the art. An extensive list of protecting groups for the carboxylate group functionality may be found in Protective Groups in Organic Synthesis, Greene, T.W.; Wuts, P. G. M., John Wiley & Sons, New York, NY, (3rd Edition, 1999) which can be added or removed using the procedures set forth therein and which is hereby incorporated by reference in its entirety and for any and all purposes as if fully set forth herein.

[0069] The term “amide” (or “amido”) includes C- and N-amide groups, i.e., -C(O)NR71R72, and -NR71C(O)R72groups, respectively. R71and R72are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. Amido groups therefore include but are not limited to carbamoyl groups (-C(O)NH2) and formamide groups (-NHC(O)H). In some embodiments, the amide is -NR71C(O)-(CI-5 alkyl) and the group is termed "carbonylamino," and in others the amide is -NHC(O)-alkyl and the group is termed "alkanoylamino."

[0070] The term “nitrile” or “cyano” as used herein refers to the -CN group.

[0071] Urethane groups include N- and O-urethane groups, i.e., -NR73C(O)OR74and -OC(O)NR73R74groups, respectively. R73and R74are independently a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein. R73may also be H.

[0072] The term “amine” (or “amino”) as used herein refers to -NR75R76groups, wherein R75and R76are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. In some embodiments, the amine is alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine is NH2, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino.

[0073] The term “sulfonamido” includes S- and N-sulfonamide groups, i.e., -SO2NR78R79and -NR78SO2R79groups, respectively. R78and R79are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein. Sulfonamido groups therefore include but are not limited to sulfamoyl groups (-SO2NH2). In some embodiments herein, the sulfonamido is - NHSCh-alkyl and is referred to as the "alkylsulfonylamino" group.

[0074] The term “thiol” refers to -SH groups, while “sulfides” include -SR80groups, “sulfoxides” include -S(O)R81groups, “sulfones” include -SO2R82groups, “sulfonyls” include -SO2OR83, and “sulfonates” include -SO3 . R80, R81, R82, and R83are each independently a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein. In some embodiments the sulfide is an alkylthio group, -S-alkyl.

[0075] The term “urea” refers to -NR84-C(O)-NR85R86groups. R84, R85, and R86groups are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclyl, or heterocyclylalkyl group as defined herein.

[0076] The term “amidine” refers to -C(NR87)NR88R89and -NR87C(NR88)R89, wherein R87, R88, and R89are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.

[0077] The term “guanidine” refers to -NR90C(NR91)NR92R93, wherein R90, R91, R92and R93are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.

[0078] The term “enamine” refers to -C(R94)=C(R95)NR96R97and -NR94C(R95)=C(R96)R97, wherein R94, R95, R96and R97are each independently hydrogen, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.

[0079] The term “halogen” or “halo” as used herein refers to bromine, chlorine, fluorine, or iodine. In some embodiments, the halogen is fluorine. In other embodiments, the halogen is chlorine or bromine.

[0080] The term “hydroxyl” as used herein can refer to -OH or its ionized form, -O . A “hydroxyalkyl” group is a hydroxyl-substituted alkyl group, such as HO-CH2-.

[0081] The term “imide” refers to -C(O)NR98C(O)R99, wherein R98and R99are each independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein.

[0082] The term “imine” refers to -CR100(NR101) and -N(CR100R101) groups, wherein R100and R101are each independently hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl aralkyl, heterocyclyl or heterocyclylalkyl group as defined herein, with the proviso that R100and R101are not both simultaneously hydrogen.

[0083] The term “nitro” as used herein refers to an -NO2 group.

[0084] The term “trifluorom ethyl” as used herein refers to -CF3.

[0085] The term “trifluorom ethoxy” as used herein refers to -OCF3.

[0086] The term “azido” refers to -N3.

[0087] The term “trialkyl ammonium” refers to a -N(alkyl)s group. A trialkylammonium group is positively charged and thus typically has an associated anion, such as halogen anion.

[0088] The term “isocyano” refers to -NC.

[0089] The term “isothiocyano” refers to -NCS.

[0090] The term “pentafluorosulfanyl” refers to -SFs.

[0091] As understood by one of ordinary skill in the art, “molecular weight” (also known as “relative molar mass”) is a dimensionless quantity but is converted to molar mass by multiplying by 1 gram / mole or by multiplying by 1 Da - for example, a compound with a weightaverage molecular weight of 5,000 has a weight-average molar mass of 5,000 g / mol and a weight-average molar mass of 5,000 Da.Biodegradable and Compostable Materials for Semi-Rigid Packaging and Products

[0092] As noted above, some conventional materials for semi-rigid container packaging suffer from a multitude of problems including being non-sustainable in manufacturing and having deleterious environmental impact upon disposal. For example, many “recyclable” plastics rely on virgin material from fossil fuel sources for their manufacture and / or are not biodegradable and compostable. Even “reclaimed” plastics are typically mixed with virgin plastic material for structural integrity during their manufacture and / or are not biodegradable and compostable, and additionally incur a large carbon footprint during the process of reclaiming, shipping, cleaning, and repelletizing.

[0093] Disclosed herein are biodegradable bioplastic compositions that include synergistic combinations of PHAs, organic biomass, and flow agents that provide a material suitable for semi-rigid packaging. The compositions include components that may be plant- and / or mineral-derived and may be free of petrochemically-derived components. The compositions may be 100% plant- and / or mineral-derived and 100% biodegradable. In some aspects, the composition is 50%, or 60%, or 70%, or 80%, or 90%, or 95% plant derived, biobased, and biodegradable. The disclosed compositions demonstrate an unexpected balance of sustainability and being non-detrimental to the environment and human users while also increasing decomposition and reducing the amount of acid after degradation as compared to other packaging compositions.

[0094] The present technology addresses unmet commercial, consumer, and environmental needs by providing composite materials that exhibit an unexpectedly unique combination of mechanical and physical properties for semi-rigid packaging, thin-walled packaging, shelflife, non-reactivity, biodegradability, and compostability that are not otherwise achievable. These biodegradable bioplastic compositions, in some cases, are directed to applications such as semi-rigid packaging containers formed by blow molding or thermoforming. Target areas include industrial or consumer applications that use semi-rigid packaging to contain liquids and gels that can be loaded at a range of temperatures and then easily dispensed by the end user (e.g., by squeezing). Examples of uses of such biodegradable bioplastic compositions include, but are not limited to, packaging for food and beverages, healthcare, hospitality, pharmaceuticals, personal care, health and beauty, and home cleaning, among many other sectors that utilize semi-rigid multi-use packaging.

[0095] Without being bound by theory, when the disclosed biodegradable bioplastic PHAs are employed with a substantial (e.g., about 1 wt.% to about 30 wt.%) loading of organic biomass, the components synergistically interact such that decomposition is accelerated and / or the amount of acid produced from decomposition of the PHA polymer is reduced.

[0096] Such packaging may be used in many industries including food and beverage products, healthcare, hospitality, pharmaceuticals, personal care, and health and beauty, among others. The packaging may be eco-friendly and fully functional to replace existing non-sustainable options. The packaging is rigid and non-porous enough to contain liquids and solids, and is also non-reactive (i.e., chemically compatible) with consumer products to provide a safe and stable barrier when in contact with consumer products.

[0097] Disclosed herein are bioplastics including biobased PHAs. Biobased or “natural” feedstocks are used in the production of biobased PHA compositions. An example of a biobased PHA composition is one that is prepared from a bioderived feedstock (e.g., from current and sustainable agricultural activities, such as fermentation-, algae-, plant- or vegetable- derived; e.g., is derived from a vegetable source, preferably using a non-genetically modified organism, or biomass, and it is not petrochemically-derived (such as being derived from sustainable tree and plant farms active in the 21st century vs. fossil sources such as petroleum, natural gas, or coal). Such feedstocks are referred to herein as “natural” and “renewable” (i.e., “sustainable”) and are known in the art as a non-petroleum-derived feedstock. Further, such materials are formed by “new” carbon and not from petroleum or other fossil fuel sources (“old” carbon). Such products are referred to herein as “natural” products and are known in the art as non-petrochemically-derived or “bio” products. Thus, a natural or bio product is not petrochemically derived and / or is made from resources that are not petrochemically derived, but rather are sustainable and renewable. True natural products (bio-compounds) are formed using biomass (e.g., material stored from carbon cycle processes in living plants, roots, and the like, or released through animal respiration or refuse, or through decomposition). When carbon decomposes and is broken down over millions of years under pressure, it creates fossil fuels (the source of petrochemically-derived carbon). Bio-compounds herein are intended to include materials derived from the carbon of plant sources / biomass that exist(ed) recently and / or are sustainable, and explicitly excludes materials derived from fossil fuels.

[0098] A composition disclosed herein can be identified, and distinguished from conventional packaging compositions by its biobased carbon content. The biobased carbon content may be measured by radiocarbon dating to determine the relative age of materials comprisedof organic (i.e., carbon-containing) matter. Radiocarbon is an unstable isotope of carbon, known as carbon-14 (i.e., “14C”).14C is an unstable isotope that emits radiation energy in the form of beta particles at a very consistent rate (i.e., a half-life for radiocarbon is 5730 years) and ultimately decays to the more stable nitrogen-14 (14N). Because, petroleum-based (i.e., petrochemically-derived) feedstocks are derived from plants and animals buried millions of years ago, such feedstocks’ radiocarbon (i.e.,14C) has been lost to radioactive decay. The ASTM International standards provide testing standards to determine the authenticity of a “bio-based compound” using radiocarbon, which may be found in ASTM D6866-16. This standard distinguishes newer carbon from carbon derived from fossil-fuel, or petroleum- and petrochemically-derived sources, i.e., “old carbon.” The amount of14C in recent or current biomass is known, so a percentage of carbon from a renewable source can be estimated from a total organic carbon analysis, which provides the data necessary to determine if a compound is truly derived from a “natural” and / or “sustainable” (“renewable”) feedstock source or is derived conversely from a compound of “old” sequestration (i.e., a petrochemically-derived or petroleum-based source). The use of petroleum-based (also termed “fossil-based”) feedstocks is generally accepted as being non-sustainable, i.e., old carbon is a non-sustainable and not a renewable feedstock and furthermore is not considered “natural” and / or “sustainable” in the art.

[0099] In some embodiments, the compositions disclosed herein include biobased carbon as substantially all of the carbon present in the mixtures of compounds, which can refer to a biobased carbon content of at least 90%, at least 95%, or at least 98% of the total carbon content. The compositions may include entirely biobased PHAs and entirely biobased reactants determined to have a biobased carbon content of at least about 98%, at least about 99%, at least about 99.5%, or about 100% of the total carbon content. The compositions disclosed herein include organic biomass, which is also biobased.

[0100] The disclosed biodegradable bioplastic compositions as formulated may be devoid of petroleum or fossil fuel components. The disclosed biodegradable bioplastic compositions may be 100% biobased, 100% biodegradable, and 100% marine biodegradable. In some aspects, the compositions may be 50%, or 60%, or 70%, or 80%, or 90%, or 95% plant derived, biobased, and biodegradable.

[0101] In one aspect, an article is disclosed. The article is made of or includes one or more biodegradable bioplastic compositions as disclosed herein. The composition may include more than 85 wt.% PHA polymers. As noted, the article may demonstrate a synergisticbalance of performance features for semi-rigid containment as well as good mechanical and physical properties, e.g., properties that are comparable to other materials available on the market for packaging, and that the article is flexible and durable enough to endure 1-5 years shelf life including multiple uses (opening and closing repeatedly) across a range of temperatures.

[0102] The disclosed biodegradable bioplastic compositions are particularly germane to disposable multi-use packaging.

[0103] The biodegradable bioplastic compositions may include one or more PHAs in an amount ranging from 70 wt.% to 99 wt.%, e.g., 75 wt.% to 98 wt.%, 80 wt.% to 95 wt.%, or 85 wt.% to 95 wt.%, or 88 wt.% to 92 wt.%; one or more organics in an amount ranging from 1 wt.% to 30 wt.%, e.g. 2 wt.% to 25 wt.%, 5 wt.% to 20 wt.%, or 5 wt.% to 15 wt.%, or 8 wt.% to 12 wt.%; and one or more flow agents in an amount ranging from 0.1 wt.% to 20 wt.%, e.g., 0.5 wt.% to 15 wt.%, 0.75 wt.% to 10 wt.%, 1 wt.% to 10 wt.%, or 3 wt.% to 8 wt.%, where all weight percentages are based on total weight of the composition.

[0104] In certain embodiments, the biodegradable bioplastic composition consists of one or more PHAs in an amount ranging from 70 wt.% to 99 wt.%, e.g., 75 wt.% to 98 wt.%, from 80 wt.% to 95 wt.%, or 85 wt.% to 95 wt.%, or 88 wt.% to 92 wt.%; one or more organics in an amount ranging from 1 wt.% to 30 wt.%, e.g., 2 wt.% to 25 wt.%, 5 wt.% to 20 wt.%, or 5 wt.% to 15 wt.%, 8 wt.% to 12 wt.%, or 10 wt.% to 12 wt.%; and one or more flow agents in an amount ranging from 0.1 wt.% to 20 wt.%, e.g., 0.5 wt.% to 15 wt.%, 0.75 wt.% to 10 wt.%, 1 wt.% to 10 wt.%, or 3 wt.% to 8 wt.%.

[0105] The components of the biodegradable bioplastic composition are now discussed individually. It is contemplated that these components may be employed with one another to form the aforementioned biodegradable bioplastic compositions.Polymers

[0106] The disclosed biodegradable bioplastics demonstrate unexpected sustainability benefits over conventional polymers such as LDPE, MDPE, HDPE, PET, PP, PVC, ABS, nylon (PA6, PA66), polystyrene (PS), and PLA for disposable packaging applications and are comparable in efficacy to these conventional polymers in terms of their mechanical performance, physical properties, food / cosmetic chemical compatibility, and environmental compatibility. Biodegradable bioplastic compositions may be formulated to have accelerated decomposition rates while maintaining critical properties such as shelf life.

[0107] Polymers of the present disclosure include one or more bioplastic polyhydroxyalkanoates (PHA). PHAs may be bio-based and biodegradable. PHAs may be produced by bacterial fermentation using bio-derived feedstocks - including agricultural waste - and thus may be an alternative to fossil fuel-derived plastics. PHAs may be polyesters synthesized and stored by various bacteria and archaea in their cytoplasm as water-insoluble inclusions.

[0108] PHA is a family of polymers including, for example, R-3-hydroxyalkanoic acids; the general structure of PHA is shown in formula (I)

[0109] PHA polymers have properties of biodegradable thermoplastics and elastomers, which can be categorized into subclasses according to the side chain of their monomers. Specifically, there may be three main categories: short-chain-length PHAs (“scl-PHA”) with three to five carbon monomers, medium-chain-length PHAs (“mcl-PHA”) with six to fourteen carbon monomers, and long-chain-length PHA (“Icl-PHA”) fifteen carbon monomers and greater. The biodegradable bioplastic compositions disclosed herein include one or more polyhydroxyalkanoates having chain lengths ranging from 3 to 5 carbons, 6 to 14 carbons, 15 carbons and greater, or any combination of two or more thereof. PHAs may also be categorized by number average molecular weight (Mn), which may range from about 50,000 to 1,400,000 Da. The biodegradable bioplastic compositions disclosed herein may include one or more polyhydroxyalkanoates having molecular weights ranging from 250,000-1,050,000 Da.

[0110] Advantageously, PHAs (polyhydroxyalkanoates) based bioplastics are waterproof, durable in sterile and dry environments providing shelf-life, and degrade in the soil. PHAs have thermoplastic properties and can be processed using common processes such as injection molding, 3D printing, blow molding, and thermoforming when suitably processed or compounded.[OHl] Suitable polyester polyhydroxyalkanoates include poly 3 -hydroxybutyrate 4-hy- droxybutyrate (P34HB), poly(3-hydroxybutyrate-co-3 -hydroxy valerate) (PHBV), or combinations or copolymers thereof. These PHAs have differing mechanical properties such as tensile strength, Young’s modulus, specific gravity, and stickiness which may allow for compounding to achieve elasticity and tensile properties suitable for blow molding.

[0112] P34HB is a random copolymer of 3 -hydroxybutyrate (3HB) and 4-hydroxybutyr- ate (4HB) having the structure according to formula (II)

[0113] PHBV is a random copolymer of 3 -hydroxybutyrate (3HB) and 3 -hydroxy valerate(3HV) having the structure according to formula (III)

[0114] The biodegradable bioplastic composition comprises PHA(s) as the major component. In one embodiment, the biodegradable bioplastic composition comprises one or more PHAs (e.g., poly 3 -hydroxybutyrate 4-hydroxybutyrate (P34HB), poly(3-hydroxybutyrate-co- 3 -hydroxy valerate) (PHBV), or combinations thereof) in an amount of about 70 wt.% to about 99 wt.% based on total weight of the composition, e.g., about 75 wt.% to about 98 wt.%, about 80 wt.% to about 95 wt.%, about 85 wt.% to about 95 wt.%, or about 88 wt.% to about 92 wt.%.

[0115] The biodegradable bioplastic composition may include more than about 60 wt.% PHAs, e.g., more than about 70 wt.%, more than about 80 wt.%, more than about 85 wt.%, or more than about 88 wt.%; and less than about 99 wt.% PHAs, e.g., less than about 98 wt.%, less than about 95 wt.%, or less than about 92 wt.%. The biodegradable bioplastic composition may include PHA in an amount of about 60 wt.% to about 99 wt.%, about 70 wt.% to about 98 wt.%, about 80 wt.% to about 95 wt.%, or about 85 wt.% to about 90 wt.%. For example, the biodegradable bioplastic composition comprises about 88 wt.% PHAs.

[0116] The biodegradable bioplastic compositions may include a first and second PHA. The biodegradable bioplastic compositions may include a first PHA in an amount ranging from 5 wt.% to 45 wt.% and a second PHA in an amount ranging from 40 wt.% to 80 wt.%, one or more organics in an amount ranging from 1 wt.% to 30 wt.%, and a non-petrochemi-cally derived flow agent in an amount ranging from 0.1 wt.% to 10 wt.%. In certain embodiments, the biodegradable bioplastic composition consists of poly 3 -hydroxybutyrate 4-hy- droxybutyrate (P34HB) in an amount ranging from 5 wt.% to 45 wt.% and poly (3 -hydroxy - butyrate-co-3 -hydroxy valerate) (PHBV) in an amount ranging from 40 wt.% to 80 wt.%, one or more organics in an amount ranging from 1 wt.% to 30 wt.%, and a non-petrochemically derived flow agent in an amount ranging from 0.1 wt.% to 10 wt.%.Organic Biomass

[0117] The biodegradable bioplastic composition further comprises an organic biomass. The organic biomass may include bamboo powder, bamboo fiber, hemp fiber, castor plant fiber, wool, charcoal powder, nutshell powder, pulp, or a combination of any two or more thereof.

[0118] The biodegradable bioplastic composition may include the organic biomass as a minor component. The biodegradable bioplastic composition may include one or more organic biomass materials in an amount of about 1 wt.% to about 30 wt.% based on total weight of the composition, e.g., about 2 wt.% to about 25 wt.%, about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 8 wt.% to about 12 wt.%, or about 10 wt.% to about 12 wt.%.

[0119] The biodegradable bioplastic composition may include greater than 1 wt.% organic biomass, e.g., greater than 2 wt.%, greater than 5 wt.%, greater than 8 wt.%, or greater than 10 wt.%; and may include less than 30 wt.% organics, e.g., less than 25 wt.%, less than 20 wt.%, less than 15 wt.%, or less than 12 wt.%. In some embodiments, the biodegradable bioplastic composition includes about 10 wt.% organic biomass.

[0120] Suitable but nonlimiting examples of organic biomass materials include any anhydrous, naturally-derived organic powders and fibers. The organic biomass materials are preferably homogenous and naturally water resistant. While the organics may include bamboo powder, bamboo fiber, hemp fiber, castor plant fiber, wool, charcoal powder, nutshell powder, pulp, or a combination of any two or more thereof.

[0121] For example, bamboo powder and bamboo fiber are suitable organic biomass materials for incorporation in the biodegradable bioplastic composition since bamboo is naturally water resistant and biodegradable, does not impart an inherently dark color to the end product, and bamboo can be farmed and harvested sustainably.

[0122] Bamboo powder, for example, is a nonpolar material, and thus presents challenges to blend uniformly with the PHAs for which there is no mutual chemical attraction. The processes herein provide uniform mixing of the compositions including major (PHAs) and minor (organics) components without plasticizers.

[0123] The organic biomass material, as blended with the polymer, may be in fiber or powder form. The organic biomass material may be in a form that is able to pass through a sieve corresponding to a range of mesh sizes of about 200 to about 4000 (e.g., about 200 to about 3500, about 500 to about 3000, or about 1500 to about 2500). For example, the mesh size may be about 2000.

[0124] The organic biomass material may be bamboo powder farmed and harvested sustainably without genetically modified organism technology. The bamboo powder may be locally sourced. For example, the chemical analysis of the bamboo powder may include about 0 wt.% to about 10 wt.% water (e.g., 5.46 wt.%), about 5 wt.% to about 20 wt.% calcium carbonate (e.g., 12.08 wt.%), about 60 wt.% to about 90 wt.% cellulose (e.g., 75.47 wt.%), about 10 wt.% to about 50 wt.% acid insoluble lignin (e.g., 31.34 wt.%), and about 1 wt.% to about 20 wt.% phenyl alcohol extract (e.g., 7.66 wt.%). This analysis is one example and, as known in the art, individual components of the bamboo can vary. The bamboo powder may be dried to remove water content and passed through a 2000 mesh size sieve prior to dispersing within the polymer.Flow Agent

[0125] The biodegradable bioplastic composition includes a flow agent, specifically a non-petrochemically derived flow agent that is consumer safe that may provide stiffness and mold release during blow molding of the compositions. The non-petrochemically derived flow agent may be a mineral-derived flow agent such as silicon dioxide (SiO2), calcium carbonate (CaCO3), clay mineral, or combinations thereof. In some aspects, the flow agent may comprise, consist of, or consist essentially of, tricalcium phosphate, powdered cellulose, magnesium stearate, sodium bicarbonate, sodium ferrocyanide, potassium ferrocyanide, calcium ferrocyanide, calcium phosphate, sodium silicate, sodium dioxide, calcium silicate, magnesium trisilicate, hydrous magnesium silicate (talcum powder), sodium aluminosilicate, potassium aluminum silicate, calcium aluminosilicate, dioxosilane (bentonite), aluminum silicate, stearic acid, poly dimethyl siloxane, kaolinite, antigorite, pyrophyllite, illite, mica, magnesium oxide magnesium hydroxide, magnesium carbonate or combinations thereof.

[0126] The clay mineral may include a hydrous aluminum phyllosilicate (e.g., kaolin (AhSi2O5(OH)4 or montmorillonite ((Na,Ca)o.33(Al,Mg)2(Si40io)(OH)2 nH20)).

[0127] The mineral-derived flow agent may be in the form of nanomaterials. For example, the mineral-derived flow agent may include nanoparticles or nanosheets having at least one dimension of about 20 nm to about 2000 nm, about 20 nm to about 1000 nm, about 1 nm to about 500 nm, including 2 nm to about 400 nm, about 2 nm to about 100 nm, about 5 nm to about 80 nm, about 10 nm to about 60 nm, or about 30 nm to about 50 nm.

[0128] The flow agent may include biobased glycerol monostearate, mono-glycerides, diglycerides, polyglycerol esters, or combinations of any two or more thereof.

[0129] The biodegradable bioplastic composition includes the flow agent as a minor component. The biodegradable bioplastic composition may include one or more flow agents. The biodegradable bioplastic composition may include two flow agents, three flow agents, four flow agents, or five flow agents. The total amount of flow agents in the composition may be about 0.1 wt.% to about 20 wt.% based on total weight of the composition, e.g., about 0.1 wt.% to about 15 wt.%, about 0.5 wt.% to about 10 wt.%, about 0.75 wt.% to about 10 wt.%, about 1 wt.% to about 10 wt.%, about 3 wt.% to about 8 wt.%, or about 7 wt.%.

[0130] The biodegradable bioplastic composition may include more than about 0.1 wt.% flow agents, e.g., more than about 0.5 wt.%, more than about 0.75 wt.%, more than about 1 wt.%, or more than about 1.5 wt.%; and less than about 20 wt.% flow agents, e.g., less than about 15 wt.%, less than about 10 wt.%, or less than about 8 wt.%. In some embodiments, the biodegradable bioplastic composition may include about 7 wt.% flow agents.Additional Components

[0131] In some particular instances, the biodegradable bioplastic compositions or articles made therefrom can comprise (other than flow agents as described above) optional aesthetic aids to add aesthetic appeal to the compositions or articles made therefrom as desired for the end consumer, e.g., inks (e.g., non-ecotoxic inks) or colorants. Processing of organic raw material may be used to lighten its color prior to mixing the biodegradable bioplastic composition. Thus, another advantage of the biodegradable bioplastic compositions described herein is the ability to bleach and / or modify the organic components for aesthetic purposes. These optional components may not affect the structure or performance of the biodegradable bio-plastic composition. Additionally, or alternatively, the compositions or articles made therefrom may include etching or printing on one or more surfaces of the container. Optional aesthetic aids such as these are for decoration only.Acid Content

[0132] Without being bound by any theory, the addition of organic biomass may have a surprising effect on the performance of the biodegradable bioplastic compositions and articles disclosed herein. As an example, the acid content generated upon degradation has been found to decrease the pH of soil or compost. Thus, the biodegradable bioplastic compositions herein may generate an acid content that may be reduced through the introduction of organics in the composition. Upon decomposition, in certain embodiments, the biodegradable bioplastic composition may demonstrate a reduction of concentration of acidic byproducts after enzymatic degradation as compared with the 100% polyhydroxyalkanoates (PHA) reference sample. Upon decomposition, in certain embodiments, the biodegradable bioplastic composition may demonstrate a reduction of concentration of acidic byproducts after enzymatic degradation as compared with a 100% pure poly(lactic acid) (PL A) reference sample.

[0133] The biodegradable bioplastic compositions may reduce the acid content generated upon degradation by a percentage as compared with a pure (100%) PHA reference sample. For example, the biodegradable bioplastic composition may reduce the acid content generated upon degradation by a percentage as compared with a pure (100%) PHA reference sample in an amount ranging from about 1% to about 30%, e.g., about 2% to about 25%, about 5% to about 20%, about 5% to about 15%, or about 8% to 12%.

[0134] The biodegradable bioplastic compositions may reduce the acid content generated upon degradation in an amount greater than 1%, e.g., greater than 2%, greater than 5%, greater than 8%, or greater than 10%; and less than 30%, e.g., less than 25%, less than 20%, or less than 15%. In some embodiments, the biodegradable bioplastic composition reduces the acid content generated upon degradation [by a percentage as compared with a pure (100%) PHA reference sample] in an amount of about 10%.

[0135] This reduction of the acid content generated upon degradation may be directly correlated to the content of organic biomass and additives, in other words, the reduction of acid content generated upon degradation may be proportional to the organic biomass and additive content. This reduction may decrease deleterious effects on the environmental soils or compost upon degradation. Thus, high organic biomass and presence of additives such asflow agents loading may be desired as with a higher organic content, the higher the reduction of acid content may be realized.Rate of Degradation

[0136] The addition of organic biomass may also surprisingly accelerate decomposition of the compositions disclosed herein. Thus, by adding as much organic matter as possible while maintaining structural integrity (e.g., mechanical properties), the biodegradable bioplastic compositions disclosed herein may accelerate decomposition. The decomposition may be accelerated as compared to pure PLA or PHA products. Upon decomposition, in certain embodiments, the biodegradable bioplastic composition may demonstrate accelerated decomposition as compared with the 100% polyhydroxyalkanoates (PHA) reference sample. Upon decomposition, in certain embodiments, the biodegradable bioplastic compositions may demonstrate accelerated decomposition as compared with a 100% pure poly(lactic acid) (PLA) reference sample. The biodegradable bioplastic compositions disclosed herein may break down at a rate of degradation that may be equal to or higher than the rate of degradation of pure PHA, e.g., a 100% polyhydroxyalkanoates (PHA) reference sample.

[0137] The biodegradable bioplastic compositions may have an increased degradation rate as compared to 100% PHA.Properties

[0138] As noted herein, by utilizing a biodegradable bioplastic composition, the resultant composition and / or article formed from the composition may be capable of providing containment of contents for a determined shelf life, may be flexible and thin-walled enough so as to dispense liquid contents when squeezed, and subsequently decompose upon disposal.Tensile Strength and Elastic Modulus

[0139] The biodegradable bioplastic compositions may be semi-rigid. The biodegradable bioplastic composition and / or articles formed therefrom, may have a tensile strength of about 25-80 MPa as determined by ASTM D638-22. As understood, while 25 MPa may be a preferred lower limit in some applications, the biodegradable bioplastic compositions and articles may have lower tensile strength as is suitable for some applications. The biodegradable bioplastic compositions and articles formed therefrom may have a tensile strength greater than 25 MPa. The tensile strength of the biodegradable bioplastic compositions disclosed herein may be comparable to that of pure (100%) PHA. The ratio of organic material, andprocessing methods as described herein, may be carefully tailored so as not to compromise the structural fidelity.

[0140] The biodegradable bioplastic compositions and / or articles may have an average tensile strength greater than about 10 MPa, e.g., greater than about 15 MPa, greater than about 20 MPa, greater than about 25 MPa, greater than about 30 MPa, greater than about 35 MPa, greater than about 40 MPa, or greater than about 45 MPa. The biodegradable bioplastic compositions may have an average tensile strength of about 20 MPa to about 80 MPa, e.g., about 25 MPa to about 65 MPa, from about 25 MPa to about 50 MPa, or from about 25 MPa to about 40 MPa. The biodegradable bioplastic compositions and / or articles may have an average tensile strength of greater than about 40 MPa.

[0141] The biodegradable bioplastic compositions and / or articles may have an elastic modulus of about 0.10-3.0 GPa, including about 0.2 GPa to about 3.0 GPa, about 0.5 GPa to about 3 GPa, about 1 GPa to about 3 GPa, about 2 GPa to about 3 GPa, about 2.5 GPa to about 3 GPa, or about 2.7 GPa.Density

[0142] The biodegradable bioplastic composition may have a specific gravity of about 1.20 g / cm3. The biodegradable bioplastic compositions and articles formed therefrom may have a density greater than 1.20 g / cm3or a density less than 1.20 g / cm3. At this density value, the density is less than half that of glass having a density of about 2.5 g / cm3. In some instances, a lower density is desirable as the articles for end use are then even lighter. In some cases, the biodegradable bioplastic compositions and / or articles may have a density from 1.00 g / cm3to 1.30 g / cm3. For biodegradable bioplastic compositions and / or articles, a density less than 1.20 g / cm3is also contemplated.

[0143] The density of the biodegradable bioplastic compositions disclosed herein may be comparable to that of to current semi-rigid plastics on the market such as HDPE, PET, PP, PVC, ABS, nylon (PA6, PA66), polystyrene (PS), PLA, as well as being comparable to that of pure (100%) PHA. Advantageously, the density of the biodegradable bioplastic composition may be much lower than commonly used glass containment articles, thus the biodegradable bioplastic composition and articles formed therefrom may be significantly lighter to transport and incur a reduced carbon footprint.Non-reactivity and Compatibility

[0144] The biodegradable bioplastic compositions may be chemically compatible (i.e., non-reactive) with solvents, where the solvents may be at various concentrations. Solvents include those found in consumer products such as, but are not limited to, water, dimethicone, glycerin, and coconut oil.

[0145] The biodegradable bioplastic compositions may be compatible with many anhydrous, aqueous, emulsified, and oil-based consumer packaged goods at standard shelf conditions throughout the lifecycle of the product.Stability

[0146] The biodegradable bioplastic composition may be semi-rigid and shelf-stable for use with consumer packaged goods to the degree that it can withstand industry standard accelerated stability testing as well as freeze-thaw cycles and varying temperature and humidity conditions without leeching into the packaged contents or becoming brittle.

[0147] The stability of the biodegradable bioplastic composition makes the composition and articles formed therefrom suitable for multiple uses, such as non-limiting example of a bottle cap that may be opened and closed repeatedly. In particular embodiments, the biodegradable bioplastic compositions and articles may be differentiated from single-use films or sachets that are utilized only once.

[0148] The biodegradable bioplastic composition may have a water vapor transmittance of about 0.1 g / m2to about 0.5 g / m2(e.g., about 0.1 g / m2to about 0.4 g / m2, about 0.2 g / m2to about 0.3 g / m2, or about 0.25 g / m2) over 24 hours at 38 °C and 90% relative humidity (RH).Shelf Life

[0149] The biodegradable bioplastic composition and articles made therefrom may have a shelf life of greater than 12 months, greater than 18 months, greater than 24 months, greater than 30 months, greater than 36 months, greater than 42 months, or greater than 48 months. The biodegradable bioplastic composition and articles made therefrom may have a shelf life of about 1 month to about 5 years, about 6 months to about 5 years, about 1 year to about 5 years, about 2 years to about 5 years, about 3 years to about 5 years, or about 4 years to about 5 years.Compostability

[0150] The biodegradable bioplastic compositions may also be compostable or "industrially compostable" according to ASTM D6400 standards. The biodegradable bioplastic compositions and articles made therefrom are non-toxic to the environment when disposed at end of life cycle.

[0151] The biodegradable bioplastic compositions may also be compostable or “home composable” according to AS4736 or AS5810 standards. The biodegradable bioplastic compositions and articles made therefrom are non-toxic to the environment when disposed at end of life cycle, and can break down quickly and in a home compost pile.Thickness

[0152] The biodegradable bioplastic compositions are suitable for a wide range of wall thicknesses for articles formed from the composition. For example, the compositions may be suitable for thinner articles in the 0.01 mm-1 mm range that cannot be formed via injection molding. The article wall thickness is defined as the thickness through the container packaging, such as, e.g., a side wall, a circumferential wall, a top, or a bottom.

[0153] In non-limiting examples, FIG. 2A and FIG. 2B show an article 200, in cross-section and perspective views respectively, of a bottle for a cosmetics container, with a wall thickness, t2oo, of about 0.5 mm, where the wall thickness ranges from 0.5 mm to 2 mm.

[0154] In some cases, the thickness, t, of the biodegradable bioplastic article wall can range from 0.01 mm to 10 mm, e.g., 0.05 mm to 8 mm, 0.1 mm to 5 mm, 0.5 mm to 3 mm, or from 1 to 2 mm.

[0155] The thickness of the biodegradable bioplastic article wall may be greater than 0.01 mm, e.g., greater than 0.05 mm, greater than 0.1 mm, greater than 0.5 mm, or greater than 1 mm. In certain aspects, the wall thickness is greater than 0.01 mm, greater than 0.015 mm, greater than 0.02 mm, greater than 0.03 mm, greater than 0.04 mm, greater than 0.05 mm, greater than 0.1 mm, or greater than 0.5 mm. The thickness of the biodegradable bioplastic article wall may be less than 10 mm, e.g., less than 8 mm, less than 5 mm, less than 3 mm, or less than 2.5 mm.Homogeneous Compositions

[0156] The biodegradable bioplastic compositions disclosed herein are suitable for forming articles, such as those for use in packaging and / or as containers. The composition according to the process herein demonstrates homogeneity. That means that the dispersed organics are uniformly distributed in the biodegradable bioplastic material. After processing for the composition, the biodegradable bioplastic material may be in pellet form, which can be directly supplied to manufactures of articles (e.g., containers) for use in further forming processes.Monolithic Articles

[0157] Advantageously, the articles made may be monolithic. In other words, the formed articles (by the further forming methods described herein) may be formed into monolithic shapes of uniform material made from the biodegradable bioplastic composition. In certain embodiments, the formed articles are devoid of other materials. Specifically, this means that the formed articles may be free of additional materials and / or layers and / or coatings. The articles disclosed herein may be made of a single material, the biodegradable bioplastic composition, formed into monolithic article(s). Monolithic single materials may provide another benefit at end of lifecycle - ease of disposal. This is because articles formed of more than one material, such as layered or laminated articles, may require separation prior to disposal. Thus, for example, laminated packaging is may be excluded as contemplated herein, as well as articles formed to have two layers or more (e.g., a formed plastic layer or material combined with another material or layer such as cork, paper, among others).Processing

[0158] The present disclosure also relates to processes for preparing the provided biodegradable bioplastic compositions and / or articles formed therefrom. The biodegradable bioplastic articles disclosed herein may be formed by blow molding and / or thermoforming to manufacture semi-rigid plastic articles for end use.

[0159] Compositions of biodegradable bioplastic as described herein and including organics and a non-petrochemically derived flow agent were prepared according to the process as described below; FIG. 1 is a flow chart of an exemplary process 100. Advantageously, the processes are compatible with existing equipment as known in the art.

[0160] The raw materials may be prepared by assembling and weighing. The bioplastic component may be thermoplastic polyhydroxyalkanoates (PHA) polymers (in pellet form),manufactured sustainably through a fermentation process and without use of petroleum raw materials (zero petroleum or fossil fuel components). The 100% biobased poly 3-hydroxy- butyrate 4-hydroxybutyrate (P34HB) and the 100% biobased poly(3-hydroxybutyrate-co-3- hydroxyvalerate) (PHBV) may be synthesized by fermenting plant biomass chosen from sugars, starches, and lipids and provided as in step 110.

[0161] The organic biomass materials may be chosen from one or more of bamboo powder, bamboo fiber, hemp fiber, castor plant fiber, wool, charcoal powder, nutshell powder, pulp, or combinations thereof. The organic biomass materials may be then sieved the through a sieve chosen from a size between 200 and 2000 mesh screen, preferably 2000 mesh screen. The petrochemically free bioplastic and organics may be provided at 120, along with a non- petrochemically derived flow agent for compounding (also referred to herein interchangeably as homogenizing). The petrochemically free bioplastics, organic biomass materials, and flow agents used herein may be non-petrochemically derived and made purely from plant-based and mineral-based raw materials.

[0162] Compounding 120 may be performed in a high-speed mixer and may include mixing the bioplastics, organic biomass materials, and flow agents at a temperature ranging from 120 °C to 160 °C. After compounding, the mixture may be cooled at step 130 in water to a temperature ranging from 0 °C to 100 °C, or more preferably ranging from 30 °C to 80 °C.

[0163] Resting the mixture at step 140 may be performed for a period ranging from 24 to 72 hours to form a compound. The rested compound may be pelletizing at step 150 to form pellets for use in forming an article.

[0164] Optionally, drying 160 the pellets may be performed at a temperature ranging from 45 °C to 85 °C. This may be useful for blow molding and / or thermoforming 170 to form a semi-rigid article.

[0165] Process 100, including steps 110-170, for preparing biodegradable bioplastic compositions and / or semi-rigid articles made therefrom may be completely (100%) free of petroleum-derived raw materials. Thus, the integrity of the biodegradable bioplastic compositions and / or articles made therefrom may be preserved without involving fossil fuel sources or eco- toxic additives.Applications

[0166] The biodegradable bioplastic composition of the processes herein may be provided in pellet form. Importantly, these pellets may be used with existing manufacturingplants and molds / tooling to replace any range of plastic parts that currently use petroleumbased thermoplastics. Thus, the industrial applicability is non-limiting.

[0167] The biodegradable bioplastic compositions and / or articles made therefrom may be formed into any of a variety of container shapes according to application for use. In some embodiments, the biodegradable bioplastic article may be a food packaging container or a consumer health and beauty container. Articles made from the biodegradable bioplastic compositions may include, but are not limited to, hollow containers (packaging vessels and closures), solid parts (toys, automotive, electronics, medical devices, tools, home goods), and other plastic products in large volumes, and the like. Specifically, these articles may be flexible, e.g., squeezable, and may be useful for dispensing liquids and gels.

[0168] Advantages of the present biodegradable bioplastic compositions and / or articles made therefrom and processes for preparing make their industrial applicability clear. They are clean and environmentally-friendly with only three ingredient components (and no conventional additives). The biodegradable bioplastic compositions and / or articles may use 100% plant-derived or mineral-derived raw materials and may be manufactured in a way that is compatible with existing blow molding and / or thermoforming machinery. For example, blow molding may be conducted at a temperature of about 130 °C to about 175 °C, including 140 °C to about 175 °C, about 150 °C to about 165 °C, about 165 °C to about 175 °C), or preferably from about 140 °C to about 160 °C.

[0169] When formed into a semi-rigid container for use in consumer product packaging, these biodegradable bioplastic compositions and / or articles may provide a safe stable barrier that can be composted at the end of its lifecycle and fill the need for an eco-friendly alternative to petroleum-based plastic or other heavier packaging materials.Examples

[0170] A sample was prepared according to the process 100 as described above. The sample included 82 wt.% PHA, 10 wt.% bamboo, 5 wt.% nanoparticulate montmorillonite (aluminum pillared clay, CAS #139264-88-3), and 3 wt.% nanoparticulate calcium carbonate (CAS #471-34-1).

[0171] The sample was characterized according to Table 1.Table 1 : Characterization of a biodegradable bioplastic sample

[0172] As demonstrated in Table 1, compared to conventional polyethylene plastic which is often used for blow molding, the biodegradable bioplastics described herein demonstrate similar or better performance metrics. The biodegradable bioplastics demonstrate similar density measurements while also having better water vapor and oxygen transmission, indicatingthat the products are surprisingly better suited for providing a barrier for consumer products than conventional plastics. The bioplastics disclosed herein also surprisingly demonstrated a higher tensile strength and elasticity than conventional low-density polyethylene, which is suitable for semi-flexible applications and usage conditions such as repeated squeezing by a consumer.

[0173] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0174] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0175] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0176] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0177] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0178] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definPitions in this disclosure.

[0179] Other embodiments are set forth in the following claims.

Claims

CLAIMSWHAT IS CLAIMED IS:

1. A biodegradable bioplastic composition comprising: a mixture of polyhydroxy alkanoate (PHA) polymers comprising poly 3 -hydroxybutyrate 4- hydroxybutyrate (P34HB) and poly(3-hydroxybutyrate-co-3 -hydroxy valerate) (PHBV); an organic biomass dispersed within the polymer; and at least one flow agent.

2. The biodegradable bioplastic composition of claim 1, wherein the at least one flow agent is non-petrochemically derived.

3. The biodegradable bioplastic composition of claim 1 or 2, wherein the P34HB and the PHBV are each independently 100% plant derived, 100% biobased, and 100% biodegradable.

4. The biodegradable bioplastic composition of any one of claims 1-3, wherein the P34HB and the PHBV each independently have a molecular weight of about 250,000 Da to about 1,050,000 Da.

5. The biodegradable bioplastic composition of any one of claims 1-3, wherein the P34HB and the PHBV each independently have an average molecular weight of about 650,000 Da.

6. The biodegradable bioplastic composition of any one of claims 1-5, wherein the biodegradable bioplastic composition comprises about 70 wt.% to about 90 wt.% of the mixture of PHA polymers.

7. The biodegradable bioplastic composition of any one of claims 1-6, comprising: about 5 wt.% to about 45 wt.% of the P34HB; about 40 wt.% to about 80 wt.% of the PHBV; about 1 wt.% to about 30 wt.% of the organic biomass; and about 0.1 wt.% to about 15 wt.% of the flow agent.

8. The biodegradable bioplastic composition of any one of claims 1-6, comprising: about 15 wt.% to about 95 wt.% PHA;about 5 wt.% to about 20 wt.% of the organic biomass; and about 0.5 wt.% to about 15 wt.% of the flow agent.

9. The biodegradable bioplastic composition of claim 1 comprising: about 82% PHA; about 10 wt.% organic biomass; and about 8 wt.% non-petrochemically derived flow agent.

10. The biodegradable bioplastic composition of claim 1, wherein the biodegradable bioplastic composition is 100% biodegradable.

11. The biodegradable bioplastic composition of claim 1, wherein the biodegradable bioplastic composition is free of petrochemically derived components.

12. The biodegradable bioplastic composition of claim 1, wherein the organic biomass comprises one or more of bamboo powder, bamboo fiber, hemp fiber, castor plant fiber, wool, charcoal powder, nutshell powder, pulp, or a combination of two or more thereof.

13. The biodegradable bioplastic composition of claim 1, wherein the flow agent comprises calcium carbonate (CaCCh).

14. The biodegradable bioplastic composition of claim 1, wherein the flow agent comprises calcium carbonate (CaCCh) and montmorillonite.

15. The biodegradable bioplastic composition of claim 14, wherein the montmorillonite has an average particle diameter of about 20 nm to about 2500 nm.

16. The biodegradable bioplastic composition of any one of claims 13-15, wherein the calcium carbonate has an average particle diameter of 5 nm to 50 nm.

17. The biodegradable bioplastic composition of any one of claims 13-15, wherein the calcium carbonate has an average particle diameter of about 20 nm.

18. The biodegradable bioplastic composition of claim 1, wherein the flow agent is selected from glycerol monostearate, mono- and di-glycerides, polyglycerol esters, or combinations thereof.

19. The biodegradable bioplastic composition of any one of claims 1-18, wherein the biodegradable bioplastic composition has an average tensile strength of about 25 MPa to about 80 MPa as determined by ASTM D638-22.

20. The biodegradable bioplastic composition of any one of claims 1-19, wherein the biodegradable bioplastic composition is chemically compatible with one or more solvents selected from water, dimethicone, glycerin, coconut oil, or combinations thereof.

21. An article comprising the biodegradable bioplastic composition of any one of claims 1-20, wherein the article has a tensile strength of about 25 MPa to about 80 MPa at 20 °C.

22. The article of claim 21, wherein the article has a wall thickness of about 0.01 mm to about 10.0 mm.

23. The article of claim 21 or 22, wherein the article is a packaging container or packaging closure.

24. The article of claim 21, wherein the article is a pellet having a diameter of about 0.01 mm to about 10.0 mm.

25. The article of any one of claims 21-24, wherein the article has a shelf life of greater than 12 months.

26. The article of any one of claims 21-24, wherein the article has a shelf life of greater than 36 months.

27. The article of claim 18, wherein the article is non-toxic to the environment when disposed at end of life cycle, and wherein the article has a decomposition rate greater than that of 100% PHA.

28. A method of making a biodegradable bioplastic composition, the method comprising: homogenizing a mixture of a poly 3 -hydroxybutyrate 4-hydroxybutyrate (P34HB), a poly (3- hydroxybutyrate-co-3 -hydroxy valerate) (PHBV), an organic biomass, a clay, and a flow agent; cooling the mixture in water at a temperature of 0 °C to 100 °C, or 30 °C to 80 °C; resting the mixture for a period of about 12 hours to 72 hours to form a compound, or 24 to 72 hours to form a compound.

29. The method of claim 28, wherein the P34HB is biobased.

30. The method of claim 28, further comprising synthesizing the P34HB by fermenting plant biomass chosen from sugars, starches, and lipids.

31. The method of any one of claims 28-30, wherein the PHBV is biobased.

32. The method of any one of claims 28-30, further comprising synthesizing the PHBV by fermenting plant biomass chosen from sugars, starches, and lipids.

33. The method of any one of claims 28-32, wherein homogenizing is conducted at a temperature of about 120 °C to about 160 °C34. The method of any one of claims 28-33, wherein the flow agent is non-petrochemi- cally derived.

35. The method of any one of claims 28-34, further comprising pelletizing the compound to form pellets.

36. The method of claim 35, further comprising forming a biodegradable bioplastic article from the pellets.

37. The method of claim 36, wherein the step of forming comprises blow molding or thermoforming.

38. The method of claim 37, wherein the step of forming comprises blow molding and blow molding comprises drying the pellets at a temperature of about 45 °C to 85 °C; and blow molding the pellets at a temperature ranging from 130 °C to 185 °C, or from about 140 °C to 175 °C, or from about 150 °C to 170 °C.

39. The method of any one of claims 28-34, wherein the biodegradable bioplastic composition is devoid of petrochemically derived components.

Images