Biodegradable compomer composition

Abstract

Disclosed herein is a biodegradable copolymer composition consisting essentially of a polyethylene terephthalate (PET) component and a polycondensation component selected from linear aliphatic diols or diamines having 3-12 carbon atoms, linear aliphatic dicarboxylic acids having 7-10 carbon atoms, branched aliphatic diols or diamines having 3-12 carbon atoms, branched aliphatic dicarboxylic acids having 3-32 carbon atoms, aliphatic hydroxy acids having 2-5 carbon atoms, aliphatic amino acids having 2-20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to polycondensation component ranges between 1:4 to 4:1.

Description

[Technical field]

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

[0002] Plastics and rubber are widely used in daily life and industrial fields, and their usage has increased significantly, while at the same time being mass-produced industrially. These synthetic polymeric materials have been used in these various applications due to their characteristic properties, including low cost, ease of processing, and high ratio of mechanical strength to density. It is desirable for products containing these plastics and rubber to withstand the forces of nature and the wear caused by their designated use. Most polymeric materials have been developed for improved mechanical properties and durability, so that they preserve their original shape and properties even after the end of their useful life. As a result, many of these types of materials and products do not degrade naturally, and they are thought to cause several environmental problems. The solution to these problems includes not only the simple recycling of plastics, but also biodegradable polymeric materials that can be broken down into small molecules by sunlight, water, or microorganisms in the ground, forming part of the solution. What is often overlooked is that degradability is a good strategy for many plastic and rubber applications that wear out, and the microplastics that are formed are dispersed in the environment and can no longer be recycled by normal industrial means. The controlled degradation of such microplastics is becoming increasingly important and attractive for the leap towards a new plastics economy. Summary of the Invention [Problem to be solved by the invention]

[0003] As a result, there is an increasing need for materials, products, and methods relating to plastic or rubber materials that can biodegrade in the natural environment. Such materials, products, and methods are described herein. [Means for solving the problem]

[0004] Thus, in a first aspect, the present invention provides a biodegradable copolymer composition comprising a polyethylene terephthalate (PET) component and a polycondensation component selected from linear aliphatic diols or diamines having 3-12 carbon atoms, linear aliphatic dicarboxylic acids having 7-10 carbon atoms, branched aliphatic diols or diamines having 3-12 carbon atoms, branched aliphatic dicarboxylic acids having 3-32 carbon atoms, aliphatic hydroxy acids having 2-5 carbon atoms, aliphatic amino acids having 2-20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to polycondensation component is in the range of between 1:4 to 4:1.

[0005] In certain embodiments, the biodegradable copolymer composition disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component selected from linear aliphatic diols or diamines having 3-12 carbon atoms, linear aliphatic dicarboxylic acids having 7-10 carbon atoms, branched aliphatic diols or diamines having 3-12 carbon atoms, branched aliphatic dicarboxylic acids having 3-32 carbon atoms, aliphatic hydroxy acids having 2-5 carbon atoms, aliphatic amino acids having 2-20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to polycondensation component ranges between 1:4 to 4:1.

[0006] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide:

[0007] the polycondensation component is a linear aliphatic diol or diamine selected from 1,2-ethanediol, 1,3-propanediol, 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-ethanediamine, 1,3-propanediamine, 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 heptanedioic acid, octanedioic acid, nonanedioic acid and / or decanedioic acid;

[0009] the polycondensation component is a branched aliphatic diol or diamine selected from alkylated or arylated 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 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 chain aliphatic dicarboxylic acid selected from alkylated malonic acid, alkylated succinic acid, alkylated pentanedioic acid, alkylated adipic acid, alkylated heptanedioic acid, alkylated octanedioic acid, alkylated nonanedioic acid, alkylated decanedioic acid, alkylated undecanedioic acid, alkylated dodecanedioic acid, alkylated tridecanedioic acid, alkylated hexadecanedioic acid, and / or dimer fatty diacids;

[0011] the polycondensation component is an aliphatic hydroxy acid selected from 2-hydroxy-propanoic acid, 3-hydroxy-propanoic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 3-hydroxy-pentanoic acid, 4-hydroxy-pentanoic acid, and / or 5-hydroxy-pentanoic acid; and / or

[0012] The polycondensation components are aliphatic amino acids selected from 2-aminopropanoic acid, 3-aminopropanoic acid, 3-aminobutyric acid, 4-aminobutyric acid, 4-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 9-aminostearic acid, 9-aminomethylstearic acid, 10-aminostearic acid, 10-aminomethylstearic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and / or 12-aminostearic acid.

[0013] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide that the PET component is a PET component from a PET post-consumer waste source.

[0014] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide a molar ratio of PET to polycondensation component ranging from between 1:3 to 3:1, more preferably between 1:2 to 2:1, more preferably about 1:1.

[0015] In a further aspect, the present invention provides a method for preparing the biodegradable copolymer composition disclosed herein, comprising: (a) preparing a PET prepolymer; (b) preparing a polycondensation prepolymer 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; (c) polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to polycondensation component ranging between 1:4 and 4:1. and

[0016] In certain embodiments, the methods disclosed herein provide that step (a) occurs by esterification between terephthalic acid or dimethyl terephthalate and ethylene glycol, or by depolymerization of PET into oligomeric PET prepolymers.

[0017] In certain embodiments, the methods disclosed herein provide that step (b) occurs by esterification.

[0018] In certain embodiments, the methods disclosed herein further comprise the step (c) (c1) melting the PET prepolymer under inert conditions at a temperature in the range of 10 to 30° C. above its softening point; (c2) adding a polycondensation prepolymer to the molten PET component; (c3) reacting the PET component with a polycondensation prepolymer in the absence or presence of a catalyst and

[0019] In certain embodiments, the methods disclosed herein provide that step (c3) occurs in the presence of a catalyst, and the catalyst is zinc acetate or titanium (IV) butoxide.

[0020] In certain embodiments, the methods disclosed herein provide for a molar ratio of PET to polycondensation components ranging from between 1:3 to 3:1, more preferably between 1:2 to 2:1, more preferably about 1:1.

[0021] In a further aspect, the present invention relates to articles of manufacture comprising the biodegradable copolymer compositions disclosed herein, particularly rubbery and soft-touch articles in the automotive industry, consumer goods, medical devices, building and construction, and outdoor equipment. [Brief description of the drawings]

[0022] [Figure 1] Stepwise change in respiration of LM polymers in soil at 30 °C compared to starch; average of three replicates; horizontal lines indicate the levels of readily biodegradable compounds in the polymers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Unless otherwise specified, all terms (including technical and scientific terms) used in disclosing the present invention have the meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better appreciate the teachings of the present invention.

[0024] All references cited herein are deemed to be incorporated herein by reference in their entirety.

[0025] As used herein, the following terms have the following meanings: "A," "an," and "the" as used herein refer to both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a compartment" refers to one or more compartments.

[0026] "About," as used herein with reference to a measurable value, e.g., a parameter, amount, duration, etc., is meant to encompass a variation of the specified value and of no more than + / - 20%, particularly no more than + / - 10%, more particularly no more than + / - 5%, even more particularly no more than + / - 1%, and even more particularly no more than + / - 0.1% from the specified value, insofar as such variations are appropriate for the practice of the disclosed invention. However, it should be understood that the value to which the "about" modifier refers is itself specifically and preferably disclosed.

[0027] "Comprise," "comprising," and "comprises," and "comprised of," as used herein, are synonymous with "include," "including," "includes," or "contain," "containing," "contains," and are inclusive or open-ended terms that, for example, specify the presence of following components and do not exclude or preclude the presence of additional, unrecited components, features, elements, materials, steps that are known in the art or disclosed therein.

[0028] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints.

[0029] The expressions "weight percent," "% wt," or "% by weight" throughout this specification, unless otherwise defined, refer to the relative weight of each component based on the total weight of the formulation.

[0030] Considering the high need for plastic or rubber materials that can be biodegraded in the natural environment, the inventors have found that a combination of a polyethylene terephthalate (PET) component and a specific polycondensation component in a specific range results in a biodegradable copolymer composition with typical elastomeric / rubber-like behavior. Depending on the type of polycondensation component used, certain properties, such as flexibility, can be further fine-tuned.

[0031] Thus, in a first aspect, the present invention relates to a biodegradable copolymer composition comprising a polyethylene terephthalate (PET) component and a polycondensation component selected from linear aliphatic diols or diamines having 3-12 carbon atoms, linear aliphatic dicarboxylic acids having 7-10 carbon atoms, branched aliphatic diols or diamines having 3-12 carbon atoms, branched aliphatic dicarboxylic acids having 3-32 carbon atoms, aliphatic hydroxy acids having 2-5 carbon atoms, aliphatic amino acids having 2-20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to polycondensation component ranges between 1:4 and 4:1.

[0032] In certain embodiments, the biodegradable copolymer composition disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component selected from linear aliphatic diols or diamines having 3-12 carbon atoms, linear aliphatic dicarboxylic acids having 7-10 carbon atoms, branched aliphatic diols or diamines having 3-12 carbon atoms, branched aliphatic dicarboxylic acids having 3-32 carbon atoms, aliphatic hydroxy acids having 2-5 carbon atoms, aliphatic amino acids having 2-20 carbon atoms and / or acetylated modifications thereof, wherein the molar ratio of PET to polycondensation component ranges between 1:4 to 4:1.

[0033] As used herein, the term "biodegradable composition" and similar terms refer to materials / compositions that are biodegradable. Biodegradable compositions typically refer to (co)polymers that have similar physical properties as general-purpose plastics in their use as materials, but that, after disposal, are rapidly decomposed into valuable materials and ultimately decomposed into carbon dioxide and water under natural conditions, such as activated sludge, soil, compost, and water, under the influence of microorganisms, mainly bacteria and fungi, temperature, humidity, and light. The extent of biodegradation can generally be determined using the biodegradation rate, which refers to the time it takes for a material to biodegrade to a particular 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.

[0034] As used herein, the term "copolymer composition" refers to a polymer composition in which the polymer is a copolymer comprising two monomers obtained by copolymerization. Additionally, as used herein, "plastic article" refers to a copolymer composition that has been processed into a film, sheet, fiber, foam, molded article, nonwoven, elastomer, or adhesive. As used herein, the copolymer referred to herein provides a polyethylene terephthalate (PET) component and a polycondensation component.

[0035] In certain embodiments, the copolymer is a linear copolymer, e.g., an alternating copolymer, a random copolymer, a statistical copolymer, or a block or segmented copolymer, or a branched copolymer, e.g., a graft copolymer of branched copolymers having different architectures, a branched copolymer of a star copolymer.

[0036] In particular, the polycondensation components are 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.

[0037] More specifically, the polycondensation component is a straight chain 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 bonded 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.

[0038] More specifically, the polycondensation component is a straight chain 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.

[0039] More specifically, the polycondensation components are branched aliphatic diols or diamines having 3 to 12 carbon atoms, preferably 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and / or acetylated modifications thereof, the acetylated modifications being preferably selected from acetylated polyols, e.g., sorbitol.

[0040] More specifically, the polycondensation components are branched chain aliphatic dicarboxylic acids 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 acetylated modifications thereof, the acetylated modifications being preferably selected from acetylated dicarboxylates, such as tartaric acid and galactaric acid.

[0041] More specifically, the polycondensation component is an aliphatic hydroxy acid having 2 to 5 carbon atoms, preferably 2, 3, 4 or 5 carbon atoms, and / or an acetylated modification thereof. As referred to herein, "aliphatic hydroxy acid" refers to a hydroxy acid that contains an aliphatic side chain functional group.

[0042] More specifically, the polycondensed component is an aliphatic amino acid 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, and / or an acetylated modification thereof, the acetylated modification being preferably selected from acetylated amino acids, such as dihydroxylysine. As referred to herein, "aliphatic amino acid" refers to an aliphatic amino acid containing a side chain functional group.

[0043] In certain embodiments, the molar ratio of PET to polycondensation component ranges between 1:4 and 4:1, more particularly between 1:3 and 3:1, more particularly between 1:2 and 2:1, and more particularly the molar ratio of PET to polycondensation component is about 1:1.

[0044] In more particular embodiments, the copolymer further comprises amide hydrogen bonding sites. In certain embodiments, the biodegradable copolymer composition disclosed herein provides that the polycondensation component is a linear aliphatic diol or diamine selected from 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 certain embodiments, the biodegradable copolymer composition disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, the polycondensation component being 1,5-pentanediol and / or 1,6-hexanediol.

[0045] In certain embodiments, the biodegradable copolymer composition disclosed herein provides that the polycondensation component is a straight chain aliphatic dicarboxylic acid selected from heptanedioic acid, octanedioic acid, nonanedioic acid, and / or decanedioic acid. In certain embodiments, the biodegradable copolymer composition disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, said polycondensation component being nonanedioic acid and / or decanedioic acid.

[0046] In certain embodiments, the biodegradable copolymer composition disclosed herein provides that the polycondensation component is a branched aliphatic diol or diamine selected from alkylated or arylated 1,2-ethanediol, 1,3-propanediol, 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 certain embodiments, the biodegradable copolymer compositions disclosed herein consist essentially of a polyethylene terephthalate (PET) component and a polycondensation component, said polycondensation component being 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.

[0047] In certain embodiments, the biodegradable copolymer composition disclosed herein provides that the polycondensation component is a branched chain aliphatic dicarboxylic acid selected from alkylated malonic acid, alkylated succinic acid, alkylated pentanedioic acid, alkylated adipic acid, alkylated heptanedioic acid, alkylated octanedioic acid, alkylated nonanedioic acid, alkylated decanedioic acid, alkylated undecanedioic acid, alkylated dodecanedioic acid, alkylated tridecanedioic acid, alkylated hexadecanedioic acid, and / or dimer fatty diacid. As referred to herein, the term "dimer fatty diacid" (also called dimer fatty acid) is well known in the art and refers to the dimerization product of mono- or polyunsaturated fatty acids and / or esters thereof. In certain embodiments, the biodegradable copolymer composition disclosed herein consists essentially of a polyethylene terephthalate (PET) component and a polycondensation component, the polycondensation component being an alkylated or arylated succinic acid, such as 2-methyl-succinate.

[0048] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide that the polycondensation component is an aliphatic hydroxy acid selected from 2-hydroxy-propanoic acid, 3-hydroxy-propanoic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 3-hydroxy-pentanoic acid, 4-hydroxy-pentanoic acid, and / or 5-hydroxy-pentanoic acid.

[0049] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide that the polycondensation component is an aliphatic amino acid selected from 2-aminopropanoic acid, 3-aminopropanoic acid, 3-aminobutyric acid, 4-aminobutyric acid, 4-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 9-aminostearic acid, 9-aminomethylstearic acid, 10-aminostearic acid, 10-aminomethylstearic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and / or 12-aminostearic acid.

[0050] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide that the PET component is derived from PET waste, such as PET post-consumer waste. During PET recycling into the materials of the present invention, the PET waste is washed, crushed, dried, further recycled, and finally chain extended using commonly known recycling and chain extension techniques.

[0051] In certain embodiments, the biodegradable copolymer compositions disclosed herein are characterized by a molar ratio of PET to polycondensation component ranging between 1:3 and 3:1, more preferably between 1:2 and 2:1, more preferably in the range of about 1:1.

[0052] In certain embodiments, the biodegradable copolymer compositions disclosed herein provide that the polymer is characterized in that it has a Mw of greater than 10 kDa, more preferably greater than 20 kDa, and most preferably greater than 30 kDa.

[0053] In a further aspect, disclosed herein is a method for preparing the biodegradable copolymer compositions disclosed herein, comprising: (a) preparing a PET prepolymer; (b) preparing a polycondensation prepolymer 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; (c) polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to polycondensation component ranging between 1:4 and 4:1. The method includes:

[0054] In certain embodiments, the copolymer is a linear copolymer, e.g., an alternating copolymer, a random copolymer, a statistical copolymer, or a block or segmented copolymer, or a branched copolymer, e.g., a graft copolymer of branched copolymers having different architectures, a branched copolymer of a star copolymer.

[0055] In particular, the polycondensation components are 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.

[0056] In certain embodiments, the methods disclosed herein provide that step (a) occurs by esterification between terephthalic acid or dimethyl terephthalate and ethylene glycol, or by depolymerization of PET into oligomeric PET prepolymers.

[0057] In certain embodiments, the method disclosed herein provides that step (b) occurs by polycondensation. In particular, the polycondensed polymer achieves a chain length that allows for an entangled structure. More specifically, the polymer is characterized by having a Mw of more than 10 kDa, more preferably more than 20 kDa, and most preferably more than 30 kDa.

[0058] In certain embodiments, the methods disclosed herein further comprise the step (c) (c1) melting the PET prepolymer under inert conditions at a temperature in the range of 10 to 30° C. above its softening point; (c2) adding a polycondensation prepolymer to the molten PET component; (c3) reacting the PET component with a polycondensation prepolymer in the absence or presence of a catalyst and

[0059] Step (c1) is carried out under a N2 atmosphere at a temperature between 230°C and 260°C, more specifically at a temperature of about 245°C.

[0060] In certain embodiments, the methods disclosed herein provide that step (c3) occurs in the presence of a catalyst, and the catalyst is zinc acetate or titanium (IV) butoxide.

[0061] In certain embodiments, the methods disclosed herein provide that step (c3) occurs in the presence of a catalyst, said catalyst being Ti(BuO)4. More specifically, step (c3) occurs at a temperature between 220° C. and 250° C. for 3 to 8 hours, more specifically at a temperature of about 235° C. for 3 to 8 hours.

[0062] In certain embodiments, the methods disclosed herein provide for a molar ratio of PET to polycondensation component ranging from between 1:3 to 3:1, more preferably between 1:2 to 2:1, more preferably about 1:1.

[0063] In a further aspect, the present invention relates to products comprising the biodegradable copolymer compositions disclosed herein, particularly rubbery and soft-touch articles in the automotive industry (under-hood hoses, buttons, dashboard panels), consumer goods (drills, shaving equipment, kitchen tools, watch wristbands), medical devices, building and construction (window liners, insulation panels) and outdoor gear (shock absorbers, shoe soles, buttons and strips on backpacks). EXAMPLES

[0064] Example 1 A biodegradable copolymer composition (LM092) according to the present invention was produced by preparing poly(decylene 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 200-225°C for esterification while continuously removing water for 3 hours (until no more water is removed). PET prepolymer was prepared by charging terephthalic acid (1 mol) and ethylene glycol (1.3 mol) into a reactor and carrying out esterification at 190°C and 5 MPa pressure for 3-4 hours.

[0065] The prepared prepolymer was polycondensed towards copolyester by charging PET prepolymer into a flask, melting it at 245 °C under N2 flow and stirring, adding polycondensed prepolymer into the flask, adding Ti(BuO)4 catalyst after 10 min, and reacting the prepared mixture at 235 °C for 3-8 h under a vacuum of 0.5 mmHg.

[0066] Another biodegradable copolymer composition (LM086) according to the present invention was made by preparing poly(decylene 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 200-225°C for esterification with continuous water removal for 3 hours (until no more water is removed). PET prepolymer was prepared by charging terephthalic acid (1 mol) and ethylene glycol (1.3 mol) into a reactor and carrying out esterification at 190°C and 5 MPa pressure for 3-4 hours.

[0067] The prepared prepolymer was polycondensed towards copolyester by charging PET prepolymer into a flask, melting it at 245 °C under N2 flow and stirring, adding polycondensed prepolymer into the flask, adding Ti(BuO)4 catalyst after 10 min, and reacting the prepared mixture at 235 °C for 3-8 h under a vacuum of 0.5 mmHg. Table 1 shows the properties of the prepared copolymers.

[0068] [Table 1]

[0069] The biodegradation of the LM086 and LM092 compositions was measured using the ASTM D5988-18 test method for biodegradation of plastics in soil conditions. Polymer LM086 was biodegraded by an average of 15% (range 10-20%) over 19 weeks, after which biodegradation appeared to stop. Polymer LM092 was degraded by an average of 46% (range between 38%-56%) over a 6 month time period, and degradation was ongoing. This average biodegradability of 46% is close to that of starch (~57%). In Figure 1, it can be seen that the biodegradation of LM092 was very similar to that of starch in replicate 1. Soil respiration studies showed that polymer LM092 was highly biodegradable, with a biodegradability close to that of starch under the same conditions.

[0070] Example 2 A biodegradable copolymer composition according to the present invention was prepared by heating PET and poly(butylene succinate-co-butylene adipate) prepolymers according to the polycondensation method of Example 1. Samples A1 and A2 are copolymers made from a 2:3 PET:PBSA prepolymer reacted at 280-290°C for 1 hour and 1.65 hours, respectively. Samples B1 and B2 are copolymers made from a 1:1 PET:PBSA prepolymer reacted at 280-290°C for 0 hour and 1.5 hour, respectively. Table 2 shows the properties of the prepared copolymers.

[0071] [Table 2]

[0072] From the Shore A hardness parameters it can be concluded that the prepared copolymer compositions have a pronounced elastomeric thermoplastic behavior.

[0073] Example 3 A biodegradable copolymer composition (LMP03) according to the present invention is manufactured by preparing 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 200-225°C for esterification while continuously removing water for 3 hours (until no more water is removed). PET prepolymer is prepared according to Example 1.

[0074] The prepared prepolymer is polycondensed towards copolyester by charging PET prepolymer into a flask, melting it at 245°C under N2 flow and stirring, adding polycondensation prepolymer into the flask, adding Ti(BuO)4 catalyst after 10 minutes, and reacting the prepared mixture at 235°C under a vacuum of 0.5 mmHg for 3-8 hours.

[0075] Example 4 The biodegradable copolymer composition (LMP04) according to the present invention is manufactured by preparing a poly(6-hydroxy-hexanoate) prepolymer by charging 1 mole of 6-hexanolactone and 0.1 mole of decyl alcohol into a reactor, heating the mixture to 150° C. under mechanical stirring and N2 atmosphere, and gradually increasing the temperature to 200° C. over 30 minutes. The PET prepolymer is prepared according to Example 1.

[0076] The prepared prepolymers are equimolarly polycondensed towards copolyesters by charging PET prepolymer into a flask, melting it at 245°C under N2 flow and stirring, adding poly(6-hydroxy-hexanoate) prepolymer into the flask, adding 20 mol% succinic anhydride, adding 250 ppm Ti(BuO)4 catalyst after 10 minutes, and reacting the prepared mixture at 235°C for 3-8 hours under a vacuum of 0.5 mmHg.

[0077] Example 5 The biodegradable copolymer composition (LMP05) according to the present invention is manufactured by preparing poly(6-amino-hexanoate) prepolymer by charging 1.0 mol of 6-amino-hexanoic 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 with continuous water removal for 8 hours. The PET prepolymer is prepared according to Example 1.

[0078] The prepared prepolymer is equimolarly polycondensed by charging PET prepolymer into a flask, melting it at 245°C under N2 flow and stirring, adding poly(6-amino-hexanoate) prepolymer into the flask, adding 20 mol% adipic anhydride, and after 10 minutes, adding 250 ppm Ti(BuO)4 catalyst, and reacting the prepared mixture at 235°C under a vacuum of 0.5 mmHg for 3-8 hours.

Claims

1. A biodegradable copolymer composition comprising a polyethylene terephthalate (PET) component and a polycondensation compound 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 polycondensation compound is in the range of 1:4 to 4:

1.

2. The biodegradable copolymer composition according to claim 1, wherein the polycondensation compound is a linear aliphatic diol or diamine selected from 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 compound is a linear aliphatic dicarboxylic acid selected from heptanediic acid, octanedioic acid, nonanediic acid and / or decanediic acid.

4. The biodegradable copolymer composition according to claim 1, wherein the polycondensation compound is a branched-chain aliphatic diol or diamine selected from alkylated or arylated 1,2-ethanediol, 1,3-propanediol, 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 compound is a branched-chain aliphatic dicarboxylic acid selected from alkylated malonic acid, alkylated succinic acid, alkylated pentanediic acid, alkylated adipic acid, alkylated heptanediic acid, alkylated octanedioic acid, alkylated nonanediic acid, alkylated decanediic acid, alkylated undecanediic acid, alkylated dodecanediic acid, alkylated tridecanediic acid, alkylated hexadecanedioic acid, and / or dimer fatty diacids.

6. The biodegradable copolymer composition according to claim 1, wherein the polycondensation compound is an aliphatic hydroxy acid selected from 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, and / or 5-hydroxypentanoic acid.

7. The biodegradable copolymer composition according to claim 1, wherein the polycondensation compound is an aliphatic amino acid selected from 2-aminopropanoic acid, 3-aminopropanoic acid, 3-aminobutyric acid, 4-aminobutyric acid, 4-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 9-aminostearic acid, 9-aminomethylstearic acid, 10-aminostearic acid, 10-aminomethylstearic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and / or 12-aminostearic acid.

8. The biodegradable copolymer composition according to claim 1, wherein the PET component is a PET component from a PET used waste source.

9. A method for preparing a biodegradable copolymer composition according to any one of claims 1 to 8, (a) A step of preparing a PET prepolymer; (b) A step of preparing a polycondensation prepolymer 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; (c) A step of polycondensing the PET prepolymer with the polycondensation prepolymer in a molar ratio of PET to polycondensation compound in the range of 1:4 to 4:

1. A method that includes [this].

10. The method according to claim 9, wherein step (a) is carried out by esterification between terephthalic acid or dimethyl terephthalate and ethylene glycol, or by depolymerization of PET into an oligomeric PET prepolymer.

11. The method according to claim 9, wherein step (b) is carried out by esterification.

12. Process (c) (c1) A step of melting the PET prepolymer under inert conditions at a temperature 10 to 30°C higher than its softening point; (c2) A step of adding the polycondensed prepolymer to the molten PET component; (c3) A step of reacting the PET component with the polycondensation prepolymer in the absence or presence of a catalyst. The method according to claim 9, which includes the following.

13. The method according to claim 12, wherein step (c3) occurs in the presence of a catalyst, the catalyst being zinc acetate or titanium(IV) butoxide.

14. The biodegradable copolymer composition according to claim 1 or the method according to claim 9, wherein the molar ratio of PET to polycondensation synthesis is in the range of 1:3 to 3:1, more preferably 1:2 to 2:1, and more preferably about 1:

1.

15. A product comprising the biodegradable copolymer composition according to any one of claims 1 to 8, wherein the product is preferably a rubbery and soft-touch article for the automotive industry, consumer goods, medical devices, building and construction, and outdoor equipment.

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