Method for removing plasticizers from polymeric materials

Abstract

A first aspect of the present invention relates to a method for removing a plasticizer from a polymeric material, the method comprising the steps of: (a) providing a polymeric material comprising a polymer and a plasticizer, and providing a solvent comprising gamma-valerolactone; and (b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, dissolved polymer, and dissolved plasticizer. In a second aspect, the present invention relates to a polymer obtained or obtainable from the method according to the first aspect. In a third aspect, the present invention relates to a plasticizer obtained or obtainable from the method according to the first aspect. In a fourth aspect, the present invention relates to the use of a polymer obtained or obtainable by the method according to the first aspect to prepare a polymeric product. In a fifth aspect, the present invention relates to the use of a plasticizer obtained or obtainable by the method according to the first aspect to prepare a soft polymer. In a sixth aspect, the present invention relates to a method for further processing a plasticizer, the method comprising one or more post-treatment steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

Description

[Technical Field]

[0001] A first aspect of the present invention relates to a method for removing a plasticizer from a polymeric material, the method comprising the steps of: (a) providing a polymeric material comprising a polymer and a plasticizer, and providing a solvent comprising gamma-valerolactone; and (b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, dissolved polymer, and dissolved plasticizer. In a second aspect, the present invention relates to a polymer obtained or obtainable from the method according to the first aspect. In a third aspect, the present invention relates to a plasticizer obtained or obtainable from the method according to the first aspect. In a fourth aspect, the present invention relates to the use of a polymer obtained or obtainable from the method according to the first aspect for producing a polymeric product. In a fifth aspect, the present invention relates to the use of a plasticizer obtained or obtainable from the method according to the first aspect for preparing a soft polymer. In a sixth aspect, the present invention relates to a method for further processing a plasticizer, the method comprising one or more steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification. [Background technology]

[0002] Synthetic polymers are generally used in two different forms: rigid and flexible, or so-called soft forms. Softening is usually achieved by adding plasticizers to the polymer material, the most widely used being phthalates. Given the increasing use of polymer materials, the need for recycling them has also arisen, considering raw material conservation and plastic waste reduction. However, recycling also requires separating the polymer material from the incorporated plasticizers, especially since the recycled polymer material may be intended for use in a different application area—for example, polymers used in window profiles may be reused in toys—particularly considering the fact that some plasticizers are toxic or associated with other environmental or health-related issues. Therefore, recycling is often only possible after extraction of the plasticizers, and a gentle method for separating the polymer material and the plasticizers would be highly desirable. "Gentle" preferably means, first, that harmless chemicals are used, and, second, that the polymer and / or plasticizer are recovered without damage. However, methods known in the art to date have relied on fossil-based chemicals that are at least partially toxic, and require complex methods for extracting plasticizers and complex solvent systems. For example, International Publication No. 01 / 70865 discloses a method for recycling plastic materials, where the plastic material may be a polar polymer, such as a polymer of vinyl chloride (PVC). This method involves dissolving the plastic material, using a solvent with a solubility parameter close to that of the plastic to be dissolved, with methyl ethyl ketone (MEK) being the only suitable solvent. Water is used to precipitate the dissolved plastic material. MEK is flammable and moderately explosive, and also poses health-related concerns, for example, because it can cause serious eye irritation.WO 02 / 14413 discloses a method for separating and recovering target polymers and their additives from polymer-containing materials, which involves dissolving the target polymer and at least one additive in a solvent and then mixing the dissolved target polymer, along with the additive, with a non-aqueous solvent II (precipitant) that is miscible with solvent I, so that the target polymer precipitates. Solvent I is selected from the group consisting of low molecular weight alcohols (C1-C5), cyclic ethers (e.g., tetrahydrofuran), aliphatic ketones (e.g., acetone, methyl ethyl ketone), cyclic ketones (e.g., cyclohexanone), dibasic acid ester mixtures (e.g., DBE-dicarboxylic acids, e.g., a mixture of dimethyl esters of glutaric acid, succinic acid, and adipic acid), and mixtures of these solvents, and solvent II is a low molecular weight alcohol (C1-C5). Again, the solvents used to dissolve the polymer are hazardous and associated with several health problems, as demonstrated, for example, with MEK above. U.S. Patent No. 4,071,479 describes a method for recovering reusable, essentially pure vinyl chloride polymer resins from polymer mixtures, comprising dissolving the vinyl chloride polymer and then using a non-solvent that is miscible with the solvent in substantially all proportions to precipitate the essentially pure vinyl chloride polymer resin. Solvents suggested for dissolving the polymer are methyl ethyl ketone, tetrahydrofuran, and dimethylformamide, while anti-solvents can be selected from methanol, isopropanol, n-butanol, or an azeotropic mixture of methyl ethyl ketone and methanol. Again, the solvents used to dissolve the polymer are hazardous and are associated with several health problems, as demonstrated, for example, with MEK above. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 01 / 70865 Brochure [Patent Document 2] International Publication No. 02 / 14413 Brochure [Patent Document 3] U.S. Patent No. 4,071,479 Summary of the Invention [Problem to be solved by the invention]

[0004] The objective underlying the present invention was therefore to provide an improved method that allows for the simple extraction of one or more plasticizers from polymeric materials, while avoiding or at least reducing the use of harmful solvents, and allowing the polymer and / or plasticizer to be recovered intact. [Means for solving the problem]

[0005] First Aspect—Method for Removing Plasticizers In a first aspect, the above problem is solved by providing a method for removing plasticizers from a polymeric material, the method comprising the following steps: (a) providing a polymeric material comprising a polymer and a plasticizer, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with a solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, the dissolved polymer, and the dissolved plasticizer; Includes.

[0006] Gamma-valerolactone (C5H8O2; IUPAC: 5-methyloxolan-2-one, abbreviated as GVL) can be obtained from carbohydrate-based biomass, for example, easily obtained from sugars, and is therefore a "green" solvent. Gamma-valerolactone has so far only been described as being able to dissolve polymeric materials. The GVL used in the context of the present invention is preferably a biorenewable solvent (biorenewable GVL), preferably a GVL that has been tested to contain biobased carbon according to ASTM standard D6866-16. It has been surprisingly discovered that, particularly for polymeric materials containing one or more polymers described below, and particularly for polymeric materials containing polyvinyl chloride (PVC, hereinafter TP.30), gamma-valerolactone enables the removal of plasticizers from the polymeric material without adversely affecting the polymeric material, i.e., the resulting polymeric material contains less plasticizer than the polymeric material prepared in (a), has at least the same number-average molecular weight Mn, and approximately the same weight-average molecular weight Mw as the polymeric material prepared in (a). Thus, the use of GVL enables the recovery of the polymer in an undamaged form. Furthermore, it has been surprisingly discovered that GVL is superior to other solvents for removing plasticizers from polymeric materials, in that it removes significantly more plasticizer from the polymeric material than other solvents.

[0007] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the method comprises: (c) precipitating the polymer from the mixture obtained in (b) by adding an anti-solvent, thereby obtaining a solid residue containing the polymer and a liquid phase containing the solvent, the anti-solvent and the dissolved plasticizer. Further includes:

[0008] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the polymer is preferably a thermoplastic polymer selected from the group consisting of: - in polymerized form, containing at least two different monomers, the monomers being C2 to C 10 Monoolefins (preferably selected from the group consisting of ethylene, propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, and mixtures of two or more of these olefins), vinyl alcohol, C2 to C6 vinyl alcohol 10 - thermoplastic copolymers (TP.1) selected from the group consisting of alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates having an alcohol component of branched or unbranched C1-C10 alcohol methacrylates having an alcohol component of branched or unbranched C1-C10 alcohols, vinyl aromatics (preferably styrene), (meth)acrylonitrile, ethylenically unsaturated mono- or dicarboxylic acids, and maleic anhydride; - Polyvinyl ester (TP.2); - Polycarbonate (TP.3); - Polyether (TP.4); - Polyetherketone (TP.5); - Thermoplastic polyurethane (TP.6); - Polysulfides (TP.7); - Polysulfone (TP.8); - Polyester (TP.9); - Polyalkylene terephthalate (TP.10); - Polyhydroxyalkanoates (TP.11); - Polybutylene succinate (TP.12); - Polybutylene succinate adipate (TP.13); - polyacrylates (TP.14) with the same or different alcohol residues from the group of C4-C8 alcohols, preferably selected from butanol, hexanol, octanol and 2-ethylhexanol; - Polymethylmethacrylate (TP.15); - methyl methacrylate-butyl acrylate copolymer (TP.16); - acrylonitrile-butadiene-styrene copolymer (TP.17); - ethylene-propylene copolymer (TP.18); - ethylene-propylene-diene copolymer (TP.19); - Polystyrene (TP.20); - styrene-acrylonitrile copolymer (TP.21); - acrylonitrile-styrene acrylate (TP.22); - styrene-butadiene-methyl methacrylate copolymer (TP.23); - styrene-maleic anhydride copolymer (TP.24); - styrene-methacrylic acid copolymer (TP.25); - Polyoxymethylene (TP.26); - Polyvinyl alcohol (TP.27); - Polyvinyl acetate (TP.28); - Polyvinyl butyral (TP.29); - Polyvinyl chloride (TP.30); - Polycaprolactone (TP.31); - Polyhydroxybutyrate (TP.32); - Polyhydroxyvaleric acid (TP.33); - Polylactic acid (TP.34); - Ethyl cellulose (TP.35); - cellulose acetate (TP.36); - cellulose propionate (TP.37); - Cellulose acetate butyrate (TP.38) and blends of two or more of these polymers.

[0009] In some preferred embodiments, polyethylene terephthalate (PET) is excluded from the list of polymers TP.1 to TP.38, and in some further preferred embodiments, the polymer is preferably a thermoplastic polymer selected from the group consisting of TP.1 to TP.9 and TP.11 to TP.38 and blends of two or more of these polymers. In some preferred embodiments, the polymer is preferably a thermoplastic polymer selected from the group consisting of TP.1 to TP.8 and TP.11 to TP.38 and blends of two or more of these polymers.

[0010] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the polymer is selected from the group consisting of copolymers comprising, in polymerized form, vinyl chloride and at least one further monomer selected from the group set forth in embodiment 3 for TP.1 (TP.1.1); polyvinyl acetate (TP.28); polyvinyl butyral (TP.29); polyvinyl chloride (TP.30); polycaprolactone (TP.31); and blends of two or more of these polymers.

[0011] In some preferred embodiments of the method for removing plasticizers from a polymeric material, the polymer comprises polyvinyl chloride (TP.30), and preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of the polymers in the polymeric material are polyvinyl chloride, based on the total weight of the polymers in the polymeric material being 100% by weight.

[0012] In some preferred embodiments of the method for removing plasticizers from polymeric materials, at least 20% by weight of the polymeric material consists of polymer, more preferably in the range of 20-90% by weight of the polymeric material consists of polymer, with the total weight of the polymeric material being 100% by weight.

[0013] Generally, polyvinyl chloride is obtained by the homopolymerization of vinyl chloride. Polyvinyl chloride is prepared, for example, by (micro)suspension polymerization or bulk polymerization. The production of polyvinyl chloride by polymerization of vinyl chloride, as well as the production and composition of plasticized polyvinyl chloride, are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Band 2 / 1: Polyvinylchlorid", 2nd edition, Carl Hanser Verlag, Munich.

[0014] In some preferred embodiments, the polymeric material is flexible PVC, preferably having a Shore stiffness in the range of 35 Shore A to 70 Shore D, determined in accordance with DIN 53505:2000-08.

[0015] In some embodiments, the polymeric material comprises a plasticizer distributed in the polymer, or in alternative embodiments, the polymer, preferably in powder form, is dispersed in a liquid plasticizer (plastisol), optionally together with possible pigments, fillers and additives such as blowing agents. The plasticizer is not chemically bonded to the polymer, but is embedded in the polymer, or the polymer is dispersed in the (liquid) plasticizer.

[0016] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the solvent comprising gamma-valerolactone is a mixture of gamma-valerolactone and, optionally, water and a log K in the range of -1.6 to +1.6. OW Preferably, the organic solvent is selected from the group consisting of water, C5 to C12 alkanes, aliphatic C1 to C10 alcohols, C3 to C10 ketones, C2 to C10 cyclic ketones, HO-[C1 to C10 alkyl-O-] n-H (n is an integer ranging from 2 to 1000), C1-C10 alkyl-O-C3-C10 alkyl ether, C3-C10 cyclic ether optionally substituted with one or more C1-C6 alkyl groups, C6-C10 aromatic hydrocarbon optionally substituted with one or more C1-C6 alkyl groups, C2-C10 aliphatic ester, C8-C11 aromatic ester, C5-C10 cyclic carboxylic acid ester (lactone), C3-C12 amide, preferably R 1 R 2 NC(=O)-R 3 (In the formula, R 1 , R 2 are independently a C1-C4 alkyl group, and R 3 is selected from the group consisting of a C1-C9 alkyl group, a C1-C10 ester group, and a C1-C6 ether group), a C3-C6 lactam optionally substituted with one or more substituents selected from a C1-C6 alkyl group, a C1-C6 ester group, and a C1-C6 ether group, and one or more solvents selected from the group consisting of a C5 imidazolidine optionally substituted with one or more C1-C6 alkyl groups, a C5-C7 imidazolidone optionally substituted with one or more C1-C6 alkyl groups.

[0017] Preferably at least 1% by weight, more preferably at least 5% by weight, more preferably at least 10% by weight, more preferably at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, more preferably at least 50% by weight, more preferably at least 60% by weight, more preferably at least 70% by weight, more preferably at least 80% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 95% by weight, more preferably at least 96% by weight, more preferably at least 97% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight of the solvent consists of gamma-valerolactone, based on the total weight of the solvent being 100% by weight.

[0018] Suitable solvents are known to those skilled in the art and are determined by the base 10 logarithm of the octanol-water partition coefficient (log K OW ) is also the octanol-water partition coefficient, K, of a given compound. OW is defined as the ratio of the chemical concentration of a compound in the octanol phase to the chemical concentration of the compound in the aqueous phase in a two-phase system of 1-octanol and water at a temperature of 25°C (298K). The octanol-water partition coefficient K of a given compound is OW Methods for determining the octanol-water partition coefficient, K, of a given compound are known to those skilled in the art. OW is determined using the shake-flask method, which involves dissolving the compound in a volume of high-purity 1-octanol and deionized water (premixed and calibrated for at least 24 hours) and measuring the concentration of the compound in the 1-octanol and aqueous phases, respectively, by a sufficiently accurate method, preferably UV / VIS spectroscopy. This method is described in OECD Guidelines for the Testing of Chemicals, No. 107, adopted July 27, 1995. K for several substances OW The values ​​of are known and can be easily found, for example, in the Dortmund Database (DDB, see http: / / www.ddbst.com / ddb-search).

[0019] Regarding suitable solvents, for example, the aliphatic C1-C10 alcohol is preferably a C1-C6 monool, more preferably one or more selected from the group consisting of methanol, ethanol, and butanol. The C3-C10 ketone is preferably acetone or methyl ethyl ketone, or a mixture of acetone and methyl ethyl ketone. The C2-C10 cyclic ketone is preferably cyclohexanone. The C3-C10 cyclic ether optionally substituted with one or more C1-C3 alkyl groups is preferably tetrahydrofuran or 2-methyltetrahydrofuran, or a mixture of tetrahydrofuran and 2-methyltetrahydrofuran. The C6-C10 aromatic hydrocarbon optionally substituted with one or more C1-C3 alkyl groups is preferably one or more selected from the group consisting of benzene, toluene, ethylbenzene, xylene (o or p), and mesitylene. The C1-C10 ester is preferably one or more selected from the group consisting of esters of C1-C6 aliphatic monools and C2-C5 aliphatic acids. The C5-C10 cyclic carboxylic acid ester (lactone) is preferably one or more selected from the group consisting of delta-valerolactone, methylated gamma-butyrolactone, ethylated gamma-butyrolactone, propylated gamma-butyrolactone, and beta-propiolactone. The C3-C6 lactam optionally substituted with one or more C1-C3 alkyl groups is preferably selected from the group consisting of 2-pyrrolidone, 3-pyrrolidone, and a mixture of 2-pyrrolidone and 3-pyrrolidone, each optionally substituted, preferably at the nitrogen atom, with one or more C1-C3 alkyl groups, more preferably N-methyl-2-pyrrolidone. The imidazolidone optionally substituted with one or more C1-C3 alkyl groups is preferably 1,3-dimethyl-2-imidazolidinone.

[0020] In some preferred embodiments of the method for removing a plasticizer from a polymeric material, the plasticizer is selected from the group consisting of: - cyclohexane-1,2-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - cyclohexane-1,3-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - cyclohexane-1,4-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - phthalic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - phthalic acid alkylaryl esters, the alkyl groups of which are selected from C4 to C13 alkyl and the aryl groups of which are selected from benzyl and phenyl; - terephthalic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - Trimellitic acid trialkyl ester; - Benzoic acid alkyl esters; - Dibenzoic esters of glycol; - Pentaerythritol esters; - saturated monocarboxylic acid alkyl esters; - unsaturated monocarboxylic acid esters; - saturated dicarboxylic acid diesters; - unsaturated dicarboxylic acid diesters; - aromatic sulfonates; - alkylsulfonates; - glycerol esters; - isosorbide esters; - phosphate esters; - Citric acid triester; - Acetylated citrate triester; - alkylpyrrolidone derivatives; - 2,5-furandicarboxylic acid dialkyl esters; - 2,5-tetrahydrofurandicarboxylic acid dialkyl esters; - polyesters of aliphatic and / or aromatic polycarboxylic acids and at least dialcohols; - epoxidized vegetable oil; - epoxidized fatty acid monoalkyl esters; and mixtures of two or more of them.

[0021] The cyclohexane-1,2-dicarboxylic acid dialkyl esters have 4 to 14 carbon atoms (carbon atoms) in the alkyl chain. The alkyl chains of the cyclohexane-1,2-dicarboxylic acid dialkyl esters may have the same or different numbers of carbon atoms, independently of one another. The cyclohexane-1,2-dicarboxylic acid dialkyl esters are preferably selected from the group consisting of di-(2-ethylhexyl)-1,2-cyclohexanedicarboxylate, di-(isononyl)-1,2-cyclohexanedicarboxylate, or di-(2-propylheptyl)-1,2-cyclohexanedicarboxylate, and mixtures of two or more thereof. The cyclohexane-1,3-dicarboxylic acid dialkyl esters have 4 to 14 carbon atoms in their alkyl chains. The alkyl chains of the cyclohexane-1,3-dicarboxylic acid dialkyl esters may have the same or different numbers of carbon atoms, independently of one another. The cyclohexane-1,4-dicarboxylic acid dialkyl esters have 4 to 13 carbon atoms in their alkyl chains. The alkyl chains of the cyclohexane-1,4-dicarboxylic acid dialkyl esters have, independently of one another, the same or different numbers of carbon atoms. The cyclohexane-1,4-dicarboxylic acid dialkyl esters are preferably selected from the group consisting of di-(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, di-(isononyl)-1,4-cyclohexanedicarboxylate, or di-(2-propylheptyl)-1,4-cyclohexanedicarboxylate, and mixtures of two or more thereof. The phthalic acid dialkyl esters have 4 to 13 carbon atoms in their alkyl chains. The alkyl chains have, independently of one another, the same or different numbers of carbon atoms. The phthalic acid dialkyl esters may be diisononyl phthalate. The terephthalic acid dialkyl esters have 4 to 13 carbon atoms in their alkyl chains. The alkyl chains have, independently of one another, the same or different numbers of carbon atoms. The trimellitic acid trialkyl esters have 4 to 13 carbon atoms in their alkyl chains. The alkyl chains of the trimellitic acid trialkyl esters have, independently of each other, the same or different number of carbon atoms. The alkyl benzoates have 7 to 13 carbon atoms in the alkyl chain.

[0022] The alkyl benzoate ester is preferably selected from the group consisting of isononyl benzoate, isodecyl benzoate, 2-propylheptyl benzoate, and mixtures of two or more thereof. The dibenzoate ester is preferably selected from the group consisting of diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, dibutylene glycol dibenzoate, and mixtures of two or more thereof. The saturated monocarboxylic acid ester is preferably selected from the group consisting of esters of acetic acid, butyric acid, valeric acid, lactic acid, and mixtures of two or more thereof. In an alternative embodiment, the saturated monocarboxylic acid ester is preferably selected from the group consisting of esters of monocarboxylic acids and polyhydric alcohols. For example, valeric acid can be esterified with pentaerythritol. The unsaturated monocarboxylic acid ester is preferably an ester of acrylic acid. The unsaturated dicarboxylic acid diester is preferably an ester of maleic acid. The alkyl sulfonic acid ester has 8 to 22 carbon atoms in the alkyl chain. The alkyl sulfonate ester is preferably a phenyl or cresyl ester of pentadecyl sulfonic acid. Isosorbide esters are typically isosorbide diesters esterified with C8-C13 carboxylic acids. The isosorbide diesters have different or identical C8-C13 alkyl chains. The phosphate ester is preferably selected from the group consisting of tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyl diphenyl phosphate, bis-2(2-ethylhexyl)phenyl phosphate, 2-ethylhexyl diphenyl phosphate, and mixtures of two or more thereof. In the citrate triester, the OH group is in a free or carboxylated form, e.g., an acetylated form. The alkyl chains of the citrate triester or acetylated citrate triester independently contain 4 to 8 carbon atoms. The alkyl pyrrolidone derivatives have 4 to 18 carbon atoms in the alkyl chain. 2,5-Furandicarboxylic acid dialkyl esters have 5 to 13 C atoms in the alkyl chain.The alkyl chains of the 2,5-furandicarboxylic acid dialkyl esters independently have different numbers of carbon atoms. The 2,5-tetrahydrofurandicarboxylic acid dialkyl esters have 5 to 13 carbon atoms in the alkyl chain. The alkyl chains of the 2,5-tetrahydrofurandicarboxylic acid dialkyl esters independently have different numbers of carbon atoms. The polyesters with aromatic or aliphatic polycarboxylic acids are preferably polyesters based on adipic acid and polyhydric alcohols, such as dialkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene unit. Examples include polyester adipates, polyglycol adipates, and polyester phthalates.

[0023] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the plasticizer comprises at least a dialkyl cyclohexane-1,2-dicarboxylic acid ester of formula (I): [ka] (In the formula, R 1 and R 2 is independently selected from the group consisting of branched C4 to C13 alkyl and straight chain C1 to C13 alkyl, preferably selected from the group consisting of branched C7 to C11 alkyl and straight chain C7 to C11 alkyl, more preferably R 1 and R 2 are, independently of each other, branched or linear C9 alkyl residues), more preferably the plasticizer comprises at least 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH).

[0024] In some preferred embodiments of the method for removing plasticizer from a polymeric material, the polymeric material contains plasticizer in an amount ranging from 20 to 490 phr, where "phr" means "parts per hundred" and refers to the amount of plasticizer per 100 parts of polymeric material.

[0025] In some specific embodiments, the polymer included in the polymeric material provided in (a) includes at least polyvinyl chloride (TP.30) and the plasticizer included in the polymeric material provided in (a) includes at least DINCH. In these specific embodiments, the method for removing a plasticizer from a polymeric material comprises the following steps: (a) providing a polymeric material comprising at least polyvinyl chloride (TP.30) as a polymer and a plasticizer comprising at least DINCH, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with a solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, dissolved polyvinyl chloride, and dissolved DINCH; Includes.

[0026] Preferably, at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of the polymers contained in the polymeric material provided in (a) are polyvinyl chloride, based on the total weight of the polymers contained in the polymeric material being 100% by weight, and the polymeric material comprises a plasticizer, preferably at least DINCH, in an amount ranging from 20 to 490 phr, more preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of the plasticizers contained in the polymeric material provided in (a) are DINCH, and wherein the total amount of plasticizers contained in the polymeric material is 100% by weight.

[0027] In addition to the plasticizer, the polymeric material may contain further additives, preferably selected from the group consisting of stabilizers, slip agents, fillers, colorants (dyes and / or optical brighteners and / or pigments), flame retardants, light stabilizers, foaming agents, polymer processing agents, impact modifiers, antistatic agents, biostabilizers, or mixtures of two or more thereof. The stabilizers are conventional polyvinyl chloride stabilizers in solid and liquid form, preferably selected from the group consisting of Ca / Zn, Ba / Zn, Pb, Sn stabilizers, acid-bonded layered silicates, carbonates (preferably hydrotalcite), and mixtures of two or more thereof. The polymeric material preferably contains a stabilizer content in the range of 0.05 to 7% by weight, based on the total weight of the polymeric material, which is 100% by weight. Preferably, the stabilizer content is in the range of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. Lubricants generally serve to reduce adhesion between the disclosed molding composition or plastisol and a surface, for example, to reduce frictional forces during mixing, plasticization, or molding. All common lubricants used in plastics processing can be used as lubricants in polymeric materials. Examples of lubricants commonly used in plastics processing include hydrocarbons, such as oil, kerosene, PE wax, or mixtures thereof; fatty alcohols containing 6 to 20 carbon atoms; ketones; carboxylic acids, such as fatty acids, montanic acid, or mixtures thereof; oxidized PE wax; metal salts of carboxylic acids; carboxylic acid amides; alcohols, such as ethanol, fatty alcohols, glycerol, ethanediol, or carboxylic acid esters resulting from the esterification of pentaerythritol with long-chain carboxylic acids. The polymeric material preferably contains a lubricant content in the range of 0.01 to 10% by weight, based on the total weight of the polymeric material, which is 100% by weight. Preferably, the lubricant content is in the range of 0.05 to 5% by weight, more preferably 0.2 to 2% by weight. Fillers are generally used to positively affect the compressive strength, tensile strength, and / or flexural strength, stiffness and / or heat distortion temperature of a polymeric material.For example, carbon black and / or inorganic fillers are preferably present as fillers in the disclosed polymeric materials. The inorganic filler is preferably selected from the group consisting of natural calcium carbonates, such as chalk, limestone, marble, synthetic calcium carbonate, dolomite, silicates, silica, sand, diatomaceous earth, aluminosilicates, such as kaolin, mica, feldspar, and any mixture of two or more of the aforementioned fillers. The polymeric materials preferably contain a filler content ranging from 0.01% to 80% by weight, based on the total weight of the molding compound or plastisol. Preferably, the filler content ranges from 0.01 to 60% by weight, more preferably from 1 to 40% by weight. Thus, the disclosed polymeric materials preferably contain a filler content ranging from 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36, or 39% by weight. Colorants can be used to adapt the disclosed molding compositions or plastisols to different applications. The colorant may be, for example, a pigment or dye. The pigment may be, for example, an inorganic and / or organic pigment contained in the polymeric material. The inorganic pigment may be a cobalt pigment, such as CoO / Al2O3, and / or a chromium pigment, such as Cr2O3. The organic pigment may be a monoazo pigment, a condensed azo pigment, an azomethine pigment, an anthraquinone pigment, a quinacridone, a phthalocyanine pigment, and / or a dioxazine pigment. The disclosed molding composition or the disclosed plastisol preferably contains a colorant content in the range of 0.01 to 10% by weight, based on the total weight of the polymeric material, which is 100% by weight. Preferably, the colorant content range is 0.05 to 5% by weight, more preferably 0.1 to 3% by weight. The flame retardant may help reduce the flammability of the disclosed molding compound or the disclosed plastisol and reduce smoke formation during combustion. The flame retardant preferably present in the disclosed polymeric material is preferably selected from the group consisting of antimony trioxide, chlorinated kerosene, phosphate esters, aluminum hydroxide, boron compounds, and mixtures of two or more of these compounds.The polymeric material preferably contains a flame retardant content in the range of 0.01 to 10% by weight, based on the total weight of the polymeric material, which is 100% by weight. The flame retardant content is preferably in the range of 0.2 to 5% by weight, more preferably in the range of 0.5 to 2% by weight. Light stabilizers, such as UV absorbers, can help protect the disclosed molding compositions or the disclosed plastisols from damage due to the effects of light. The light stabilizer is preferably selected from the group consisting of hydroxybenzophenone, hydroxyphenylbenzotriazole, cyanoacrylate, hindered amine light stabilizers, such as derivatives of 2,2,6,6-tetramethylpiperidine, and mixtures of two or more of these compounds. The polymeric material preferably contains a light stabilizer content in the range of 0.01 to 7% by weight, based on the total weight of the polymeric material, which is 100% by weight. Preferably, the light stabilizer content is in the range of 0.02 to 4% by weight, more preferably in the range of 0.05 to 3% by weight.

[0028] <Contact> In some preferred embodiments of the method for removing plasticizers from polymeric materials, in (b), contacting the polymeric material with the solvent comprising gamma-valerolactone is carried out at a temperature T1 less than 190°C, preferably less than 180°C, more preferably less than 170°C, more preferably at a temperature T1 in the range of 90 to less than 170°C, more preferably at a temperature T1 in the range of 95 to 165°C, more preferably at a temperature T1 in the range of 100 to 150°C.

[0029] In some preferred embodiments of the method for removing plasticizers from polymeric materials, in (b), contacting the polymeric material with a solvent containing gamma-valerolactone is carried out for at least 0.1 hours, preferably for a time in the range of 0.1 to 10 hours, preferably for a time in the range of 0.1 to 6 hours, and more preferably for a time in the range of 0.1 to 4 hours. In some preferred embodiments of the method for removing plasticizers from polymeric materials, in (b), contacting the polymeric material with a solvent containing gamma-valerolactone is carried out at a pressure in the range of 800 to 200,000 hPa. In some preferred embodiments of the method for removing plasticizers from polymeric materials, in (b), contacting the polymeric material with a solvent containing gamma-valerolactone is carried out at a polymeric material:solvent weight ratio in the range of 1:1 to 1:100, more preferably in the range of 1:1 to 1:20, and more preferably in the range of 1:1 to 1:10.

[0030] "Contacting" preferably means that the polymer is at least partially immersed in the solvent. Preferably, the polymer is at least partially immersed in the solvent in that at least 60%, more preferably at least 70%, more preferably at least 80%, more preferably at least 90%, more preferably at least 95%, more preferably at least 99% of the surface of the polymer is in contact with the solvent, based on the total surface of the polymeric material being 100%.

[0031] <Poor solvent> In some preferred embodiments of the method for removing plasticizers from polymeric materials, step (c) comprises the steps of: (c.1) adjusting the temperature to a temperature T2 less than T1, preferably in the range of 10°C to 100°C, preferably in the range of 15 to 90°C, more preferably in the range of 20 to 80°C; (c.2) Precipitating the polymer from the mixture obtained in (b) at T2 by addition of an antisolvent; thereby obtaining a solid residue comprising the polymer and a liquid phase comprising the solvent, the anti-solvent and the dissolved plasticizer; Includes.

[0032] According to ULLMANN'S Encyclopedia of Industrial Chemistry (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2012, Vol. 33, Chapter "Solvents," pp. 619-688, especially p. 626; DOI: 10.1002 / 14356007.a24_437), a solvent is defined as one that can dissolve a given substance, e.g., a polymer (solute), at room temperature, and the solubility parameters of the solvent and solute are similar. A non-solvent (also known as a poor solvent) is defined as one that cannot dissolve the substance of interest. The solubility and hydrogen bonding parameters of a poor solvent are outside the solubility region of the polymer but within the solubility region of the substance to be dissolved, especially the plasticizer.

[0033] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the anti-solvent used in step (c) or (c.2) is selected from the group consisting of water, C1-C5 monoalcohols, C1-C6 dialcohols, and mixtures of two or more of these solvents, preferably selected from the group consisting of water, C1-C5 monoalcohols, C1-C5 dialcohols, and mixtures of two or more of these solvents, more preferably selected from the group consisting of water, C1-C3 monoalcohols, and mixtures of two or more of these solvents. More preferably, the anti-solvent used in step (c) or (c.2) comprises isopropanol, and more preferably, at least 95% by weight of the anti-solvent used in step (c) or (c.2) consists of isopropanol. Like GVL, the isopropanol used is preferably a biorenewable solvent (biorenewable isopropanol), i.e., obtained from carbohydrate-based biomass and is therefore a "green" solvent. Biorenewable solvents are derived from renewable and sustainable bio-based materials, significantly reducing their environmental impact. The bio-renewable solvent is preferably tested to contain bio-based carbon according to ASTM standard D6866-16.

[0034] In some specific embodiments, the polymer included in the polymeric material provided in (a) comprises at least polyvinyl chloride (TP.30), the plasticizer included in the polymeric material provided in (a) comprises at least DINCH, and the anti-solvent used in step (c) or (c.2) comprises at least isopropanol. In these specific embodiments, the method for removing a plasticizer from a polymeric material comprises the following steps: (a) providing a polymeric material comprising at least polyvinyl chloride (TP.30) as a polymer and a plasticizer comprising at least DINCH, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with a solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, dissolved polyvinyl chloride, and dissolved DINCH; (c) precipitating at least polyvinyl chloride from the mixture obtained in (b) by adding an anti-solvent comprising isopropanol, or (alternatively to (c)): (c.1) adjusting the temperature to a temperature T2 less than T1, preferably in the range of 10°C to 100°C, preferably in the range of 15 to 90°C, more preferably in the range of 20 to 80°C; and (c.2) precipitating polyvinyl chloride from the mixture obtained in (b) at T2 by addition of an anti-solvent comprising isopropanol, preferably bio-renewable isopropanol; thereby obtaining a solid residue containing polyvinyl chloride and a liquid phase containing the solvent, (bio-renewable) isopropanol and dissolved DINCH; Includes.

[0035] In these specific embodiments, at least 90 wt. % of the polymer in the polymeric material provided in (a) is polyvinyl chloride, more preferably at least 95 wt. %, more preferably at least 98 wt. %, based on the total weight of polymer in the polymeric material being 100 wt. %, the polymeric material comprises a plasticizer, preferably at least DINCH, in an amount ranging from 20 to 490 phr, more preferably at least 90 wt. %, more preferably at least 95 wt. %, more preferably at least 98 wt. % of the plasticizer in the polymeric material provided in (a) is DINCH, the total amount of plasticizer in the polymeric material is 100 wt. %, and preferably at least 95 wt. % of the anti-solvent used in step (c) or (c.2) consists of isopropanol.

[0036] Preferably, the anti-solvent is added in step (c) or (c.2) in a weight ratio of anti-solvent to polymeric material in the range of 4:1 to 75:1, more preferably in the range of 5:1 to 50:1, more preferably in the range of 5:1 to 10:1, where the weight of polymeric material is the weight of the polymeric material including the polymer and plasticizer initially provided in (a).

[0037] <Amount of residual plasticizer> In some preferred embodiments of the methods for removing plasticizers from polymeric materials, the solid residue polymer obtained in (c) or (c.2) contains less than 5%, preferably less than 1%, of the amount of plasticizer that was present in the polymeric material provided in (a).

[0038] <Post-processing steps> In some preferred embodiments of the method for removing plasticizers from polymeric materials, the method comprises: (d) separating the polymer-containing solid residue obtained in (c) or (c.2) from a liquid phase containing the solvent, anti-solvent, and dissolved plasticizer, thereby obtaining a polymer-containing solid residue and a liquid phase containing the solvent, anti-solvent, and dissolved plasticizer; (e) optionally washing the solid residue obtained in (d) with an anti-solvent; (f) drying the solid residue obtained in (d) or the washed solid residue obtained in (e); Further includes:

[0039] The separation in (d) is carried out by methods and means known to those skilled in the art, in particular by solid-liquid separation methods, such as filtration, for example hot pressure filtration, sedimentation, or centrifugation (see Handbuch der mechanischen Fest-Flussig-Trennung Taschenbuch - April 29, 2004, von Klaus Lückert (Herausgeber)).

[0040] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the method comprises one or more post-treatment steps, the one or more post-treatment steps preferably comprising the following steps: (g) separating the solvent and anti-solvent by distillation and / or separating the solvent from the dissolved plasticizer by distillation, thereby preferably obtaining a liquid fraction comprising the plasticizer and one or more liquid fractions comprising the solvent and / or anti-solvent. Includes.

[0041] The plasticizer obtained in (g) is preferably in liquid form, but due to the higher molar mass and higher boiling point of the resulting plasticizer compared to the solvent and antisolvent, the plasticizer cannot be removed by distillation.

[0042] In some preferred embodiments of the method for removing plasticizers from polymeric materials, the method further comprises at least partially recycling the separated solvent obtained in (g) to (b) and / or at least partially recycling the separated anti-solvent obtained in (g) to (c).

[0043] Second Aspect - Polymer Obtained or Obtainable by the Method In a second aspect, the present invention relates to a polymer obtained or obtainable by a method according to the first aspect, preferably from (e) and / or (f) by the method of the first aspect. All details, embodiments and preferred embodiments described above in the section relating to the first aspect also apply to the second aspect.

[0044] Third Aspect - Plasticizers Obtained or Obtainable by the Method In a third aspect, the present invention relates to a plasticizer obtained or obtainable from a process according to the first aspect, preferably (g). All details, embodiments and preferred embodiments described above in the section relating to the first aspect also apply to the third aspect.

[0045] Fourth Aspect—Use of Polymers According to a fourth aspect, the present invention relates to the use of a polymer obtained or obtainable from a process according to the first aspect, preferably from (e) and / or (f) by the process of the first aspect, for preparing a polymeric product, preferably a soft polymeric product, comprising at least one plasticizer, the at least one plasticizer preferably being REACH approved. All details, embodiments and preferred embodiments described above in the section relating to the first aspect also apply to the fourth aspect.

[0046] REACH approved plasticizer means a plasticizer that is registered under Regulation (EC) No 1907 / 2006 "Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)" and is not listed in Annex 17 to the Regulation.

[0047] In some preferred embodiments, as set out above, the polymer obtained or obtainable from the method according to the first aspect, preferably (e) and / or (f) according to the method of the first aspect, is used in the preparation of a soft polymer product.

[0048] In one aspect of said preferred embodiment, the present invention also provides a method for preparing a product, comprising the steps of: (I) providing a polymer resulting from a method according to the first aspect, preferably from (e) and / or (f) according to the method of the first aspect; (II) preparing a polymer product, preferably a soft polymer product, from the polymer provided in (I) by adding at least one plasticizer, preferably REACH approved; The present invention relates to a method, including:

[0049] In some alternative preferred embodiments, the polymer obtained or obtainable from the process according to the first aspect, preferably (e) and / or (f) by the process of the first aspect, is used in the preparation of a rigid polymer product, without the addition of a plasticizer.

[0050] In certain aspects of the alternative preferred embodiment, the present invention also provides a method for preparing a rigid polymeric article, the method comprising: (I) providing a polymer resulting from a method according to the first aspect, preferably from (e) and / or (f) according to the method of the first aspect; (II) preparing a rigid polymer article from the polymer provided in (I), preferably by molding; Including, In both (I) and (II), no plasticizer is added.

[0051] "No added plasticizer" and "in both (I) and (II) no added plasticizer" mean that even if a certain amount of plasticizer is present, said amount is too small to affect the rigidity properties of the rigid polymer product.

[0052] The resulting rigid polymer product, i.e. a rigid polymer material made from the polymer obtained or obtainable from the process according to the first aspect, preferably (e) and / or (f) by the process of the first aspect, is used for example in the manufacture of plates, tubes, pipes, profiles, blisters, records, windows, window profiles, traffic management, floor coverings, or thermoformed sheets.

[0053] Fifth Aspect—Use of Plasticizers According to a fifth aspect, the present invention relates to the use of a plasticizer obtained or obtainable from a process according to the first aspect, preferably from (g) by a process of the first aspect, optionally after one or more post-treatment steps, for preparing a soft polymer. All details, embodiments and preferred embodiments described above in the section relating to the first aspect also apply to the fifth aspect. The same applies to the definitions according to REACH given in the section above relating to the fourth aspect of the invention.

[0054] In some preferred embodiments, the present invention also provides a method for preparing a flexible polymeric product, comprising the steps of: (I) providing a plasticizer and a polymer obtained or obtainable by a method according to the first aspect, preferably from (g) by the method of the first aspect; (II) preparing a soft polymer material from the polymer and plasticizer provided in (I); The present invention relates to a method, including:

[0055] Preferably, the polymers provided in (I) are (virgin or recycled) polymers as defined as TP.1 to TP.38 in the section relating to the first embodiment.

[0056] The soft polymeric material obtained as described in the sections relating to the fourth and fifth aspects in some embodiments comprises a plasticizer distributed in the polymer, or in alternative embodiments the polymer, preferably in powder form, is dispersed in a liquid plasticizer (plastisol), optionally together with pigments, fillers and additives such as blowing agents, in some cases. The plasticizer is not chemically bound to the polymer but is embedded in the polymer or the polymer is dispersed in the (liquid) plasticizer.

[0057] The obtained soft polymeric material, which is either a soft polymeric material made from a polymer obtained or obtainable from the process according to the first aspect, preferably (e) and / or (f) by the process of the first aspect, or a soft polymeric material made from a plasticizer obtained or obtainable from the process according to the first aspect, preferably (g) by the process of the first aspect, is used for example for the production of moulded bodies, gloves, films, wallpaper or heterogeneous floor coverings or for textile coatings.

[0058] The molded article is, for example, a container, an apparatus, or a foamed device. The container is, for example, an electrical appliance, such as a kitchen appliance housing or a computer housing, a pipe, a hose, such as a water or irrigation hose, an industrial rubber hose, a chemical hose, a wire or cable covering, a tool covering, a bicycle, scooter, or wheelbarrow handle, a metal coating, or a packaging container. The apparatus is, for example, a tool, furniture, such as a chair, a shelf, a table, a record, a profile, such as a window profile, an outdoor floor profile, or a profile for a conveyor belt, a component for a vehicle structure, such as a body component, an underbody protection, or a vibration damper, or an eraser. The foamed device is, for example, a cushion, a mattress, a foam, or a thermal insulation material. Examples of films include tarpaulins, such as truck tarpaulins, roof tarpaulins, geomembrane tarpaulins, stadium roofs, or tent tarpaulins, gaskets, laminated films, such as laminated safety glass films, self-adhesive films, laminated films, shrink films, outdoor floor coverings, adhesive tape films, coatings, swimming pond films, decorative pond films, tablecloths, and artificial leather. Molding compounds are used to produce molded articles or films that come into direct contact with humans or food. Examples of molded articles or films that come into direct contact with humans or food include medical products, hygiene products, food packaging, indoor products, infant and pediatric products, childcare products, sports or leisure products, clothing, textiles, or fabrics. Examples of medical products produced using molding compounds include enteral feeding tubes or hemodialysis tubes, ventilation tubes, drainage tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves, and respiratory masks. Food packaging products made using the molding compound are, for example, cling films, food tubes, drinking water tubes, food storage or freezer containers, lid seals, closure caps, crown caps, or artificial wine corks.Interior products manufactured using molding compounds include, for example, floor coverings, which may be homogeneous or comprise multiple layers, each consisting of at least one foamed layer, such as floor coverings, mud mats, sports floors, luxury vinyl tiles (LVT), artificial leather, wall coverings, foamed or non-foamed wallpaper for buildings, and vehicle trim or console covers. Baby and pediatric products manufactured using molding compounds include, for example, toys, such as dolls, play figures, or plasticines; inflatable toys, such as balls or rings; non-slip socks; swimming aids, stroller covers, diaper changing pads; hot water bottles; teething rings or bottles. Sports or recreational products manufactured using molding compounds include, for example, exercise balls, exercise mats, seat cushions, massage balls or rollers, shoes, shoe soles, balls, air mattresses, safety goggles, gloves, or water bottles. Clothing manufactured using molding compounds includes, for example, latex clothing, protective clothing, rain jackets, or rubber boots.

[0059] In a preferred embodiment, when the resulting soft polymeric material is a plastisol, said plastisol is typically used as follows.

[0060] Plastisols are typically formed into the shape of the final product by various processes, such as coating, casting (e.g., shell casting or rotational molding), dipping, printing (e.g., screen printing), spraying, etc. They are then heated to gel, and after cooling, a homogeneous, somewhat flexible product is obtained. Plastisols are used for the production of films, wallpaper, seamless hollow bodies, gloves, heterogeneous flooring, or for applications in the textile sector, such as textile coatings. Films include, for example, truck tarpaulins, roof tarpaulins, general covers such as boat covers, stroller covers, or stadium roofs, tent tarpaulins, geomembranes, tablecloths, coatings, swimming pond films, artificial leather, or decorative pond films. Gloves include, for example, gardening gloves, medical gloves, chemical gloves, protective gloves, or disposable gloves. Furthermore, plastisols are used, for example, to manufacture gaskets, lid seals, trim or console covers in vehicles, dolls, play figures or plasticines, inflatable toys such as balls or rings, non-slip socks, swimming aids, diaper changing pads, exercise balls, exercise mats, seat cushions, vibrators, massage balls or rollers, latex clothing, protective clothing, rain jackets or rubber boots.

[0061] Sixth Aspect—Further Processing of the Plasticizer According to a sixth aspect, the present invention relates to a method for further processing a plasticizer, preferably a plasticizer obtained or obtainable from a method according to the first aspect, preferably (g) by the method of the first aspect, which method comprises one or more steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

[0062] All details, embodiments and preferred embodiments described above in the sections relating to the first or fifth aspect also apply to the sixth aspect.

[0063] In some preferred embodiments of the further processing method, hydrolysis comprises contacting the plasticizer with water, and optionally with a base or an acid, and / or optionally under electromagnetic radiation, preferably light.

[0064] In some preferred embodiments of the further processing method, hydrogenation comprises contacting the plasticizer with a hydrogen (H)-containing gas under hydrogenation conditions, preferably hydrogenation conditions that allow hydrogenation of the aromatic ring core, more preferably under conditions disclosed in WO 99 / 032427.

[0065] Regarding plasticizers, isosorbide esters are excluded from transesterification.

[0066] In some preferred embodiments of the further processing method, transesterification comprises contacting the plasticizer with an alcohol having a higher boiling point than the alcohol contained in the alcohol portion of the plasticizer, optionally in the presence of an acidic or basic catalyst, the acidic catalyst preferably comprising a Bronsted acid and a Lewis acid, and the basic catalyst preferably comprising NaHCO, more preferably NaHCO.

[0067] The present invention is further described by the following embodiments and combinations of embodiments indicated by their respective dependencies and back-references. In particular, it should be noted that whenever a range of embodiments is mentioned, for example in connection with a term such as "the method according to any one of embodiments 1 to 4," it means that all embodiments within this range are expressly disclosed to those skilled in the art, that is, the wording of this term should be understood by those skilled in the art to be synonymous with "the method according to any one of embodiments 1, 2, 3, and 4."

[0068] 1. A method for removing plasticizers from a polymeric material, comprising the steps of: (a) providing a polymeric material comprising a polymer and a plasticizer, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with a solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, the dissolved polymer, and the dissolved plasticizer; A method comprising:

[0069] 2. (c) Precipitating the polymer from the mixture obtained in (b) by adding an anti-solvent, thereby obtaining a solid residue containing the polymer and a liquid phase containing the solvent, the anti-solvent, and the dissolved plasticizer. 2. The method of embodiment 1, further comprising:

[0070] 3. The polymer is preferably a thermoplastic polymer, more preferably, in polymerized form, comprises at least two different monomers, at least two of which are C2 to C6 10 Monoolefins (preferably selected from the group consisting of ethylene, propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, and mixtures of two or more of these olefins), vinyl alcohol, C2 to C6 vinyl alcohol 10copolymers (TP.1) selected from the group consisting of alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates having an alcohol component of branched or unbranched C1-C10 alcohols, methacrylates having an alcohol component of branched or unbranched C1-C10 alcohols, vinyl aromatics (preferably styrene), (meth)acrylonitrile, ethylenically unsaturated mono- or dicarboxylic acids, and maleic anhydride; polyvinyl esters (TP.2); polycarbonates (TP.3); polyethers (TP.4); polyetherketones (TP.5); thermoplastic polyurethanes (TP.6); polysulfides (TP.7); polysulfones (TP.8); polyesters (TP.9); polyalkylene terephthalates (TP.10); polyhydroxyalkanoates (TP.11); polybutylene succinates (TP.12); polybutylene succinate adipates (TP.13); C4 to C8 alcohols, preferably selected from butanol, hexanol, octanol, and 2-ethylhexanol. Polyacrylates with the same or different alcohol residues from the alcohol group (TP.14); polymethyl methacrylate (TP.15); methyl methacrylate-butyl acrylate copolymer (TP.16); acrylonitrile-butadiene-styrene copolymer (TP.17); ethylene-propylene copolymer (TP.18); ethylene-propylene-diene copolymer (TP.19); polystyrene (TP.20); styrene-acrylonitrile copolymer (TP.21); acrylonitrile-styrene acrylate (TP.22); styrene-butadiene copolymer (TP.23); Diene-methyl methacrylate copolymer (TP.23); styrene-maleic anhydride copolymer (TP.24); styrene-methacrylic acid copolymer (TP.25); polyoxymethylene (TP.26); polyvinyl alcohol (TP.27); polyvinyl acetate (TP.28); polyvinyl butyral (TP.29); polyvinyl chloride (TP.30); polycaprolactone (TP.31); polyhydroxybutyric acid (TP.32); polyhydroxyvaleric acid (TP.33); polylactic acid (TP.34); ethyl cellulose (TP.35); cellulose acetate (TP.36); cellulose propionate (TP.37); and cellulose acetate butyrate (TP.38), and blends of two or more of these polymers.

[0071] 4. The method of any one of embodiments 1 to 3, wherein the polymer is selected from the group consisting of copolymers comprising, in polymerized form, vinyl chloride and at least one further monomer selected from the group set forth in embodiment 3 for TP.1; polyvinyl acetate (TP.28); polyvinyl butyral (TP.29); polyvinyl chloride (TP.30); polycaprolactone (TP.31); and blends of two or more of these polymers.

[0072] 5. The method of any one of embodiments 1 to 4, wherein the polymer comprises polyvinyl chloride (TP.30), and preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of the polymers in the polymeric material are polyvinyl chloride, based on the total weight of the polymers in the polymeric material being 100% by weight.

[0073] 6. The method of any one of the preceding embodiments, wherein at least 20% by weight of the polymeric material consists of polymer, more preferably in the range of 20-90% by weight of the polymeric material consists of polymer, the total weight of the polymeric material being 100% by weight.

[0074] 7. The solvent containing gamma-valerolactone is a mixture of gamma-valerolactone and, optionally, water and a log K in the range of -1.6 to +1.6. OW Preferably, the organic solvent is selected from the group consisting of water, C5 to C12 alkanes, aliphatic C1 to C10 alcohols, C3 to C10 ketones, C2 to C10 cyclic ketones, HO-[C1 to C10 alkyl-O-] n-H (n is an integer ranging from 2 to 1000), C1-C10 alkyl-O-C3-C10 alkyl ether, C3-C10 cyclic ether optionally substituted with one or more C1-C6 alkyl groups, C6-C10 aromatic hydrocarbon optionally substituted with one or more C1-C6 alkyl groups, C2-C10 aliphatic ester, C8-C11 aromatic ester, C5-C10 cyclic carboxylic acid ester (lactone), C3-C12 amide, preferably R 1 R 2 NC(=O)-R 3 (In the formula, R 1 , R 2 are independently a C1-C4 alkyl group, and R 3 is selected from the group consisting of a C1-C9 alkyl group, a C1-C10 ester group, and a C1-C6 ether group), a C3-C6 lactam optionally substituted with one or more substituents selected from a C1-C6 alkyl group, a C1-C6 ester group, and a C1-C6 ether group, and one or more solvents selected from the group consisting of a C5 imidazolidine optionally substituted with one or more C1-C6 alkyl groups, a C5-C7 imidazolidone optionally substituted with one or more C1-C6 alkyl groups.

[0075] 8. Plasticizers - cyclohexane-1,2-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - cyclohexane-1,3-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - cyclohexane-1,4-dicarboxylic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - phthalic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - phthalic acid alkylaryl esters, the alkyl group of which is selected from C4 to C13 alkyl and the aryl group of which is selected from benzyl and phenyl; - terephthalic acid dialkyl esters, the alkyl groups of which are independently selected from C4 to C13 alkyl; - Trimellitic acid trialkyl ester; - Benzoic acid alkyl esters; - Dibenzoic esters of glycol; - Pentaerythritol esters; - saturated monocarboxylic acid alkyl esters; - unsaturated monocarboxylic acid esters; - saturated dicarboxylic acid diesters; - unsaturated dicarboxylic acid diesters; - aromatic sulfonates; - alkylsulfonates; - glycerol esters; - isosorbide esters; - phosphate esters; - Citric acid triester; - Acetylated citrate triester; - alkylpyrrolidone derivatives; - 2,5-furandicarboxylic acid dialkyl esters; - 2,5-tetrahydrofurandicarboxylic acid dialkyl esters; - polyesters of aliphatic and / or aromatic polycarboxylic acids and at least dialcohols; - epoxidized vegetable oil; - epoxidized fatty acid monoalkyl esters; and mixtures of two or more of these 8. The method of any one of embodiments 1 to 7, selected from the group consisting of:

[0076] 9. The plasticizer comprises at least one dialkyl cyclohexane-1,2-dicarboxylic acid ester of formula (I) [ka] (In the formula, R 1 and R 2 is independently selected from the group consisting of branched C4 to C13 alkyl and straight chain C1 to C13 alkyl, preferably selected from the group consisting of branched C7 to C11 alkyl and straight chain C7 to C11 alkyl, more preferably R 1 and R 2 are, independently of each other, branched or linear C9 alkyl residues) and more preferably, the plasticizer comprises at least 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH).

[0077] 10. The method of any one of the preceding claims, wherein the polymeric material comprises a plasticizer in an amount ranging from 20 to 490 phr.

[0078] 11. The method of any one of embodiments 1 to 10, wherein in (b), the contacting of the polymeric material with the solvent comprising gamma-valerolactone is carried out at a temperature T1 of less than 190°C, preferably less than 180°C, more preferably less than 170°C, more preferably at a temperature T1 in the range of 90 to less than 170°C, more preferably at a temperature T1 in the range of 95 to 165°C, more preferably at a temperature T1 in the range of 100 to 150°C.

[0079] 12. The method of any one of embodiments 1 to 11, wherein in (b), contacting the polymeric material with the solvent comprising gamma-valerolactone is carried out for a period of at least 0.1 hours, preferably for a period in the range of 0.1 to 10 hours, preferably for a period in the range of 0.1 to 6 hours, more preferably for a period in the range of 0.1 to 4 hours.

[0080] 13. The method of any one of embodiments 1 to 12, wherein in (b), contacting the polymeric material with a solvent comprising gamma-valerolactone is carried out at a pressure in the range of 800 to 200,000 hPa.

[0081] 14. The method of any one of embodiments 1 to 13, wherein in (b), contacting the polymeric material with a solvent comprising gamma-valerolactone is carried out at a weight ratio of polymeric material to solvent in the range of 1:1 to 1:100, more preferably in the range of 1:1 to 1:20, more preferably in the range of 1:1 to 1:10.

[0082] 15. Step (c) is (c.1) adjusting the temperature to a temperature T2 less than T1, preferably in the range of 10°C to 100°C, preferably in the range of 15 to 90°C, more preferably in the range of 20 to 80°C; (c.2) Precipitating the polymer from the mixture obtained in (b) at T2 by addition of an antisolvent; thereby obtaining a solid residue comprising the polymer and a liquid phase comprising the solvent, the antisolvent and the dissolved plasticizer; 15. The method of any one of embodiments 2 to 14, comprising:

[0083] 16. The method of any one of embodiments 2 to 15, wherein the anti-solvent used in step (c) or (c.2) is selected from the group consisting of water, C1-C5 monoalcohols, C1-C6 dialcohols, and mixtures of two or more of these solvents, preferably selected from the group consisting of water, C1-C5 monoalcohols, C1-C5 dialcohols, and mixtures of two or more of these solvents, more preferably selected from the group consisting of water, C1-C3 monoalcohols, and mixtures of two or more of these solvents, more preferably the anti-solvent used in step (c) or (c.2) comprises isopropanol, more preferably at least 95% by weight of the anti-solvent used in step (c) or (c.2) consists of isopropanol.

[0084] 17. The method of any one of embodiments 2 to 16, wherein the anti-solvent is added in step (c) or (c.2) in a weight ratio of anti-solvent to polymeric material in the range of 4:1 to 75:1, preferably in the range of 5:1 to 50:1, more preferably in the range of 5:1 to 10:1.

[0085] 18. The method of any one of the preceding embodiments, wherein the solid residue polymer obtained in (c) or (c.2) contains less than 5%, preferably less than 1%, of the amount of plasticizer that was present in the polymer material provided in (a).

[0086] 19. (d) Separating the polymer-containing solid residue obtained in (c) or (c.2) from a liquid phase containing the solvent, anti-solvent, and dissolved plasticizer, thereby obtaining a polymer-containing solid residue and a liquid phase containing the solvent, anti-solvent, and dissolved plasticizer; (e) optionally washing the solid residue obtained in (d) with an anti-solvent; (f) drying the solid residue obtained in (d) or the washed solid residue obtained in (e); 19. The method of any one of embodiments 1 to 18, further comprising:

[0087] 20. One or more post-processing steps, preferably comprising: (g) separating the solvent and anti-solvent by distillation and / or separating the solvent from the dissolved plasticizer by distillation, thereby preferably obtaining a liquid fraction comprising the plasticizer and one or more liquid fractions comprising the solvent and / or anti-solvent. 20. The method of any one of embodiments 1 to 19, comprising:

[0088] 21. The method of embodiment 20, further comprising at least partially recycling the separated solvent obtained in (g) to (b), and / or at least partially recycling the separated anti-solvent obtained in (g) to (c).

[0089] 22. A polymer obtained or obtainable by the method according to any one of embodiments 1 to 21, preferably (e) and / or (f) of embodiment 19, and / or a polymer as defined in embodiment 18.

[0090] 23. A plasticizer obtained or obtainable by the method according to any one of embodiments 1 to 21, preferably (g).

[0091] 24. Use of a polymer obtained or obtainable from the method according to any one of embodiments 1 to 21, preferably (e) and / or (f), and / or a polymer according to embodiment 22, for preparing a polymer product, preferably a soft polymer product, comprising at least one plasticizer, wherein the at least one plasticizer is preferably REACH approved.

[0092] 25. Use of a plasticizer obtained or obtainable from the method according to any one of embodiments 1 to 21, preferably (g), and / or a plasticizer according to embodiment 23, optionally after one or more post-treatment steps, for preparing a soft polymer.

[0093] 26. A method for producing a product, comprising: (I) providing a polymer according to embodiment 22; (II) producing a polymer product, preferably a flexible polymer product, from the polymer provided in (I) by adding at least one plasticizer, preferably REACH approved; A method comprising:

[0094] 27. A method for producing a flexible polymer product, comprising: (I) providing a plasticizer according to embodiment 23 and a polymer; (II) preparing a soft polymer material from the polymer and plasticizer provided in (I); A method comprising:

[0095] 28. The method of embodiment 27, wherein the polymer provided in (I) is a polymer as defined in any one of embodiments 3 to 5.

[0096] 29. A method for further processing a plasticizer, preferably the plasticizer according to embodiment 23, more preferably a plasticizer obtained or obtainable from the method according to any one of embodiments 1 to 21, preferably (g), comprising one or more post-treatment steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

[0097] 30. The method of further processing according to embodiment 29, wherein the hydrolysis comprises contacting the plasticizer with water, and optionally with a base or an acid, and / or optionally under electromagnetic radiation, preferably light.

[0098] 31. The method of further processing according to embodiment 29, wherein hydrogenating comprises contacting the plasticizer with a hydrogen (H2)-containing gas under hydrogenating conditions, preferably hydrogenating conditions that allow hydrogenation of the aromatic ring core.

[0099] 32. A method of further processing according to embodiment 29, wherein the transesterification comprises contacting the plasticizer with an alcohol having a higher boiling point than the alcohol constituting the alcohol portion of the plasticizer, optionally in the presence of an acidic or basic catalyst.

[0100] The present invention will be further illustrated by the following Reference Examples, Comparative Examples, and Examples.

[0101] Example method <Hazen color index>: The Hazen color index (APHA color number) was determined in accordance with DIN EN ISO 6271:2016-05 (Pt / Co, APHA, ASTM D1209, D5386).

[0102] <gpc>: Sample preparation Approximately 20 mg of the sample was dissolved in 10 ml of eluent (THF) overnight. All sample solutions were filtered through Macherey-Nagel PTFE (0.2 μm) before injection. The sealed sample vials were placed in an autosampler.

[0103] Experimental conditions An Agilent 1200 HPLC system consisting of an isocratic pump, a vacuum degasser, an autosampler, and a column oven (35 °C) was used. As detectors, a differential refractive index (DRI) detector and a variable ultraviolet (UVW) detector were used. Data acquisition and data processing of conventional SEC data were performed by WinGPC Unichrom of PSS (Polymer Standard Services), build 9666. A combination of an Agilent Plgel 10μ Guard (7.5×50 mm) column and three PLgel MIXED-B columns (7.5×300 mm, 10 μ) was connected in series. As the eluent, THF was used at a flow rate of 1 mL / min. 100 μL of each sample solution was injected. Calibration was performed with a narrow molar mass distribution polystyrene standard (Polymer Standard Services) having a molar mass range from M = 580 to M = 6,870,000 g / mol. Molar masses outside this range were extrapolated. The lowest possible integration limit was set to 25 ml (M(1800) approximately). Due to the possibility of polymer additives or solvent impurities, lower molar masses could not be obtained.

[0104] <GC area %>: The sample was analyzed by gas chromatography (GC), and the individual components of the sample were detected depending on their individual retention times by this method. The concentration of the individual components in the sample was given as GC area % in its percent peak area.

Table 1

[0105] <Reference Example 1: General procedure for extracting plasticizer from flexible PVC> A flexible PVC sample was cut / shredded into small pieces and placed in a reaction vessel (e.g., flask, tube, or reactor). Gamma-valerolactone (GVL) was added (at a polymer material:GVL mass ratio ranging from 1:1 to 1:100, preferably 1:1 to 1:10), and the mixture was heated to a temperature ranging from 100 to 150 °C using an appropriate heating system (e.g., oil bath, heating block, or mini-plant). After 0.1 to 4 hours, the mixture was cooled to 80 °C, 60 °C, or room temperature, and iPrOH was added at that temperature to precipitate the PVC. The mixture was filtered at room temperature, yielding a liquid phase containing plasticizer-enriched iPrOH and GVL, and a solid residue containing PVC. The PVC residue was washed with a small amount of iPrOH. The resulting PVC residue was dried (e.g., in a vacuum compartment dryer).

[0106] Example 1: Removal of plasticizer from flexible PVC Samples of flexible PVC were treated as described in Reference Example 1. All samples contained a known amount of the same plasticizer, Hexamoll DINCH (60 phr, i.e., 36.9% by weight, based on the total weight of the flexible PVC sample, including PVC and plasticizer, which was 100% by weight). After treatment, the liquid phase containing the plasticizer-enriched iPrOH and GVL was analyzed by GC. The PVC residue was further extracted by conventional extraction methods (using methylal) to determine the residual amount of plasticizer. The treatment conditions for GVL extraction and the residual amount of Hexamoll DINCH in the PVC after GVL extraction, i.e., the amount extracted in a subsequent step using methylal, are shown in Table 1 below.

[0107] [Table 2]

[0108] The molecular weights and dispersities of the polymers before and after treatment are listed in Table 2 below:

[0109] [Table 3]

[0110] Recycling of solvent GVL and obtaining plasticizers To recycle the solvent used, first the iPrOH was distilled off, and then the GVL was distilled off. The following parameters were applied to distill the GVL: temperature in the range of 50-200°C, pressure in the range of 2 hPa to ambient pressure (1013 hPa). Preferably, a temperature in the range of 70-110°C and a pressure in the range of 5-30 hPa were applied. After evaporation of the solvent, the remaining liquid was Hexamol DINCH.

[0111] The resulting GVL was more than 99% pure by GC. For GVL, the Hazen color index was determined to be 15 after distillation. For isopropanol, the Hazen color index was determined to be 0 after distillation.

[0112] Comparative Example 1: Removal of plasticizer from flexible PVC using different solvents A flexible PVC sample was cut / shredded into small pieces and placed in a reaction vessel (e.g., flask, tube, or reactor). iPrOH was added, and the mixture was stirred under reflux (approximately 82°C) for 2 hours. Visual inspection revealed that the PVC did not dissolve—in contrast to Reference Example 1 / Examples 1-7, no iPrOH was added to precipitate the PVC. The mixture was cooled to room temperature and then filtered, yielding a liquid phase containing the respective solvents enriched with the plasticizers and a solid residue containing the PVC. The PVC residue was washed with a small amount of iPrOH. The PVC thus obtained was dried (e.g., in a vacuum compartment dryer).

[0113] The dried PVC residue thus obtained was further extracted by a conventional extraction method - the same as in Example 1 (using methylal) - to determine the residual amount of plasticizer. The process conditions for solvent extraction and the residual amount of Hexamoll DINCH in the PVC after solvent extraction, i.e. the amount extracted in a subsequent step using methylal, are shown in Table 3 below.

[0114] Comparative Examples 2 and 3: Removal of plasticizer from flexible PVC using different solvents with extended extraction A flexible PVC sample was cut / shredded into small pieces and placed in a reaction vessel (e.g., flask, tube, or reactor). The respective solvent was added, and the mixture was stirred under reflux at ambient pressure in the range of 1000-1050 hPa for 4 hours. Visual inspection revealed that PVC did not dissolve in MeOH and in the mixture of MeOH and methyl propanoate—in contrast to Reference Example 1 / Examples 1-7, no iPrOH was added to precipitate the PVC. The mixture was cooled to room temperature and then filtered, yielding a liquid phase containing the respective solvent enriched with the plasticizer and a solid residue containing the PVC. The PVC thus obtained was dried (e.g., in a vacuum compartment dryer).

[0115] The dry PVC residue thus obtained was further extracted by a conventional extraction method - the same as in Example 1 (using methylal) - to determine the residual amount of plasticizer. The process conditions for solvent extraction and the residual amount of Hexamoll DINCH in the PVC after solvent extraction, i.e. the amount extracted in a subsequent step using methylal, are shown in Table 3 below.

[0116] [Table 4]

[0117] <Result> As can be seen when considering Examples 1-7 and Comparative Examples 1-3, the use of GVL for plasticizer extraction allowed significantly higher removal of plasticizer from flexible PVC compared to the use of iPrOH, MeOH, or a mixture of MeOH + methyl propanoate - with GVL more than 95% of the plasticizer was removed, compared to at most 81.6% with the different solvents.

[0118] <Cited documents> International Publication No. 01 / 70865 Brochure International Publication No. 02 / 14413 Brochure U.S. Patent No. 4,071,479 Becker / Braun, Kunststoff-Handbuch, Band 2 / 1: Polyvinylchlorid”, 2nd edition, Carl Hanser Verlag, Munich ULLMANN'S Encyclopedia of Industrial Chemistry (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2012, Volume 33, Chapter "Solvents", pages 619-688; DOI: 10.1002 / 14356007.a24_43 Handbuch der mechanischen Fest-Flussig-Trennen Taschenbuch-April 29, 2004 von Klaus Luckert(Herausgeber)< / gpc>

Claims

1. 1. A method for removing plasticizers from a polymeric material, comprising: (a) providing a polymeric material comprising a polymer and a plasticizer, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with a solvent comprising the gamma-valerolactone, thereby obtaining a liquid mixture comprising the solvent, a dissolved polymer, and a dissolved plasticizer; A method comprising:

2. (c) precipitating the polymer from the mixture obtained in (b) by adding an anti-solvent, thereby obtaining a solid residue comprising the polymer and a liquid phase comprising the solvent, the anti-solvent and the dissolved plasticizer. The method of claim 1 further comprising:

3. The polymer is a thermoplastic polymer selected from the group consisting of thermoplastic polymers, preferably copolymers, wherein the thermoplastic polymer comprises at least two different monomers in polymerized form, the at least two monomers being selected from the group consisting of C ２ ~C １０ Monoolefins (preferably selected from the group consisting of ethylene, propylene, 1,3-butadiene, 2-chloro-1,3-butadiene and mixtures of two or more of these olefins), vinyl alcohol, C of vinyl alcohol ２ ~C １０ copolymers (TP.1) selected from the group consisting of alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates having an alcohol component of branched or unbranched C1-C10 alcohols, methacrylates having a branched or unbranched C1-C10 alcohol component, vinyl aromatics (preferably styrene), (meth)acrylonitrile, ethylenically unsaturated mono- or dicarboxylic acids, and maleic anhydride; polyvinyl esters (TP.2); polycarbonates (TP.3); polyethers (TP.4); polyether ketones (TP.5); thermoplastic polyurethanes (TP.6); polysulfides (TP.7); polysulfones (TP.8); polyesters (TP.9); polyalkylene terephthalates (TP.10); polyhydroxyalkanoates (TP.11); polybutylene succinate (TP.12); polybutylene succinate adipate (TP.13); from C4 to C8 alcohols, preferably butanol, hexanol, octanol, and 2-ethylhexanol. Polyacrylates with the same or different alcohol residues from the group consisting of selected alcohols (TP.14); polymethyl methacrylate (TP.15); methyl methacrylate-butyl acrylate copolymer (TP.16); acrylonitrile-butadiene-styrene copolymer (TP.17); ethylene-propylene copolymer (TP.18); ethylene-propylene-diene copolymer (TP.19); polystyrene (TP.20); styrene-acrylonitrile copolymer (TP.21); acrylonitrile-styrene acrylate (TP. 22); styrene-butadiene-methyl methacrylate copolymer (TP.23); styrene-maleic anhydride copolymer (TP.24); styrene-methacrylic acid copolymer (TP.25); polyoxymethylene (TP.26); polyvinyl alcohol (TP.27); polyvinyl acetate (TP.28); polyvinyl butyral (TP.29); polyvinyl chloride (TP.30); polycaprolactone (TP.31); polyhydroxybutyric acid (TP.32); polyhydroxyvaleric acid (TP.33); polylactic acid (TP.34); ethyl cellulose (TP.35);3. The method of claim 1 or 2, wherein the thermoplastic polymer is selected from the group consisting of cellulose acetate (TP.36); cellulose propionate (TP.37); and cellulose acetate butyrate (TP.38), and blends of two or more of these polymers.

4. 4. The method according to claim 1, wherein the polymer is selected from the group consisting of copolymers comprising vinyl chloride in polymerized form and at least one further monomer selected from the group set out in claim 3 for TP.1; polyvinyl acetate (TP.28); polyvinyl butyral (TP.29); polyvinyl chloride (TP.30); polycaprolactone (TP.31); and blends of two or more of these polymers; the polymer preferably comprises polyvinyl chloride (TP.30), wherein more preferably at least 90%, more preferably at least 95%, more preferably at least 98% by weight of the polymers contained in the polymeric material are polyvinyl chloride, based on the total weight of the polymers contained in the polymeric material being 100% by weight.

5. The gamma-valerolactone-containing solvent comprises gamma-valerolactone and, optionally, water and a log K ＯＷ one or more solvents selected from the group consisting of organic solvents having the formula: ｎ -H (n is an integer ranging from 2 to 1000), C1 to C10 alkyl-O-C3 to C10 alkyl ether, C3 to C10 cyclic ether optionally substituted with one or more C1 to C6 alkyl groups, C6 to C10 aromatic hydrocarbon optionally substituted with one or more C1 to C6 alkyl groups, C2 to C10 aliphatic ester, C8 to C11 aromatic ester, C5 to C10 cyclic carboxylic acid ester (lactone), C3 to C12 amide, preferably R １ R ２ N-C(=O)-R ３ (In the formula, R １ , R ２ are independently a C1-C4 alkyl group, and R ３ is selected from the group consisting of a C1-C9 alkyl group, a C1-C10 ester group, and a C1-C6 ether group; a C3-C6 lactam optionally substituted with one or more substituents selected from a C1-C6 alkyl group, a C1-C6 ester group, and a C1-C6 ether group; and one or more solvents selected from the group consisting of a C5 imidazolidine optionally substituted with one or more C1-C6 alkyl groups, and a C5-C7 imidazolidone optionally substituted with one or more C1-C6 alkyl groups.

6. The plasticizer is selected from the group consisting of: - cyclohexane-1,2-dicarboxylic acid dialkyl esters, wherein the alkyl groups are independently selected from C4 to C13 alkyl; - cyclohexane-1,3-dicarboxylic acid dialkyl esters, wherein the alkyl groups are independently selected from C4 to C13 alkyl; - cyclohexane-1,4-dicarboxylic acid dialkyl esters, wherein the alkyl groups are independently selected from C4 to C13 alkyl; - phthalic acid dialkyl esters, wherein the alkyl groups are independently selected from C4 to C13 alkyl; - phthalic acid alkylaryl esters, in which the alkyl group is selected from C4 to C13 alkyl and the aryl group is selected from benzyl and phenyl; - terephthalic acid dialkyl esters, wherein the alkyl groups are independently selected from C4 to C13 alkyl; - Trimellitic acid trialkyl ester; - alkyl benzoates; - dibenzoic esters of glycols; - pentaerythritol esters; saturated monocarboxylic acid alkyl esters; - unsaturated monocarboxylic acid esters; saturated dicarboxylic acid diesters; - unsaturated dicarboxylic acid diesters; aromatic sulfonates; alkylsulfonates; - glycerol esters; - isosorbide esters; - phosphate esters; - citric acid triester; - acetylated citrate triester; - alkylpyrrolidone derivatives; 2,5-furandicarboxylic acid dialkyl esters; 2,5-tetrahydrofurandicarboxylic acid dialkyl esters; polyesters of aliphatic and / or aromatic polycarboxylic acids and at least dialcohols; - epoxidized vegetable oil; epoxidized fatty acid monoalkyl esters; and mixtures of two or more thereof; 6. The method of claim 1, wherein the compound is selected from the group consisting of:

7. 7. The method of any one of claims 1 to 6, wherein in (b), contacting the polymeric material with the solvent comprising gamma-valerolactone is carried out at a temperature T1 of less than 190°C; and / or in (b), contacting the polymeric material with the solvent comprising gamma-valerolactone is carried out for a time period of at least 0.1 hours; and / or in (b), contacting the polymeric material with the solvent comprising gamma-valerolactone is carried out at a pressure in the range of 800 to 200,000 hPa.

8. Step (c) (c.1) adjusting the temperature to a temperature T2 less than T1, preferably in the range of 10°C to 100°C, preferably in the range of 15 to 90°C, more preferably in the range of 20 to 80°C; (c.2) precipitating the polymer from the mixture obtained in (b) at T2 by addition of an anti-solvent; thereby obtaining a solid residue comprising said polymer and a liquid phase comprising said solvent, said anti-solvent and dissolved plasticizer; 8. The method of claim 2, comprising:

9. 9. The process of any one of claims 2 to 8, wherein the anti-solvent used in step (c) or (c.2) is selected from the group consisting of water, C1-C5 monoalcohols, C1-C6 dialcohols, and mixtures of two or more of these solvents, preferably selected from the group consisting of water, C1-C5 monoalcohols, C1-C5 dialcohols, and mixtures of two or more of these solvents, more preferably selected from the group consisting of water, C1-C3 monoalcohols, and mixtures of two or more of these solvents, more preferably said anti-solvent used in step (c) or (c.2) comprises isopropanol, more preferably at least 95% by weight of the anti-solvent used in step (c) or (c.2) consists of isopropanol.

10. (d) separating the polymer-containing solid residue obtained in (c) or (c.2) from a liquid phase comprising the solvent, the anti-solvent and the dissolved plasticizer, thereby obtaining a polymer-containing solid residue and a liquid phase comprising the solvent, the anti-solvent and the dissolved plasticizer; (e) optionally washing the solid residue obtained in (d) with an anti-solvent; (f) drying the solid residue obtained in (d) or the washed solid residue obtained in (e); and preferably includes one or more post-processing steps, wherein the one or more post-processing steps preferably include: (g) separating the solvent and anti-solvent by distillation and / or separating the solvent from the dissolved plasticizer by distillation, thereby preferably obtaining a liquid fraction comprising said plasticizer and one or more liquid fractions comprising said solvent and / or said anti-solvent.

10. The method of claim 1, comprising:

11. A polymer obtained or obtainable from a process according to any one of claims 1 to 10, preferably (e) and / or (f) according to claim 10.

12. A plasticizer obtained or obtainable from the method according to any one of claims 1 to 10, preferably (g).

13. 12. Use of a polymer obtained or obtainable from the method according to any one of claims 1 to 10, preferably (e) and / or (f) according to claim 10, and / or a polymer according to claim 11, for producing a polymer product, preferably a soft polymer product, comprising at least one plasticizer, said at least one plasticizer preferably being REACH approved.

14. Use of a plasticizer obtained or obtainable from the method according to any one of claims 1 to 10, preferably (g) according to claim 10, and / or a plasticizer according to claim 12, optionally after one or more post-treatment steps, for preparing a soft polymer.

15. 13. A method for further processing a plasticizer, preferably a plasticizer according to claim 12, more preferably a plasticizer obtained or obtainable from a method according to any one of claims 1 to 10, preferably (g), comprising one or more steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

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