Biodegradable copolymer composition

Abstract

Disclosed herein are biodegradable copolymer compositions consisting essentially of a polyethylene terephthalate (PET) component and a polycondensation component, the polycondensation component is selected from the group consisting of a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, and a branched aliphatic diol or diamine having 3 to 12 carbon atoms. An aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modifier thereof, wherein the molar ratio of PET to the polycondensation component ranges from 1: 4 to 4: 1.

Description

Technical Field

[0001] The present invention relates to biodegradable copolymer compositions and methods for making the same. Background Art

[0002] Plastics and rubbers are industrially produced on a large scale and are widely used in daily life and in the industrial field at the same time, and their usage has greatly increased. These synthetic polymer materials are used for these various applications due to their characteristic characteristics including low cost, easy processing and high mechanical strength to density ratio. It is expected that products containing these plastics and rubbers will withstand natural forces and wear from their designated uses. Since most polymer materials are developed for improved mechanical properties and durability, they also maintain their original shape and characteristics even after their service life ends. Therefore, many of these types of materials and products will not decompose naturally, and it is believed that they will cause some environmental problems. The solution to these problems not only involves the simple recycling of plastics, but also biodegradable polymer materials form part of the solution, which can be degraded into small molecules by microorganisms in sunlight, water or soil. It is often overlooked that for many plastic and rubber applications that are worn (the microplastics formed spread in the environment and can no longer be recycled by normal industrial means), degradability is a good strategy. The controlled degradation of such microplastics is becoming more and more important and attractive to achieve a leap to a new plastic economy.

[0003] Therefore, there is a growing need for materials, products and methods related to plastic or rubber materials that can biodegrade in natural environments. Such materials, products and methods are described herein. Summary of the invention

[0004] Therefore, in a first aspect, the present invention provides a biodegradable copolymer composition comprising a polyethylene terephthalate (PET) component and a condensation polymerization component, wherein the condensation polymerization component is selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof, wherein the molar ratio of PET to the condensation polymerization component ranges from 1:4 to 4:1.

[0005] In a specific embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a condensation polymerization component, wherein the condensation polymerization component is selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof, wherein the molar ratio of PET to the condensation polymerization component ranges from 1:4 to 4:1.

[0006] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides:

[0007] the polycondensation component is a linear aliphatic diol or diamine selected from the group consisting of 1,2-ethanediol, 1,3-propylenediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine and / or 1,12-dodecanediamine;

[0008] The polycondensation component is a linear aliphatic dicarboxylic acid selected from pimelic acid, suberic acid, azelaic acid and / or sebacic acid;

[0009] the polycondensation component is a branched aliphatic diol or diamine selected from the group consisting of alkylated or arylated 1,2-ethanediol, 1,3-propylenediol, 1,4-butylenediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and / or 1,10-decanediamine;

[0010] The polycondensation component is a branched aliphatic dicarboxylic acid selected from the group consisting of alkylated malonic acid, alkylated succinic acid, alkylated glutaric acid, alkylated adipic acid, alkylated pimelic acid, alkylated suberic acid, alkylated azelaic acid, alkylated sebacic acid, alkylated undecanedioic acid, alkylated dodecanedioic acid, alkylated tridecanedioic acid, alkylated hexadecanedioic acid and / or dimerized fatty diacids;

[0011] The polycondensation component is an aliphatic hydroxy acid selected from the group consisting of 2-hydroxy-propionic acid, 3-hydroxy-propionic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 3-hydroxy-valeric acid, 4-hydroxy-valeric acid and / or 5-hydroxy-valeric acid; and / or;

[0012] The polycondensation component is an aliphatic amino acid selected from the group consisting of 2-amino-propionic acid, 3-amino-propionic acid, 3-amino-butyric acid, 4-amino-butyric acid, 4-amino-pentanoic acid, 5-amino-pentanoic acid, 6-amino-hexanoic acid, 9-amino-stearic acid, 9-aminomethyl-stearic acid, 10-amino-stearic acid, 10-aminomethyl-stearic acid, 11-amino-undecanoic acid, 12-amino-dodecanoic acid and / or 12-amino-stearic acid.

[0013] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides that the PET component is a PET component derived from a PET post-consumer waste source.

[0014] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides for a molar ratio of PET to polycondensation component ranging from 1:3 to 3:1, more preferably from 1:2 to 2:1, and more preferably in the range of about 1:1.

[0015] In another aspect, the present invention relates to a method for preparing a biodegradable copolymer composition as disclosed herein, comprising the steps of:

[0016] (a) preparing PET prepolymer;

[0017] (b) preparing a polycondensation prepolymer selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof;

[0018] (c) polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to the polycondensation component ranging from 1:4 to 4:1.

[0019] In a particular embodiment, the process as disclosed herein provides that step (a) occurs by an esterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol or by a depolymerization reaction of PET to an oligomeric PET prepolymer.

[0020] In a particular embodiment, the methods as disclosed herein provide that step (b) occurs by an esterification reaction.

[0021] In a particular embodiment, the method as disclosed herein provides that step (c) comprises the following steps:

[0022] (c1) melting the PET prepolymer at a temperature 10° C. to 30° C. above its softening point under inert conditions;

[0023] (c2) adding a polycondensation prepolymer to the molten PET component; and

[0024] (c3) reacting the PET component with a polycondensation prepolymer in the absence or presence of a catalyst.

[0025] In a particular embodiment, the process as disclosed herein provides that step (c3) occurs in the presence of a catalyst, and wherein the catalyst is zinc acetate or titanium (IV) butoxide.

[0026] In a particular embodiment, the process as disclosed herein provides for a molar ratio of PET to polycondensation component in the range of 1:3 to 3:1, more preferably in the range of 1:2 to 2:1, and more preferably in the range of about 1:1.

[0027] In another aspect, the present invention relates to products comprising the biodegradable copolymer composition as disclosed herein. In particular, the products are rubber-like and soft-touch articles in the automotive industry, consumer products, medical devices, building and construction, and outdoor equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Respiration evolution of LM polymers in soil at 30 °C compared with starch; average of 3 replicates; horizontal lines indicate the levels of readily biodegradable compounds in the polymers. DETAILED DESCRIPTION

[0029] Unless otherwise defined, all terms (including technical and scientific terms) used in disclosing the present invention have the meanings commonly understood by ordinary technicians in the field to which the present invention belongs. By way of further guidance, term definitions are included to better understand the teachings of the present invention.

[0030] All references cited in this specification are hereby deemed to be incorporated by reference in their entirety.

[0031] As used herein, the following terms have the following meanings:

[0032] Unless the context clearly dictates otherwise, as used herein, unmodified nouns refer to both singular and plural references.As an example, "a compartment" refers to one or more than one compartment.

[0033] "About" as used herein in reference to a measurable value such as a parameter, amount, length of time, etc., is meant to encompass the specified value and variations of + / -20% or less, particularly + / -10% or less, more particularly + / -5% or less, even more particularly + / -1% or less, and still more particularly + / -0.1% or less relative to the specified value, as long as such variations are suitable for implementation in the disclosed invention. However, it is to be understood that the value referred to by the modifier "about" itself is also expressly disclosed.

[0034] As used herein, "comprise", "comprising", "comprises" and "comprised of" are synonymous with "include", "including", "includes" or "contain", "containing", "contains", and are inclusive or open-ended terms that specify the presence of what follows it (e.g., components) without excluding or excluding the presence of additional non-recited components, features, elements, members, steps known in the art or disclosed herein.

[0035] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints.

[0036] Unless otherwise defined, here and throughout the specification, the expression "weight percent", "%wt" or "weight %" refers to the relative weight of each component based on the total weight of the formulation.

[0037] In view of the high demand for plastic or rubber materials that can be biodegraded in the natural environment, the present inventors have found that after combining a polyethylene terephthalate (PET) component and a specific polycondensation component in a specific range, a biodegradable copolymer composition with a typical elastomeric / rubber-like behavior is obtained. Depending on the type of polycondensation component used, certain properties, such as softness, can be further adjusted.

[0038] Therefore, in a first aspect, the present invention relates to a biodegradable copolymer composition comprising a polyethylene terephthalate (PET) component and a condensation polymerization component, wherein the condensation polymerization component is selected from linear aliphatic diols or diamines having 3 to 12 carbon atoms, linear aliphatic dicarboxylic acids having 7 to 10 carbon atoms, branched aliphatic diols or diamines having 3 to 12 carbon atoms, branched aliphatic dicarboxylic acids having 3 to 32 carbon atoms, aliphatic hydroxy acids having 2 to 5 carbon atoms, aliphatic amino acids having 2 to 20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to the condensation polymerization component ranges from 1:4 to 4:1.

[0039] In a specific embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a condensation polymerization component, wherein the condensation polymerization component is selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof, wherein the molar ratio of PET to the condensation polymerization component ranges from 1:4 to 4:1.

[0040] As used herein, the term "biodegradable composition" and similar terms refer to biodegradable materials / compositions. Biodegradable compositions generally refer to (co)polymers that have almost the same physical properties as general-purpose plastics in their use as materials, however, after disposal, those polymers are rapidly decomposed and converted into valuable products by natural conditions (such as microorganisms, mainly bacteria and fungi, temperature, moisture and light) in natural environments (such as activated sludge, soil, compost and water), which ultimately decompose into carbon dioxide and water. The degree of biodegradation can generally be determined using the biodegradation rate, which refers to the time it takes for a material to biodegrade to a specific extent. For example, a material that biodegrades 30% in 20 days has a higher biodegradation rate than a material that biodegrades 10% in 20 days.

[0041] As used herein, the term "copolymer composition" refers to a polymer composition, wherein the polymer is a copolymer obtained by copolymerization comprising two monomers. In addition, as used herein, "plastic article" refers to a copolymer composition processed into a film, sheet, fiber, foam, molded article, nonwoven fabric, elastomer or adhesive. As used herein, the copolymer as referred to herein is provided with a polyethylene terephthalate (PET) component and a polycondensation component.

[0042] In a particular embodiment, the copolymer is a linear copolymer (eg, alternating copolymers, random copolymers, statistical copolymers, or block or multiblock copolymers), or a branched copolymer (eg, graft copolymers, star copolymers with branched copolymers of different structures).

[0043] In particular, the polycondensation component is selected from linear aliphatic diols or diamines having 3 to 12 carbon atoms, linear aliphatic dicarboxylic acids having 7 to 10 carbon atoms, branched aliphatic diols or diamines having 3 to 12 carbon atoms, branched aliphatic dicarboxylic acids having 3 to 32 carbon atoms, aliphatic hydroxy acids having 2 to 5 carbon atoms, aliphatic amino acids having 2 to 20 carbon atoms and / or acetylated modifications thereof.

[0044] More particularly, the polycondensation component is a linear aliphatic diol or diamine having 3 to 12 carbon atoms, preferably 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. As referred to herein, the term "aliphatic" refers to an organic compound containing carbon and hydrogen linked together in a straight chain (linear), branched chain or non-aromatic ring. As referred to herein, "aliphatic diol" refers to an aliphatic compound containing two hydroxyl (-OH) groups. As referred to herein, "aliphatic diamine" refers to an aliphatic compound containing two amino groups.

[0045] More particularly, the polycondensation component is a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, preferably 7, 8, 9 or 10 carbon atoms.As referred to herein, "aliphatic dicarboxylic acid" refers to an aliphatic compound containing two carboxyl (-COOH) groups.

[0046] More particularly, the polycondensation component is a branched aliphatic diol or diamine having 3 to 12 carbon atoms, preferably 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and / or an acetylated modification thereof, the acetylated modification being preferably selected from acetylated polyols such as sorbitol.

[0047] More particularly, the polycondensation component is a branched aliphatic dicarboxylic acid having 3 to 36 carbon atoms, preferably 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32 carbon atoms, and / or an acetylated modification thereof, the acetylated modification being preferably selected from acetylated dicarboxylates such as tartaric acid and galactaric acid.

[0048] More specifically, the polycondensation component is an aliphatic hydroxy acid and / or an acetylated modification thereof having 2 to 5 carbon atoms, preferably 2, 3, 4 or 5 carbon atoms. As referred to herein, "aliphatic hydroxy acid" refers to a hydroxy acid containing an aliphatic side chain functional group.

[0049] More particularly, the polycondensation component is an aliphatic amino acid and / or acetylated modification thereof having 2 to 20 carbon atoms, preferably 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, the acetylated modification being preferably selected from acetylated amino acids such as dihydroxy-lysine. As referred to herein, "aliphatic amino acid" refers to an aliphatic amino acid containing a side chain functional group.

[0050] In a particular embodiment, the molar ratio of PET to the polycondensation component ranges from 1:4 to 4:1, more particularly from 1:3 to 3:1, more particularly from 1:2 to 2:1, and more particularly, the molar ratio of PET to the polycondensation component is about 1:1.

[0051] In another specific embodiment, the copolymer further comprises amide hydrogen bonding sites.

[0052] In a specific embodiment, the biodegradable copolymer composition as disclosed herein provides that the polycondensation component is a linear aliphatic diol or diamine selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and / or 1,10-decanediamine. In a specific embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, wherein the polycondensation component is 1,5-pentanediol and / or 1,6-hexanediol.

[0053] In a specific embodiment, the biodegradable copolymer composition as disclosed herein provides that the polycondensation component is a linear aliphatic dicarboxylic acid selected from pimelic acid, suberic acid, azelaic acid and / or sebacic acid. In a specific embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, wherein the polycondensation component is azelaic acid and / or sebacic acid.

[0054] In a specific embodiment, the biodegradable copolymer composition as disclosed herein provides that the polycondensation component is a branched aliphatic diol or diamine selected from the group consisting of alkylated or arylated 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and / or 1,10-decanediamine. In a particular embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, wherein the polycondensation component is an alkylated or arylated, preferably 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 1-phenylethane-1,2-diol and / or 2-methyl-1,5-pentanediamine.

[0055] In a specific embodiment, the biodegradable copolymer composition as disclosed herein provides that the polycondensation component is a branched aliphatic dicarboxylic acid selected from the group consisting of alkylated malonic acid, alkylated succinic acid, alkylated glutaric acid, alkylated adipic acid, alkylated pimelic acid, alkylated suberic acid, alkylated azelaic acid, alkylated sebacic acid, alkylated undecane dioic acid, alkylated dodecanedioic acid, alkylated tridecanedioic acid, alkylated hexadecanedioic acid and / or dimerized fatty diacids. As referred to herein, the term "dimerized fatty diacid" (also referred to as dimerized fatty acid) is well known in the art and refers to the dimerization product of monounsaturated fatty acids or polyunsaturated fatty acids and / or their esters. In a specific embodiment, the biodegradable copolymer composition as disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, wherein the polycondensation component is an alkylated or arylated succinic acid, such as 2-methyl-succinate.

[0056] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides that the condensation component is an aliphatic hydroxy acid selected from the group consisting of 2-hydroxy-propionic acid, 3-hydroxy-propionic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 3-hydroxy-valeric acid, 4-hydroxy-valeric acid and / or 5-hydroxy-valeric acid.

[0057] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides that the condensation component is an aliphatic amino acid selected from the group consisting of 2-amino-propionic acid, 3-amino-propionic acid, 3-amino-butyric acid, 4-amino-butyric acid, 4-amino-pentanoic acid, 5-amino-pentanoic acid, 6-amino-hexanoic acid, 9-amino-stearic acid, 9-aminomethyl-stearic acid, 10-amino-stearic acid, 10-aminomethyl-stearic acid, 11-amino-undecanoic acid, 12-amino-dodecanoic acid and / or 12-amino-stearic acid.

[0058] In a particular embodiment, the biodegradable copolymer compositions as disclosed herein provide that the PET component is derived from PET waste, such as PET post-consumer waste. During the recycling of PET into the materials of the present invention, the PET waste is washed, crushed, dried and further recycled using commonly known recycling and chain extension techniques, and ultimately chain extended.

[0059] In a particular embodiment, the biodegradable copolymer composition as disclosed herein is characterized in that the molar ratio of PET to the polycondensation component ranges from 1:3 to 3:1, more preferably from 1:2 to 2:1, and more preferably in the range of about 1:1.

[0060] In a particular embodiment, the biodegradable copolymer composition as disclosed herein provides that the polymer is characterized by a Mw greater than 10 kDa, more preferably greater than 20 kDa, and most preferably greater than 30 kDa.

[0061] In another aspect, disclosed herein is a method for preparing a biodegradable copolymer composition as disclosed herein, comprising the steps of:

[0062] (a) preparing PET prepolymer;

[0063] (b) preparing a polycondensation prepolymer selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof;

[0064] (c) polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to the polycondensation component ranging from 1:4 to 4:1.

[0065] In a particular embodiment, the copolymer is a linear copolymer (eg, alternating copolymers, random copolymers, statistical copolymers, or block or segmented copolymers), or a branched copolymer (eg, graft copolymers, star copolymers with branched copolymers of different structures).

[0066] In particular, the polycondensation component is selected from linear aliphatic diols or diamines having 3 to 12 carbon atoms, linear aliphatic dicarboxylic acids having 7 to 10 carbon atoms, branched aliphatic diols or diamines having 3 to 12 carbon atoms, branched aliphatic dicarboxylic acids having 3 to 32 carbon atoms, aliphatic hydroxy acids having 2 to 5 carbon atoms, aliphatic amino acids having 2 to 20 carbon atoms and / or acetylated modifications thereof.

[0067] In a particular embodiment, the process as disclosed herein provides that step (a) occurs by an esterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol or by a depolymerization reaction of PET to an oligomeric PET prepolymer.

[0068] In a particular embodiment, the method as disclosed herein provides that step (b) occurs by polycondensation. In particular, the polycondensation polymer achieves a chain length that allows for entanglement structures. More particularly, the polymer is characterized by a Mw greater than 10 kDa, more preferably greater than 20 kDa, and most preferably greater than 30 kDa.

[0069] In a particular embodiment, the method as disclosed herein provides that step (c) comprises the following steps:

[0070] (c1) melting the PET prepolymer at a temperature 10° C. to 30° C. above its softening point under inert conditions;

[0071] (c2) adding a polycondensation prepolymer to the molten PET component; and

[0072] (c3) reacting the PET component with a polycondensation prepolymer in the absence or presence of a catalyst.

[0073] Particularly, step (c1) is carried out under N2 atmosphere at a temperature of 230°C to 260°C, more particularly, at a temperature of about 245°C.

[0074] In a particular embodiment, the process as disclosed herein provides that wherein step (c3) occurs in the presence of a catalyst, and wherein the catalyst is zinc acetate or titanium (IV) butoxide.

[0075] In a particular embodiment, the process as disclosed herein provides that step (c3) occurs in the presence of a catalyst, and wherein the catalyst is Ti(BuO) 4. More particularly, step (c3) is performed at a temperature of 220° C. to 250° C. for a period of 3 to 8 hours, more particularly, at a temperature of about 235° C. for a period of 3 to 8 hours.

[0076] In a particular embodiment, the process as disclosed herein provides for a molar ratio of PET to polycondensation component in the range of 1:3 to 3:1, more preferably in the range of 1:2 to 2:1, and more preferably in the range of about 1:1.

[0077] In another aspect, the present invention relates to products comprising the biodegradable copolymer composition as disclosed herein. In particular, the products are rubber-like and soft-touch articles in the automotive industry (hoses under the hood, buttons, dashboard panels), consumer goods (drills, shaving sets, kitchen tools, clock wristbands), medical devices, building and construction (window linings, insulation panels) and outdoor equipment (shock absorbers, soles, buttons and strips on backpacks).

[0078] Example

[0079] Example 1

[0080] The biodegradable copolymer composition (LM092) according to the present invention is prepared by preparing a poly(decene methyl succinate) prepolymer by charging 2-methylsuccinic acid (0.66 mol) and 1,10-decanediol (0.69 mol) into a reactor, heating the mixture to 135°C under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 200°C to 225°C for esterification reaction while continuously removing water for 3 hours (until no more water is removed). A PET prepolymer is prepared by charging terephthalic acid (1 mol) and ethylene glycol (1.3 mol) into a reactor, and performing an esterification reaction at 190°C under a pressure of 5 MPa for 3 to 4 hours.

[0081] The prepared prepolymer was polycondensed into copolyester by charging the PET prepolymer into a flask and melting it at 245°C under N2 flow and stirring, adding the polycondensate prepolymer to the flask, adding Ti(BuO)4 catalyst after 10 minutes, and reacting the prepared mixture at 235°C under 0.5 mmHg vacuum for 3 to 8 hours.

[0082] Another biodegradable copolymer composition (LM086) according to the present invention was prepared by preparing a poly(decene methyl succinate) prepolymer by charging succinic acid (0.66 mol) and 1,10-decanediol (0.69 mol) into a reactor, heating the mixture to 135°C under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 200°C to 225°C for esterification reaction while continuously removing water for 3 hours (until no more water is removed). A PET prepolymer was prepared by charging terephthalic acid (1 mol) and ethylene glycol (1.3 mol) into a reactor and conducting an esterification reaction at 190°C under a pressure of 5 MPa for 3 to 4 hours.

[0083] The prepared prepolymer was polycondensed into copolyester by charging the PET prepolymer into a flask and melting it at 245°C under N2 flow and stirring, adding the polycondensate prepolymer to the flask, adding Ti(BuO)4 catalyst after 10 minutes, and reacting the prepared mixture at 235°C under 0.5 mmHg vacuum for 3 to 8 hours.

[0084] Table 1 provides the properties of the copolymers prepared.

[0085]

[0086] The biodegradation of the LM086 and LM092 compositions was measured under soil conditions using the ASTM D5988-18 test method for biodegradation of plastics.

[0087] Polymer LM086 biodegraded an average of 15% (range 10% to 20%) over 19 weeks, after which biodegradation appeared to cease. Polymer LM092 degraded an average of 46% (range 38% to 56%) over a 6-month period, and degradation is still ongoing. This 46% average biodegradability is close to the biodegradability of starch (approximately 57%). Figure 1 As can be seen in Figure 1, the biodegradation of LM092 is very similar to that of starch in replicate 1. The soil respiration test showed that polymer LM092 is highly biodegradable and its biodegradability is close to that of starch under the same conditions.

[0088] Example 2

[0089] According to the polycondensation method in Example 1, the biodegradable copolymer composition according to the present invention was manufactured by heating PET and poly(butylene succinate-co-butylene adipate) prepolymer.

[0090] Samples A1 and A2 are copolymers that have been reacted from a 2:3 prepolymer of PET:PBSA at 280°C to 290°C for 1 hour and 1.65 hours, respectively. Samples B1 and B2 are copolymers that have been reacted from a 1:1 prepolymer of PET:PBSA at 280°C to 290°C for 0 hour and 1.5 hour, respectively.

[0091] Table 2 provides the properties of the copolymers prepared.

[0092]

[0093] From the Shore A hardness parameter it can be concluded that the prepared copolymer composition has a distinct elastomeric thermoplastic behavior.

[0094] Example 3

[0095] The biodegradable copolymer composition (LMP03) according to the present invention was made by preparing a poly(neopentyl sebacate) prepolymer by charging sebacic acid (0.66 mol) and neopentyl glycol (0.69 mol) into a reactor, heating the mixture to 135°C under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 200°C to 225°C for esterification reaction while continuously removing water for 3 hours (until no more water was removed). The PET prepolymer was prepared according to Example 1.

[0096] The prepared prepolymer was polycondensed into copolyester by charging the PET prepolymer into a flask and melting it at 245°C under N2 flow and stirring, adding the polycondensate prepolymer to the flask, adding Ti(BuO)4 catalyst after 10 minutes, and reacting the prepared mixture at 235°C under 0.5 mmHg vacuum for 3 to 8 hours.

[0097] Example 4

[0098] The biodegradable copolymer composition (LMP04) according to the present invention was prepared by preparing a poly(6-hydroxy-hexanoate) prepolymer by charging 1 mol of 6-caprolactone and 0.1 mol of decanol into a reactor, heating the mixture to 150° C. under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 200° C. for 30 minutes. The PET prepolymer was prepared according to Example 1.

[0099] The prepared prepolymer was equimolarly polycondensed into a copolyester by charging a PET prepolymer into a flask and melting it at 245° C. under a N 2 flow and stirring, adding a poly(6-hydroxy-hexanoate) prepolymer into the flask, adding 20 mol % of succinic anhydride, adding 250 ppm of Ti(BuO) 4 catalyst after 10 minutes, and reacting the prepared mixture at 235° C. under a vacuum of 0.5 mmHg for 3 to 8 hours.

[0100] Example 5

[0101] The biodegradable copolymer composition (LMP05) according to the present invention was manufactured by preparing a poly(6-amino-caproate) prepolymer by charging 1.0 mol of 6-amino-caproic acid and 0.05 mol of acetic acid into a reactor, heating the mixture to 180° C. under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 260° C. for amidation while continuously removing water for 8 hours. The PET prepolymer was prepared according to Example 1.

[0102] The prepared prepolymer was subjected to equimolar polycondensation by charging a PET prepolymer into a flask and melting it at 245° C. under a N 2 flow and stirring, adding a poly(6-amino-caproate) prepolymer into the flask, adding 20 mol % of adipic anhydride, adding 250 ppm of a Ti(BuO) 4 catalyst after 10 minutes, and reacting the prepared mixture at 235° C. under a vacuum of 0.5 mmHg for 3 to 8 hours.

Claims

1. A biodegradable copolymer composition consisting essentially of a polyethylene terephthalate (PET) component and a polycondensation component selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to the polycondensation component ranges from 1:4 to 4:

1.

2. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is a linear aliphatic diol or diamine selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and / or 1,10-decanediamine.

3. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is a linear aliphatic dicarboxylic acid selected from pimelic acid, suberic acid, azelaic acid and / or sebacic acid.

4. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is a branched aliphatic diol or diamine selected from the group consisting of alkylated or arylated 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine and / or 1,10-decanediamine.

5. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is a branched aliphatic dicarboxylic acid selected from the group consisting of alkylated malonic acid, alkylated succinic acid, alkylated glutaric acid, alkylated adipic acid, alkylated pimelic acid, alkylated suberic acid, alkylated azelaic acid, alkylated sebacic acid, alkylated undecanedioic acid, alkylated dodecanedioic acid, alkylated tridecanedioic acid, alkylated hexadecanedioic acid and / or dimerized fatty diacids.

6. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is an aliphatic hydroxy acid selected from the group consisting of 2-hydroxy-propionic acid, 3-hydroxy-propionic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 3-hydroxy-valeric acid, 4-hydroxy-valeric acid and / or 5-hydroxy-valeric acid.

7. The biodegradable copolymer composition according to claim 1, wherein the polycondensation component is an aliphatic amino acid selected from the group consisting of 2-amino-propionic acid, 3-amino-propionic acid, 3-amino-butyric acid, 4-amino-butyric acid, 4-amino-pentanoic acid, 5-amino-pentanoic acid, 6-amino-hexanoic acid, 9-amino-stearic acid, 9-aminomethyl-stearic acid, 10-amino-stearic acid, 10-aminomethyl-stearic acid, 11-amino-undecanoic acid, 12-amino-dodecanoic acid and / or 12-amino-stearic acid.

8. The biodegradable copolymer composition according to any one of claims 1 to 7, wherein the PET component is a PET component derived from a PET post-consumer waste source.

9. A method for preparing a biodegradable copolymer composition according to any one of claims 1 to 8, comprising the following steps: (a) preparing PET prepolymer; (b) preparing a polycondensation prepolymer selected from a linear aliphatic diol or diamine having 3 to 12 carbon atoms, a linear aliphatic dicarboxylic acid having 7 to 10 carbon atoms, a branched aliphatic diol or diamine having 3 to 12 carbon atoms, a branched aliphatic dicarboxylic acid having 3 to 32 carbon atoms, an aliphatic hydroxy acid having 2 to 5 carbon atoms, an aliphatic amino acid having 2 to 20 carbon atoms and / or an acetylated modification thereof; (c) polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to the polycondensation component ranging from 1:4 to 4:

1.

10. The process according to claim 9, wherein step (a) occurs by an esterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol or by a depolymerization reaction of PET to an oligomeric PET prepolymer.

11. The process according to claim 9 or 10, wherein step (b) occurs by an esterification reaction.

12. The method according to any one of claims 9 to 11, wherein step (c) comprises the following steps: (c1) melting the PET prepolymer at a temperature 10° C. to 30° C. above its softening point under inert conditions; (c2) adding the polycondensation prepolymer to the molten PET component; as well as (c3) reacting the PET component with the polycondensation prepolymer in the absence or presence of a catalyst.

13. The process of claim 12, wherein step (c3) occurs in the presence of a catalyst, and wherein the catalyst is zinc acetate or titanium (IV) butoxide.

14. The biodegradable copolymer composition according to any one of claims 1 to 8 or the method according to any one of claims 9 to 13, wherein the molar ratio of PET to the polycondensation component ranges from 1:3 to 3:1, more preferably from 1:2 to 2:1, and more preferably in the range of about 1:

1.

15. A product comprising the biodegradable copolymer composition according to any one of claims 1 to 8 or 14, wherein the product is preferably rubber-like and soft-touch articles in the automotive industry, consumer goods, medical devices, building and construction, and outdoor equipment.

Images