Biodegradable polymeric composition comprising pha

Abstract

A biodegradable polymeric composition is disclosed. The biodegradable polymeric composition comprising: 15 to 94 wt.% of a first semi-crystalline PolyHydroxyAlkanoate (PHA) characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C; 5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to 0 °C; between 0 to 15 wt.% Polylactic acid (PLA), and 1 to 15 wt.% plasticizer.

Description

BIODEGRADABLE POLYMERIC COMPOSITION COMPRISING PHACROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of Israeli Patent Application No. 317695, filed 12 December 2024. The contents of the above application is all incorporated by reference as if fully set forth herein in its entirety.FIELD OF THE INVENTION

[0002] The invention relates generally to the field of biodegradable polymers, and methods of production and uses thereof. More specifically, the invention relates to biodegradable polymers comprising PolyHydroxy Alkanoate (PHA).BACKGROUND

[0003] PolyHydroxy Alkanoate (PHA) is a class of biodegradable polymers produced by microbial fermentation. Structurally, PHAs are polyesters composed of hydroxyalkanoate monomers, which can vary in length and composition, leading to a range of material properties. The general structure of PHA includes a repeating unit of (-O-CHR-CO-)n, where R represents a side chain that can be tailored to modify the polymer's characteristics. PHAs are known for their biocompatibility, biodegradability, and thermoplastic properties, making them suitable for various applications. They exhibit a wide range of mechanical properties, from rigid and brittle to flexible and elastic, depending on their monomer composition. Due to these properties, PHAs are used in medical applications, packaging, agricultural films, and as a sustainable alternative to petrochemical-based plastics.

[0004] However, PHAs are also known to have very limited formability and processability, therefore are usually mixed with Polylactic acid (PLA) at large amount, mostly above 30 wt.% PLA. PHAs, particularly polyhydroxybutyrate PHB, suffer from severe thermal instability that creates an extremely narrow processing window. The melting temperature of PHB is around 170 to 180°C, yet processing temperatures must reach at least 180 to 190°C to achieve adequate melt flow. This proximity creates a fundamental problem:PHB undergoes rapid thermal degradation at temperatures very close to those required for processing.

[0005] The thermal degradation mechanism in PHAs occurs through cis-elimination reactions involving a-hydrogens in the polymer repeat units. This degradation proceeds via a six- membered ring transition state, leading to random chain cleavage and the formation of olefinic compounds, carboxylic acids, cro tonic acid, and oligomers. The degradation causes a rapid decrease in molecular weight, severely limiting the acceptable residence time in processing equipment to only a few minutes.

[0006] In contrast PLA demonstrates significantly superior thermal stability during processing compared to PHA. PLA can be successfully processed across a wide temperature range from 170°C to 220°C for injection molding applications. Research shows that PLA maintains processability even at temperatures as low as 180 to 190°C, with optimal conditions often achieved at 185°C for injection molding. Unlike PHA's rapid degradation, PLA exhibits greater resistance to thermal degradation during processing. Studies demonstrate that PLA can be processed at 200°C for film extrusion applications, and even withstand temperatures up to 220 °C in certain molding operations without the severe molecular weight degradation characteristic of PHAs.

[0007] PLA can be well processed using any one of extrusion, injection molding, 3D printing, and the like.

[0008] However, PLA has poor biodegradability. PLA degrades slowly in most natural environments like soil, home compost, or landfills, requiring specific conditions found only in industrial composting facilities. While PLA is considered biodegradable, its degradation requires high temperatures, specific microorganisms, and sufficient oxygen, which are typically not present outside of an industrial composting environment. In a typical landfill, PLA can take centuries to break down and may end up fragmenting into microplastics.

[0009] In order to receive the combined properties of improved strength, and elasticity, a modification of the known PHA polymers, with one or as little as possible PLA, may be required.SUMMARY

[0010] The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools, and methods which are meant to be exemplary and illustrative, not limiting in scope.

[0011] Some aspects of the invention may be directed to a biodegradable polymeric composition, comprising: 15 to 94 wt.% of a first semi-crystalline PolyHydroxyAlkanoate(PHA) characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C; 5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to 0 °C; between 0 to 15 wt.% Polylactic acid (PLA) and 1 to 15 wt.% plasticizer.

[0012] In some embodiments, the biodegradable polymeric composition may further include: 5 to 35 wt.% of a second semi-crystalline PHA, and wherein the first semicrystalline PHA is characterized by a melting point of between 130 to 200 °C, and the second semi-crystalline PHA is characterized by a melting point of between 140 to 180 °C.

[0013] In some embodiments, the biodegradable polymeric composition may further include: a second amorphous PHA, different from the first amorphous PHA, and wherein the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%.

[0014] In some embodiments, the first amorphous PHA may be selected from Poly(3- hydroxybutyrate-co-4-hydroxybutyrate) (PH3B4HB), Poly(3-hydroxybutyrate-co-3- hydroxyhexanoate) (PH3BHHx), Poly(3-hydroxybutyrate-co-3 -hydroxyoctanoate)(PHBO), homopolymers, and any copolymers thereof. In some embodiments, the first semicrystalline PHA is selected from: Poly(3 -hydroxybutyrate) (PHB), Poly(3 -hydroxybutyrate - co-3-hydroxyvalerate (PHBV), Poly(3 -Hydroxy valerate) (PH3B), Poly(3 -hydroxy valerate) (PHV), Poly(3-hydroxyhexanoate) (PHHex), Poly(4-hydroxybutyrate) (P(4HB)), Poly(5- hydroxyvalerate) (P(5HV)) Poly(3 -hydroxypropionate) (PHP), Poly(3-hydroxybutanoates)(PHB), Poly(3-hydroxyoctanoate) (PHO), Poly(3-hydroxydecanoate) PHD, and any copolymer thereof.

[0015] In some embodiments, the plasticizer may be selected from, Acetyl-tributyl-citrate (ATBC), Poly(ethylene glycol) (PEG), Epoxidized Soybean Oil (ESBO), Jojoba oil,Glycerol, Sorbitol, Glycerol ester, Isosorbide diester, and polymeric plasticizers. In some embodiments, the biodegradable polymeric composition further comprising one or more additives, selected from: ultraviolet (UV) absorber, UV reflector, pigment, stabilizer, dyes, oxidation stabilizer, thermal stabilizer, degradation or decomposition inhibitors or promoters, mold release agent, nucleating agents, mineral fillers, carbon based fillers and reinforcing agents, glass based fillers and reinforcing agents, fire or flame inhibitors suppressors, thickening agents, additional modifying polymers such as impact modifiers, and stiffeners.

[0016] Some aspects of the invention may be related to an article comprising the composition according to any one of the embodiments disclosed herein.

[0017] Some additional aspects of the invention may be related to a method of making a biodegradable polymeric composition, comprising: melt mixing at 120-220 C, a mixture comprising: 15 to 94 wt.% of a first semi-crystalline PolyHydroxyAlkanoate (PHA) characterized by a Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C; 5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to -0 °C; between 0 to 15 wt.% Polylactic acid (PLA); and 1 to 15 wt.% plasticizer; and shaping the molten mixture.

[0018] In some embodiments, shaping may include, at least one of, extruding, casting, filament drawing, 3D Printing, pelletizing, injection molding, and compression molding. In some embodiments, the melt mixing is done continuously and comprises a continuous provision of the mixture. In some embodiments, shaping the molten mixture may be done continuously. In some embodiments, the melt mixing and the shaping of the molten mixture may be done in a batch.

[0019] In some embodiments, the method may further comprise adding to the mixture between 5 to 35 wt.% of a second semi-crystalline PHA, and wherein the first semicrystalline PHA is characterized by a melting point of between 130 to 200 °C, and the second semi-crystalline PHA is characterized by a melting point of between 140 to 180 °C. In some embodiments, the method may further comprise adding to the mixture a second amorphous PHA, different from the first amorphous PHA, and wherein the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%.BRIEF DESCRIPTION OF THE FIGURES

[0020] Fig. 1 is a flowchart of a method of making a biodegradable polymeric composition according to some embodiments of the invention.

[0021] Fig. 2 includes a table showing compositions according to some embodiments of the invention.

[0022] Fig. 3 which includes a table showing additional compositions according to some embodiments of the invention.

[0023] Fig. 4 includes a table showing additional compositions according to some embodiments of the invention.

[0024] Fig. 5 includes a table showing additional compositions according to some embodiments of the invention.DETAILED DESCRIPTION

[0025] The present invention in some embodiments thereof is at least partially based on a surprising finding, that in order to achieve an improvement in opposing properties, such as stiffness and ductility, a combination of more than one type of PHA may be required together with the addition of a plasticizer.

[0026] Traditional biodegradable polymers, such as PolyHydroxyAlkanoates (PHAs), often face challenges in achieving a balance between stiffness and ductility. This limitation restricts their application in areas requiring both durability and flexibility, such as packaging, fashion, and medical devices. Additionally, the high production costs and variability in mechanical properties further hinder their widespread adoption as sustainable alternatives to conventional plastics. The invention addresses these challenges by developing a biodegradable polymeric composition comprising a blend of amorphous and semicrystalline PHAs, along with a plasticizer. This composition enhances the mechanical properties by combining the flexibility of amorphous PHAs with the strength of semicrystalline PHAs. The inclusion of a plasticizer further improves elasticity, making the material suitable for a broader range of applications. This innovative approach not only optimizes the performance of PHAs but also promotes their use as a viable, eco-friendly alternative to petrochemical-based plastics.

[0027] PHAs are usually mixed with at least 30 wt% PLA to increase their ductility and formability. However, these high amounts of PLA harm the biodegradability of the composition, reducing it’s eco-friendly behavior. Therefore, a composition accoridng to embodiments of the invention may include at most 15 wt.% PLA.

[0028] In some embodiments, a composition of the invention may be included in an article. As used herein “an article, may include any object that is made at least partially from the composition. For example, the article, may be a wearable article (e.g., a shoe, a garment, etc.), a fashion article (e.g., a neckless, a belt, etc.) a package, a housing for electronic devices, and the like.

[0029] A composition according to embodiments of the invention may include a mixture of amorphous PHA characterized by a glass transition temperature (Tg) of between 0 to -20 °C, semi-crystalline PHA characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C, and a plasticizer.

[0030] In some embodiments, an amorphous PHA is a type of PHA characterized by its lack of crystalline structure, resulting in unique material properties. This amorphous nature imparts a lower glass transition temperature (Tg), typically between -20 to 0 °C, which contributes to its flexibility and elasticity. Unlike semi-crystalline PHAs, amorphous PHAs do not have a defined melting point, allowing them to be more pliable and less brittle. Amorphous PHA may not have a melting point. Some nonlimiting examples for amorphous PHA may include, Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (PH3B4HB), Poly(3- hydroxybutyrate-co-3-hydroxyhexanoate) (PH3BHHx), Poly(3-hydroxybutyrate-co-3- hydroxyoctanoate) (PHBO), homopolymers any copolymers thereof, the like.

[0031] In some embodiments, semi-crystalline PHA is a type of PHA that features both amorphous and crystalline regions within its structure. This dual-phase composition imparts a balance of strength and flexibility, making semi-crystalline PHAs suitable for a variety of applications. They are characterized by a Tg of between -10 to 10 °C (e.g., -8 °C, - 6 °C, -4 °C, -2, °C, 0 °C, 2 °C, 4 °C, 6, °C, 8 °C, and any value or range in between) and a melting point ranging from 120 to 220 °C (e.g., 140 °C, 160 °C, 180 °C, 200 °C, 210 °C, and any value o range in between). The crystalline regions provide rigidity and thermal stability, while the amorphous regions contribute to elasticity. In some embodiments, more than one type of semi-crystalline PHA may be included in the composition. The types of PHA maydiffer at least in the Tg, for example, the composition may include a first semi-crystalline PHA characterized by a melting point of between 170 to 220 °C, and a second semicrystalline PHA characterized by a melting point of between 120 to 180 °C.

[0032] In some embodiments, the semi-crystalline PHA is selected from Poly(3- hydroxybutyrate) (PHB), Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV),, Poly(3- hydroxyvalerate) (PHV), Poly(3-hydroxyhexanoate) (PHHex), Poly(4-hydroxybutyrate) (P(4HB) Poly(5-hydroxyvalerate) (P(5HV)) Poly(3-hydroxypropionate) (PHP), Poly(3- hydroxybutanoates) (PHB), Poly(3 -hydroxyoctanoate) (PHO), Poly(3-hydroxydecanoate) PHD, any copolymers thereof, and the like.

[0033] In some embodiments, the composition may include 15 to 94 wt.% of a first semicrystalline PHA characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C. For example, the composition may include semi-crystalline PHA at an amount of, 15 wt%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 94 wt.%, and any value or range in between.

[0034] In some embodiments, the composition may include 5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to 0 °C. For example, the amount of the first amorphous PHA in the composition may be 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 50 wt.%, 60 wt.% and any value or range in between.

[0035] In some embodiments, the composition may include a second amorphous PHA, different from the first amorphous PHA, for example, in at least one of the type of PHA, the molecular weight, the Tg, and the like. In some embodiments, the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%

[0036] In some embodiments, the composition may further include at least another second semi-crystalline PHA at an amount of between 5 to 35 wt.%. In some embodiments, the first semi-crystalline PHA may be characterized by a melting point of between 170 to 200 °C, and the second semi-crystalline PHA may be characterized by a melting point of between 140 to 180 °C. For example, the amount of the second semi-crystalline PHA in the composition may be 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%., 25 wt.%, 30 wt.%, 35 wt.%, and any value or range in between.

[0037] In some embodiments, the composition may further include between 0 to 15 wt.% PLA. Some composition may be PLA free, and some may include minor amount of PLA, such as, 1 wt.% PLA, 3 wt.% PLA, 5 wt.% PLA, 7 wt.% PLA, 10 wt.% PLA, 12 wt.% PLA, 15 wt.% PLA, and any value or range in between. The PLA may have different microstructures, crystalline, semi- crystalline, and / or amorphous. The inventors surprisingly found that all type of PLA have a similar effect of the mixture, when added and an amount not exceeding 15 wt.%.

[0038] In some embodiments, the composition may include between 1 to 15 wt.% plasticizer, for example, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.% and any value or range in between. In some embodiments, the plasticizer is selected from, Acetyl-tributyl-citrate (ATBC), Poly(ethylene glycol) (PEG), Epoxidized Soybean Oil (ESBO), Jojoba oil, Glycerol, Sorbitol, Glycerol- ester, Isosorbide diester, polymeric plasticizers, and the like.

[0039] In some embodiments, the composition may include one or more additives, selected from: ultraviolet (UV) absorber, UV reflector, pigment, dyes, Polylactic acid (PLA), oxidation stabilizer, thermal stabilizer, degradation or decomposition inhibitors or promoters, mold release agent, nucleating agents, mineral fillers, carbon based fillers and reinforcing agents, glass based fillers and reinforcing agents, fire or flame inhibitors suppressors, thickening agents, additional modifying polymers such as impact modifiers, stiffeners, and the like. Some nonlimiting examples for UV absorbers may include, Benzophenone derivatives, Benzotriazole derivatives, Triazine-based UV absorbers, Hindered amine light stabilizers (HALS), Oxalanilide compounds, and the like. Some nonlimiting examples for UV reflectors may include, Titanium Dioxide (TiO2), Zinc Oxide (ZnO), Aluminum Oxide (AI2O3), Silica (SiO2), Mica-based pigments, and the like. Some nonlimiting examples of stabilizers may include, Hindered amine light stabilizers (HALS), Phenolic Antioxidants, Phosphite Stabilizers, Thioester Stabilizers, and the like. Some other examples for additives may include: Orotic acid, Nicotinic acid, Boron Nitride, Talc, Pentaerythritol, Calcium Carbonate, and the like.

[0040] In some embodiments, the composition may include a crosslinker, for example, peroxides, selected based on their ability to efficiently generate free radicals, facilitating the crosslinking process to enhance the mechanical and thermal properties of PHAs. Somenonlimiting examples for such peroxides may include, Dicumyl peroxide, organic dialkyl peroxide, Benzoyl Peroxide, Di-tert-butyl Peroxide, 2,5-Dimethyl-2,5-di(tert- butylperoxy)hexane, t-Butyl Peroxybenzoate, t-Butyl Cumyl Peroxide, and the like.

[0041] Reference is now made to Fig. 1 which is a flowchart of the method of making a biodegradable polymeric composition, according to some embodiments of the invention. In step 10 the method may include melt- mixing a mixture comprising the composition according to any one of the embodiments disclosed herein above. For example, step 10 may include melt-mixing the following mixture, between 5 to 80 wt.% of an amorphous PolyHydroxyAlkanoate (PHA) characterized by a Tg of between —20 to 0 °C, between 15 to 95 wt.% of a first semi-crystalline PHA characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C, and between 1 to 15 wt.% plasticizer. The meltmixing may be conducted at a temperature of between 120-220 °C, for example, inside an extruder.

[0042] In some embodiments, the method may include adding to the mixture between 5 to 35 wt.% of a second semi-crystalline PHA, and wherein the first semi-crystalline PHA is characterized by a melting point of between 130 to 200 °C, and the second semi-crystalline PHA is characterized by a melting point of between 140 to 170 °C.

[0043] In some embodiments, the method may further include adding to the mixture a second amorphous PHA, different from the first amorphous PHA, and wherein the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%.

[0044] In step 20, the method may include shaping the molten mixture, using any suitable method. For example, the molten composition may be shaped using extruding, casting, filament drawing, 3D printing, pelletizing, injection molding, compression molding and the like.

[0045] In some embodiments, steps 10 and 20 are done continuously. For example, the mixture may be provided continuously to an extruder to be extruded.

[0046] In some embodiments, steps 10 and 20 are conducted in a batch. Therefore, a predetermined amount of mixture may be mixed at a mixer to be processed in a batch process, such as, casting.

[0047] Various embodiments and aspects of the present invention as delineated hereinabove and as claimed in the claims section below find experimental support in the following examples.EXAMPLESExample 1

[0048] Several compositions according to embodiments of the invention have been tested and their mechanical properties were measured. The experiments studied the effect of various plasticizers on the mechanical properties and formability. The compositions included 70 wt.% semi-crystalline PHA, 25 wt.% amorphous PHA, and 5 wt.% of different plasticizers. The table in Fig. 2 summarizes the results. As shown in Table in Fig. 2 using Jojoba oil, may result in an injectable molten mixture. The tensile properties were measured according to ISO 527, and the impact resistance according to Izod Pendulum Impact Resistance of Plastics, ASTM D 256, 7.5 J. The best composition was composition D that had the highest modulus of elasticity, together with the highest elongation at break and the best impact resistance.

[0049] The plasticizer of composition D was selected for studying the influence of various amounts and types of PHs.Example 2

[0050] Reference is now made to Fig. 3 which includes a table showing additional compositions according to some embodiments of the invention and their mechanical properties. Composition I included only semi-crystalline PHA and has a very poor elongation and impact resistance. Compositions II, III and IV included semi-crystalline PHA wt.% and amorphous PHA with (III, IV) and without (II) plasticizer, showing the positive effect the plasticizer has on the elongation and impact resistance. Composition V included two types of semi-crystalline PHA, the amorphous PHA and the plasticizer, showing the highest elongation at break together with good impact resistance, however with a lower tensile module.Example 3

[0051] Reference is now made to Fig. 4 which includes a table showing additional compositions according to some embodiments of the invention and their mechanical properties. Compositions Cl to CIO vary in the amounts of semi-crystalline PHA wt.%, amorphous PHA wt.%, PLA and plasticizer. The plasticizer was Isosorbide diester or ESBO. As shown in composition Cl, C2, and C3, all compositions having 5 wt.% plasticizer with or without PLA showed high elongation at break % and were not broken. The PLA addition increased the elongation at break % by about 15 %. C9 and CIO showed similar behavior although having lower elongation at break % due to the lower amount of amorphous PHA. All other compositions, with or without PLA having 0 or 3 wt.% plasticizers completely broke.Example 4

[0052] Reference is now made to Eig. 5 which includes a table showing additional compositions according to some embodiments of the invention and their mechanical properties. Compositions Bl to BIO vary in the amounts of semi-crystalline PHA wt.%, amorphous PHA wt.%, PLA (either semicrystalline or amorphuse) and plasticizer. The plasticizer was Isosorbide diester or ESBO. As shown in the table in Eig. 5 the best compositions B9 and BIO did not break.

[0053] Erom the tables in Figs. 4 and 5 one can see that the addition of PLA to the composition in minor amounts increases the elongation at break %, however the influence on the impact resistance is minor in comparison to the influence of the amount amorphous PHA on both the elongation at break % and the impact resistance. Increasing the amount of PLA had only minor influence on the mechanical properties, as shown in compositions C8- C10 of the table in Fig. 4.

[0054] The examples show the potential of PHA-based compositions having a combined amorphous and semi-crystalline PHA and a plasticizer for producing articles.General

[0055] As used herein the term “about” refers to ± 10 %.

[0056] The terms "comprises", "comprising", "includes", "including", “having” and their conjugates mean "including but not limited to".

[0057] The term “consisting of means “including and limited to”.

[0058] The term "consisting essentially of" means that the composition, method or structure may include additional ingredients, steps and / or parts, but only if the additional ingredients, steps and / or parts do not materially alter the basic and novel characteristics of the claimed composition, method or structure.

[0059] The word “exemplary” is used herein to mean “serving as an example, instance or illustration”. Any embodiment described as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments and / or to exclude the incorporation of features from other embodiments.

[0060] The word “optionally” is used herein to mean “is provided in some embodiments and not provided in other embodiments”. Any particular embodiment of the invention may include a plurality of “optional” features unless such features conflict.

[0061] As used herein, the singular form "a", "an" and "the" include plural references unless the context clearly dictates otherwise. For example, the term "a compound" or "at least one compound" may include a plurality of compounds, including mixtures thereof.

[0062] As used herein, the term “substantially” refers to at least 80%, at least 85%, at least 90%, at least 92%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, including any range or value therebetween.

[0063] As used herein, the term “enhance” including any grammatical forms thereof, refers to least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 100%, between 100 and 200%, between 200 and 300%, between 300 and 500%, between 500 and 1000%, between 1000 and 10000% including any range between, compared to a control.

[0064] Throughout this application, various embodiments of this invention may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0065] Whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range. The phrases “ranging / ranges between” a first indicate number and a second indicate number and “ranging / ranges from” a first indicate number “to” a second indicate number are used herein interchangeably and are meant to include the first and second indicated numbers and all the fractional and integral numerals therebetween.

[0066] As used herein the term "method" refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of the chemical, pharmacological, biological, biochemical and medical arts.

[0067] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination or as suitable in any other described embodiment of the invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperative without those elements.

Claims

CLAIMS1. A biodegradable polymeric composition, comprising:15 to 94 wt.% of a first semi-crystalline PolyHydroxyAlkanoate (PHA) characterized by Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C ;5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to 0 °C;0 to 15 wt.% Polylactic acid (PLA); and1 to 15 wt.% plasticizer.

2. The biodegradable polymeric composition of claim 1, further comprising:5 to 35 wt.% of a second semi-crystalline PHA, and wherein the first semicrystalline PHA is characterized by a melting point of between 130 to 200 °C, and the second semi-crystalline PHA is characterized by a melting point of between 140 to 180 °C.

3. The biodegradable polymeric composition of claim 1 or claim 2, further comprising a second amorphous PHA, different from the first amorphous PHA, and wherein the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%.

4. The biodegradable polymeric composition of any one of claims 1 to 3, wherein the first amorphous PHA is selected from Poly(3-hydroxybutyrate-co-4- hydroxybutyrate) (PH3B4HB), Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PH3BHHx), Poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (PHBO), homopolymers, and any copolymers thereof.

5. The biodegradable polymeric composition of any one of claims 1 to 4, wherein the first semi-crystalline PHA is selected from: Poly(3 -hydroxybutyrate) (PHB), Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), Poly(3 -Hydroxy valerate) (PH3B), Poly(3-hydroxyvalerate) (PHV), Poly(3 -hydroxyhexanoate) (PHHex), Poly(4-hydroxybutyrate) (P(4HB)), Poly(5-hydroxyvalerate) (P(5HV)) Poly(3- hydroxypropionate) (PHP), Poly(3-hydroxybutanoates) (PHB), Poly(3- hydroxyoctanoate) (PHO), Poly(3-hydroxydecanoate) PHD, and any copolymer thereof.

6. The biodegradable polymeric composition of any one of claims 1 to 5, wherein the plasticizer is selected from, Acetyl-tributyl-citrate (ATBC), Poly(ethylene glycol) (PEG), Epoxidized Soybean Oil (ESBO), Jojoba oil, Glycerol, Sorbitol, Glycerol ester, Isosorbide diester, and polymeric plasticizers.

7. The biodegradable polymeric composition of any one of claims 1 to 6, further comprising one or more additives, selected from: ultraviolet (UV) absorber, UV reflector, pigment, stabilizer, dyes, oxidation stabilizer, thermal stabilizer, degradation or decomposition inhibitors or promoters, mold release agent, nucleating agents, mineral fillers, carbon based fillers and reinforcing agents, glass based fillers and reinforcing agents, fire or flame inhibitors suppressors, thickening agents, additional modifying polymers such as impact modifiers, and stiffeners.

8. An article comprising the composition of any one of claims 1 to 7.

9. A method of making a biodegradable polymeric composition, comprising: melt mixing at 120-220 C, a mixture comprising:15 to 94 wt.% of a first semi-crystalline PolyHydroxyAlkanoate (PHA) characterized by a Tg of between -10 to 10 °C and a melting point of between 120 to 220 °C ;5 to 80 wt.% of a first amorphous PHA characterized by a Tg of between -20 to -0 °C;0 to 15 wt.% Polylactic acid (PLA); and1 to 15 wt.% plasticizer; and shaping the molten mixture.

10. The method of claim 9, where in shaping comprises, at least one of, extruding, casting, filament drawing, 3D printing, pelletizing, injection molding, and compression molding.

11. The method of claim 9 or claim 10, wherein the melt mixing is done continuously and comprises a continuous provision of the mixture.

12. The method of claim 9, wherein shaping the molten mixture is done continuously.

13. The method of claim 9 or claim 12, wherein the melt mixing and the shaping of the molten mixture is done in batch.

14. The method of any one of claims 9 to 13, further comprising adding to the mixture between 5 to 35 wt.% of a second semi-crystalline PHA, and wherein the first semi-crystalline PHA is characterized by a melting point of between 130 to 200 °C, and the second semi-crystalline PHA is characterized by a melting point of between 140 to 170 °C.

15. The method of any one of claims 9 to 14, further comprising adding to the mixture a second amorphous PHA, different from the first amorphous PHA, and wherein the total amount of both the first amorphous PHA and the second amorphous PHA is between 5 to 80 wt.%.

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