Method for removal of an additive from a polymeric material

Abstract

The present invention relates in a first aspect to a method for removal of an additive from a polymeric material comprising: (a) providing a polymeric material, which comprises a polymer and a metal cation containing additive, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, and obtaining an undissolved part of the additive comprising the metal cation; and (c) filtrating the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b), and a residue comprising the undissolved part of the additive. In a second aspect, the present invention is directed to a polymer obtained or obtainable from the method according to the first aspect. A third aspect of the invention is related to a plasticizer obtained or obtainable from the method according to the first aspect. In a fourth aspect, the invention is related to the use of the polymer of the second aspect of the invention for preparing a polymeric product. A fifth aspect of the invention is related 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 invention is related to a process for further processing a plasticizer, the process comprising one or more work-up steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification. A seventh aspect of the invention is directed to a polymer comprising in the range of from 0.001 to 0.1 weight-% of gamma-valerolactone, based on the total weight of the polymer being 100 weight-%.

Description

[0001] Method for removal of an additive from a polymeric material

[0002] The present invention relates in a first aspect to a method for removal of an additive from a polymeric material comprising: (a) providing a polymeric material, which comprises a polymer and a metal cation containing additive, and providing a solvent comprising gamma-valerolac- tone; (b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, and obtaining an undissolved part of the additive comprising the metal cation; and (c) filtrating the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b), and a residue comprising the undissolved part of the additive. In a second aspect, the present invention is directed to a polymer obtained or obtainable from the method according to the first aspect. A third aspect of the invention is related to a plasticizer obtained or obtainable from the method according to the first aspect. In a fourth aspect, the invention is related to the use of the polymer of the second aspect for preparing a polymeric product. A fifth aspect of the invention is related 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 invention is related to a process for further processing a plasticizer, the process comprising one or more steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification. A seventh aspect of the invention is directed to a polymer comprising in the range of from 0.001 to 0.1 weight-% of gamma-valerolactone, based on the total weight of the polymer being 100 weight-%.

[0003] State of the art

[0004] Synthetic polymers are commonly used in two different forms, i.e. in rigid form or in flexible, so called soft form. Softening is normally achieved by the addition of plasticizers to the polymeric materials, the most widely used being phthalates. Furthermore, additives are normally to be found in synthetic polymers, especially additives containing metal cations such as lead (Pb) cations, which were used as stabilizers. These are so called “Legacy additives”, which are plastic additives that were not subject to regulation during production of the respective polymers, but are now regulated by REACh, RoHS or other legal requirements in new products and therefore also in recyclates.

[0005] In view of the increasing use of polymeric materials, also the need for recycling of polymeric materials has arisen in view of saving of raw materials as well as in view of reduction of plastic waste. However, for recycling, there is also a need to separate the polymeric materials from the incorporated additives, especially in view of the fact that several metal cation containing additives are toxic or are connected with other environmental or health related issues, especially since it is sometimes intended to use the recycled polymeric materials in a different area of application - for example, a polymer used for a window profile shall be reused for a toy. Thus, recycling is in most cases only possible after extraction of additives, wherein a mild method for separation of polymeric material and additive would be highly desirable. “Mild” preferably meaning that first, harmless chemicals are used and second, that the polymers) and optionally further components contained in the material such as plasticizer(s) are recovered undamaged. However, so far, the methods known in the art use fossil-based chemicals, which are at least partly toxic and the processes for additive extraction are complicated and required complex solvent systems.

[0006] WO 02 / 14413 A1 discloses a process for separating and recovering target polymers and their additives from a material containing polymers, wherein the target polymer and at least one additive are dissolved in a solvent, the dissolved target polymer with the additives is mixed with a non-aqueous solvent II (precipitating agent), which is miscible with the solvent I, in such a manner that the target polymer is precipitated. Solvent I is selected from the group of low molecular alcohols (C1-C5), cyclic ethers (e.g. tetrahydrofuran), aliphatic ketones (e.g. acetone, methylethylketone), cyclic ketones (e.g. cyclohexanone), dibasic ester mixtures (e.g. DBE -mixtures of dimethyl esters of dicarboxylic acids such as glutaric acid, succinic acid and adipic acid) and mixtures of these solvents, the solvent II is a low molecular alcohol (C1-C5). Also here, the solvents used for dissolution of the polymer are dangerous and connected to several health issues, as indicated, for example, for MEK above. US 4,071,479 A relates to a process for recovering a reusable essentially pure vinyl chloride polymer resin from a polymer mixture including dissolution of the vinyl chloride polymers and subsequently use of a non-solvent which is miscible with the solvent in substantially all proportions to precipitate an essentially pure vinyl chloride polymer resin. The solvents indicated for dissolution of the polymer are methyl ethyl ketone, tetrahydrofuran, and dimethyl formamide, the antisolvent being selectable from methanol, isopropanol, n-butanol, or an azeotrope of methyl ethyl ketone and methanol. Also here, the solvents used for dissolution of the polymer are dangerous and connected to several health issues, as indicated, for example, for MEK above. CN 115784886 A discloses a method for removing plasticizer from PVC leather including use of a mixture of alkane and alcohol as solvent.

[0007] However, very few methods are known for separating additives from a polymeric material wherein the polymeric material can be recovered undamaged and additive free. The object underlying the present invention was thus the provision of an improved process, which enables a simple extraction of one or more additives(s) from a polymeric material while avoiding or at least reducing the use of hazardous solvent(s) and which enables to recover the polymer(s) and optionally further components such as plasticizer(s) undamaged.

[0008] In a first aspect, the invention thus relates to a method for removal of an additive from a polymeric material comprising:

[0009] (a) providing a polymeric material, which comprises a polymer and a metal cation containing additive, and providing a solvent comprising gamma-valerolactone;

[0010] (b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, and obtaining an undissolved part of the additive comprising the metal cation;

[0011] (c) filtrating the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b), and a residue comprising the undissolved part of the additive.

[0012] It has been surprisingly found that, especially for polymeric materials comprising one or more polymer(s) as described below, especially for polymeric materials comprising polyvinylchloride (PVC, TP.30 below), gamma-valerolactone enables a removal of metal containing additive, and optionally also of plasticizer, from the polymeric material without detrimental effects on the polymeric material, i.e. the polymeric material obtained, which is depleted in metal containing additive and optionally in plasticizer, compared to the polymeric material provided in (a), has at least the same number average molar mass Mn and has about the same weight average molar mass Mw as the polymeric material provided in (a). That is, using GVL, combined with precipitation as described in more detail below, enables to recover the polymer(s) in undamaged form.

[0013] “Depleted of metal cation compared to the liquid mixture obtained in (b)“ means that the liquid mixture, which comprises the solvent and dissolved polymer, obtained in (c) comprises at least 15 weight-%, preferably at least 40 weight-%, more preferably at least 50 weight-%, more preferably at least 60 weight-%, more preferably at least 70 weight-%, more preferably at least 80 weight-%, more preferably at least 90 weight-%, more preferably at least 95 weight-%, less metal cation compared to the liquid mixture obtained in (b). The liquid mixture, which comprises the solvent and dissolved polymer, obtained in (c), is also called “the filtrate”. The “undissolved part of the additive” remains after the filtration of (c) on the filter. The additive is preferably composed of the metal cation, which has a positive charge, and an organic component having a negative charge equivalent to the positive charge of the metal cation. Said organic component having a negative charge is preferably also at least partially dissolved in the liquid mixture after filtration, i.e. then forms a part of the filtrate.

[0014] Gamma-valerolactone (CsHsCh; IIIPAC: 5-methyloxolan-2-one, abbreviation: GVL) is obtainable from carbohydrate-based biomasses, for example, it is readily obtained from sugar, and is thus a "green" solvent. It had so far only been described at the outmost 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 GVL tested to comprise biobased carbon according to ASTM Standard D6866-16.

[0015] Additive

[0016] In some preferred embodiments of the method for removal of additive, the metal cation contained in the additive is a metal cation having a charge of >2, preferably the metal cation contained in the additive is selected from divalent metal cation, trivalent metal cation, tetravalent metal cation and mixtures of two or more thereof, wherein the metal cation comprised in the additive is preferably selected from the group consisting of Sn4+, Zn2+, Ba2+, Cd2+, Ca2+, Pb2+, Mg2+, Al3+and mixtures of two or more of these metal cations, preferably from the group consisting of Cd2+, Pb2 +, Zn2+, Ba2+and mixtures of two or more of these metal cations, more preferably from the group consisting of Cd2+, Pb2 +and mixtures of Cd2+and Pb2 +or from the group consisting of Zn2+, Ba2+and mixtures of Zn2+and Ba2+.

[0017] In some preferred embodiments of the method for removal of additive, the additive, which comprises a metal cation, is selected from the group consisting of organo tin(IV) mercaptide, organo tin(IV) sulfide, organo tin(IV) carboxylate, substituted or unsubstituted barium(ll) phenolate, barium(ll) salt of carboxylic acid, cadmium(ll) salt of carboxylic acid, calcium(ll) salt of carboxylic acid, aluminum(lll) salt of carboxylic acid, zinc(ll) salt of carboxylic acid, substituted or unsubstituted zinc(ll) phenolate, lead(ll) sulfate, lead(ll) phosphite, lead(ll) carbonate, lead(ll) salt of carboxylic acid, magnesium(ll) salt of carboxylic acid, hydroxide carbonate hydrate of two or more of metal cations, and mixtures of two or more of these compounds, preferably from the group consisting of aluminum stearate, barium laurate, barium stearate, cadmium laurate, cadmium stearate, calcium laurate, calcium stearate, lead stearate [Pb(OOC-Ci7H35)2], dibasic lead stearate [2PbO Pb(OOC-Ci7H35)2], tribasic lead sulphate (3PbO PbSO4'H2O), tetrabasic lead sulphate ( 4PbO • PbSO4 ), dibasic lead phthalate, basic lead carbonate and mixtures of two or more of these compounds. The polymeric material preferably contains the metal cation containing additive in the range of from 0.05 to 7 weight-% based on the total weight of the polymeric material being 100 weight-%. Preferably, the content of the metal cation containing additive is in the range of from 0.1 to 5 weight-%, more preferably in the range of from 0.5 to 3 weight-%.

[0018] Contacting in step (b)

[0019] In some preferred embodiments of the method for removal of additive, contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done at a temperature T1 below 190 °C, preferably below 180°C, more preferably below 170°C, more preferably at a temperature T1 in the range of from 90 to < 170°C, more preferably a temperature T 1 in the range of from 95 to 165 °C, more preferably a temperature T1 in the range of from 100 to 150 °C.

[0020] In some preferred embodiments of the method for removal of additive, contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done for a period of time of at least 0.1 h, preferably for a period of time in the range of from 0.1 to 10 h, preferably for a period of time in the range of from 0.1 to 6 h, more preferably for a period of time in the range of from 0.1 to 4 h.

[0021] In some preferred embodiments of the method for removal of additive, contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done at a pressure in the range of from 800 to 200,000 hPa.

[0022] In some preferred embodiments of the method for removal of additive, contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done with a mass based ratio polymeric material : solvent in the range of 1 :1 to 1 :100 more preferably in the range of from 1 :1 to 1:20, more preferably in the range of from 1 :1 to 1:10.

[0023] “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 polymer’s surface are in contact with the solvent, based on the total surface of the polymer material being 100%.

[0024] Filtration in step (c) In some preferred embodiments of the method for removal of additive, filtration in (c) is done by heated filtration, more preferably by heated filtration at a temperature in the range of T1 ± 20°C, more preferably by heated filtration at a temperature in the range of T1 ± 10°C.

[0025] In heated filtration, the solution, filter, and funnel are heated, more preferably heated so that each has temperature T1 ± 20°C or T1 ± 10°C.

[0026] In some preferred embodiments of the method for removal of additive, filtration in (c) is done at a pressure of >1 ,000 hPa, more preferably at a pressure in the range of from 1 ,000 to 30,000 hPa, preferably in the range of from 1,000 to 10,000 hPa, more preferably in the range of from 1 ,000 to 6,000 hPa (heated pressure filtration).

[0027] In some preferred embodiments of the method for removal of additive, filtration in (c) is done using a filter having a nominal rating of < 30 pm, more preferably < 25 pm, more preferably <10 pm, more preferably < 5 pm.

[0028] In some embodiments, the filter has preferably a nominal rating in the range of from 0.1 to 30 pm, more preferably in the range of from 0.1 to 25 pm, more preferably in the range of from 0.2 to 10 pm. The nominal rating values indicated herein preferably mean that the filter prevents 90% of all particles having the indicated average diameter or having a larger average diameter from passing through. In case of unsymmetrical particles, the average diameter is related to the particle’s largest diameter.

[0029] In some preferred embodiments of the method for removal of additive, filtration in (c) is done using a filter comprising an organic material or an inorganic material, more preferably a filter comprising an organic material, more preferably a filter comprising a cellulose matrix.

[0030] In some preferred embodiments of the method for removal of additive, (c) comprises

[0031] (c.1a) adding a filteraid to the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, an undissolved part of the additive comprising the metal cation, and filteraid; and

[0032] (c.2a) filtrating the liquid mixture obtained in (c.1a); or

[0033] (c.1b) providing a filter having deposited thereon filteraid; and

[0034] (c.2b) filtrating the liquid mixture obtained in (b) over the filter provided in (c.1b); thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b) or (c.1a), and a residue comprising the undissolved part of the additive.

[0035] In some preferred embodiments of the method for removal of additive, the filteraid is selected from the group consisting of powdered cellulose, diatomaceous earth, perlite, activated carbon, aluminum oxide, clay, silica, glass wool, absorbend cotton (cotton wool), magnesium silicate, (MgAI)2Si4O (OH) ■ 4 H2O, (MgAQsSisCho ■ 4 H2O, aluminum phyllosilicate clay composed of montmorillonite, (Ca,Na)o,3(AI,Mg)2Si40 (OH)2 n H2O, sodium alumino ortho silicate (Na2O.AI2O3.xSiO2.yH2O), aluminosilicate, sawdust, chitosan, agriculture or industrial waste, mud, fly ash, paper mill waste, AI2O3, SiO2, Fe2O3, FesO4, TiO2, ZnO, MgO a composite of two or more of these metal oxides, mesoporouse ball clays (MBCs), ZnFe2O4, MnFe2O4, NiFe2O4, CoFe2O4, CuFe2O4, ion exchanger resin, and mixtures of two or more thereof. An ion exchanger resin is preferably a cation exchanger resin, more preferably an acidic cation exchanger resin, for example Amberlyst 15 (CAS no. 39389-20-3).

[0036] In some preferred embodiments of the method for removal of additive, the filteraid in mixture with water and / or organic solvent has a pH value > 7, preferably in the range of from 7 to 11. The pH value of an aqueous mixture of the respective filteraid, or of a mixture of the respective filteraid in a suitable organic solvent, for example, DMSO, is preferably determined by a pH sensitive electrode, preferably a pH sensitive glass electrode, and / or by pH paper]

[0037] In some preferred embodiments of the method for removal of additive, the filteraid is selected from the group consisting of powdered cellulose, diatomaceous earth, perlite, activated carbon, clay, silica, glass wool, absorbend cotton (cotton wool), magnesia silicate, and mixtures of two or more thereof, preferably from the group consisting of powdered cellulose, diatomaceous earth, perlite, and mixtures of two or three thereof, more preferably the filteraid is powdered cellulose, diatomaceous earth, magnesia silicate or a mixture of two or more thereof.

[0038] In some preferred embodiments of the method for removal of additive, the filteraid is added in (c.1a) in a weight-based ratio with respect to the amount of polymeric material provided in (a) in the range of from 0.5 to 50 weight-%, preferably in the range of from 1 to 20 weight-%.

[0039] In some preferred embodiments of the method for removal of additive, the filteraid is deposited on the filter, which has a diameter D(f), in (c.1b) as a layer having a thickness LT(f) with 0.01 <LT(f) / D(f) < 2, preferably 0.05 <LT(f) / D(f) < 1. A filteraid is normally used for improving filtering efficiency by building up a porous, permeable and rigid lattice structure and preventing clogging of the filter. However, in the present invention, it has surprisingly found that using a filteraid also improves the retaining of a metal cation containing residue on the filter, thus reducing the amount of metal cation in the filtrate and, consequently, also in the polymeric material once precipitated from the liquid mixture. The liquid mixture obtained from the filtration in (c), (c.2a) or (c.2b) comprises less than 1 weight-%, preferably less than 0.5 weight-%, of the filteraid added in (c.1a) or deposited on the filter in (c.2a).

[0040] Plasticizer

[0041] In some preferred embodiments of the method for removal of additive, the polymeric material provided in (a) comprises a polymer, a metal cation containing additive and a plasticizer.

[0042] In some preferred embodiments of the method for removal of additive, the liquid mixture obtained in (b) comprises the solvent, dissolved polymer, at least partially dissolved plasticizer, and at least partially undissolved additive.

[0043] In some preferred embodiments of the method for removal of additive, the liquid mixture obtained from filtration in (c) comprises the solvent, dissolved polymer, and at least partially dissolved plasticizer.

[0044] In some preferred embodiments, the method for removal of additive further comprises:

[0045] (d) precipitating the polymer from the liquid mixture obtained from filtration in (c) by addition of an anti-solvent, thereby obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the at least partially dissolved plasticizer.

[0046] The solid residue, which comprises the polymer, comprises at least 15 weight-%, preferably at least 40 weight-%, more preferably at least 50 weight-%, more preferably at least 60 weight-%, more preferably at least 70 weight-%, more preferably at least 80 weight-%, more preferably at least 90 weight-%, more preferably at least 95 weight-%, less metal cation compared to polymeric material provided in (a). The additive, as described above, is preferably composed of the metal cation, which has a positive charge, and an organic component having a negative charge equivalent to the positive charge of the metal cation. Said organic component remains also on the filter and / or is dissolved in the liquid mixture (the filtrate) after filtration. In cases where the organic component or at least a part thereof is dissolved in the liquid mixture after filtration, step (d) results in obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the dissolved plasticizer as well as the organic component of the additive or the part thereof.

[0047] In some preferred embodiments of the method for removal of additive, step (d) comprises: (d.1) adjusting the temperature to a temperature T2, which is below T1 , preferably a temperature in the range of from 10 °C to 100 °C, more preferably a temperature in the range of from 15 to 90°C, more preferably in the range of from 20 to 80°C;

[0048] (d.2) precipitating the polymer from the liquid mixture obtained from filtration in (c) at T2 by addition of an anti-solvent; thereby obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the dissolved plasticizer.

[0049] A solvent is defined according to ULLMANN'S Encyclopedia of Industrial Chemistry (Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim, 2012, Vol. 33, Chapter ..Solvents", pages 619 to 688, especially page 626; DOI: 10.1002 / 14356007. a24_437) as being able to dissolve a given substance such as a polymer (the solute) at room temperature; the solubility parameters of the solvent and the solute are similar. A non-solvent (synonymously named: anti-sol- vent) is defined as being unable to dissolve the substance in question. The solubility parameters and hydrogen bond parameters of an anti-solvent lie outside the solubility regions of the polymer(s) but inside the solubility regions of the substances to be dissolved, especially inside the solubility regions of the plasticizer(s).

[0050] In some preferred embodiments of the method for removal of additive, the anti-solvent used in step (d) or (d.2) is selected from the group consisting of water, C1 to C5 monoalcohol, C1 to C6 dialcohol and mixtures of two or more of these solvents, more preferably from the group consisting of water, C1 to C5 monoalcohol, C1 to C5 dialcohol and mixtures of two or more of these solvents, more preferably from the group consisting of water, C1 to C3 monoalcohol and mixtures of two or more of these solvents, more preferably the anti-solvent used in step (d) or (d.2) comprises iso-propanol, more preferably at least 95 weight-% of the antisolvent used in step (d) or (d.2) consist of iso-propanol.

[0051] In some preferred embodiments of the method for removal of additive, the anti-solvent is added in step (d) or (d.2) in a weight-based ratio anti-solvent : polymeric material in the range of from 4:1 to 75:1 , more preferably in the range of from 5:1 to 50:1 , more preferably in the range of from 5:1 to 20:1. In some preferred embodiments of the method for removal of additive, the polymer of the solid residue obtained in (d) or (d.2) comprises <40 %, more preferably < 35 % of the amount of metal cation, which had been present in the polymeric material provided in (a) and optionally comprises <5 %, preferably < 1 % of the amount of plasticizer, which had been present in the polymeric material provided in (a). In some preferred embodiments, wherein the metal cation is selected from Cd2+, Pb2+, and mixtures of Cd2+, Pb2+, the polymer of the solid residue obtained in (d) or (d.2) comprises <5 %, more preferably < 1 % of the amount of metal cation, which had been present in the polymeric material provided in (a) and optionally comprises <5 %, preferably < 1 % of the amount of plasticizer, which had been present in the polymeric material provided in (a).

[0052] In some preferred embodiments, the method for removal of additive further comprises:

[0053] (e) separating the solid residue, which comprises the polymer obtained in (d) or (d.2) from the liquid phase, which comprises the solvent, the anti-solvent and optionally the dissolved plasticizer, thereby obtaining the solid residue, which comprises the polymer and the liquid phase, which comprises the solvent, the anti-solvent and optionally the dissolved plasticizer;

[0054] (f) optionally washing the solid residue obtained in (e) with anti-solvent;

[0055] (g) drying the solid residue obtained in (e) or the washed solid residue obtained in (f).

[0056] The separation in (e) is done by methods and means known to the skilled person, especially solid-liquid separation methods such as filtration, for example, heated pressure filtration, sedimentation or centrifugation (see Handbuch der mechanischen Fest-Flussig-Tren- nung Taschenbuch - 29. April 2004 von Klaus Luckert (Herausgeber)).

[0057] In some preferred embodiments, the method for removal of additive comprises one or more work-up step(s), wherein the one or more work-up step(s) preferably comprise

[0058] (h) separating solvent and anti-solvent by distillation and / or separating solvent from optionally dissolved plasticizer by distillation, thereby optionally obtaining a, preferably liquid fraction comprising the plasticizer and one or more liquid fraction(s) comprising the solvent and / or the anti-solvent.

[0059] The optional plasticizer obtained in (h) is preferably in liquid form. Due to the higher molar masses and the resulting higher boiling temperatures of the plasticizer compared to solvent and anti-solvent, the plasticizer is not removed in distillation. In some preferred embodiments, the method for removal of additive further comprises recycling the separated solvent obtained in (h) at least partially to (a) and / or recycling the separated anti-solvent obtained on (h) at least partially to (d).

[0060] In some preferred embodiments of the method for removal of an additive from a polymeric material, the polymer is preferably a thermoplastic polymer selected from the group consisting of

[0061] - thermoplastic copolymer, which comprises in polymerized form at least two different monomers, the monomers being selected from the group consisting of C2 to C10 mono olefin (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), vinylalcohol, C2 to C10- alkylester of vinyl alcohol, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylate with alcohol component of branched or unbranched C1 to C10 alcohol methacrylate with alcohol components of branched or unbranched C1 to C10 alcohol, vinyl aromatic (preferably styrene), (meth)acrylonitrile, ethylenically unsaturated mono- or dicarboxylic acid, and maleic anhydride (TP.1); polyvinyl ester (TP.2); polycarbonate (TP.3); polyether (TP.4); polyether ketone (TP.5);

[0062] - thermoplastic polyurethane (TP.6); polysulfide (TP.7); polysulfone (TP.8); polyester (TP.9); polyalkylene terephthalate (TP.10); polyhydroxyalkanoate (TP.11); polybutylene succinate (TP.12); polybutylene succinate adipate (TP.13); polyacrylate with the same or different alcohol residues from the group of C4 to C8 alcohols, preferably selected from butanol, hexanol, octanol, and 2-ethylhexanol (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); cellulose acetate (TP.36); cellulose propionate (TP.37); cellulose acetate / butyrate (TP.38) and blends of two or more of these polymers.

[0063] In some preferred embodiments, polyethylene terephthalate (PET) is excluded from the list of polymers of TP.1 to TP.38, 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.

[0064] In some preferred embodiments, the polymer is selected from the group consisting of copolymer comprising in polymerized form vinyl chloride and at least one further monomer selected from the group consisting of C2 to C10 mono olefin (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), vinylalcohol, C2 to C10- alkylester of vinyl alcohol, vinyl acetate, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylate with alcohol component of branched or unbranched C1 to C10 alcohol methacrylate with alcohol components of branched or unbranched C1 to C10 alcohol, vinyl aromatic (preferably styrene), (meth)acrylonitrile, ethylenically unsaturated mono- or dicarboxylic acid, and maleic anhydride, more preferably copolymer comprising in polymerized form vinyl chloride and at least vinyl acetate (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.

[0065] In some preferred embodiments, the polymer comprises polyvinyl chloride (TP.30), wherein preferably at least 90 weight-%, more preferably at least 95 weight-%, more preferably at least 98 weight-%, of the polymer comprised in the polymeric material are polyvinyl chloride, based on the overall weight of the polymer comprised in the polymeric material being 100 weight-%.

[0066] In some preferred embodiments, at least 20 weight-% of the polymeric material consists of the polymer, more preferably in the range of from 20 to 90 weight-% of the polymeric material consist of the polymer, the overall weight of the polymeric material being 100 weight-%.

[0067] In general, polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl chloride is prepared, for example, by (micro)suspension polymerization, emulsion polymerisation or mass polymerization. The production of polyvinyl chloride by polymerization of vinyl chloride and 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.

[0068] In some preferred embodiments, the solvent comprising gamma-valerolactone comprises gamma-valerolactone and optionally one or more solvent(s) selected from the group consisting of water and organic solvents having a log Kow in the range of from -1 .6 to +1 .6, preferably selected from the group consisting of water, C5 to C12 alkane, aliphatic C1 to C10 alcohol, C3 to C10 ketone, C2 to C10 cyclic ketone, HO-[C1 to C10 alkyl-O-]n-H, with n being an integer in the range of 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 group(s), C6 to C10 aromatic hydrocarbon, optionally substituted with one or more C1 to C6 alkyl group(s), C2 to C10 aliphatic ester, C8 to C11 aromatic ester, C5 to C10 cyclic carboxylic ester (lactone), C3 to C12 amide, preferably R1R2N-C(=O)-R3, wherein R1, R2are independently a C1 to C4 alkyl group and R3is selected from the group consisting of C1 to C9 alkyl group, C1 to C10 ester group and C1 to C6 ether group, C3 to C6 lactame, optionally substituted with one or more substituent selected from C1 to C6 alkyl group, C1 to C6 ester group and C1 to C6 ether group, and C5 imidazolidine, optionally substituted with one or more C1 to C6 alkyl group(s), C5 to C7 imidazolidone, optionally substituted with one or more C1 to C6 alkyl group(s).

[0069] Preferably at least 1 weight-%, more preferably at least 5 weight-%, more preferably at least 10 weight-%, more preferably at least 20 weight-%, more preferably at least 30 weight-%, more preferably at least 40 weight-%, more preferably at least 50 weight-%, more preferably at least 60 weight-%, more preferably at least 70 weight-%, more preferably at least 80 weight-%, more preferably at least 90 weight-%, more preferably at least 95 weight-%, more preferably at least 95 weight-%, more preferably at least 96 weight-%, more preferably at least 97 weight-%, more preferably at least 98 weight-%, more preferably at least 99 weight-%, of the solvent consists of gamma-valerolactone based on the total weight of the solvent being 100 weight-%.

[0070] Suitable solvents are known to the skilled person, as well as the decadic logarithm of the octanol-water partition coefficient (log Ko ). The octanol-water partition coefficient Kow of a given compound is defined as the ratio of said compound’s chemical concentration in the octanol phase relative to said compound’s chemical concentration in the aqueous phase in a two-phase system of 1 -octanol and water at a temperature of 25 °C (298 K). Methods to determine the octanol-water partition coefficient Kow of a given compound are known to the skilled person. For example, the octanol-water partition coefficient Kow of a given compound is determined using the shake-flask method which consists of dissolving the compound in a volume of high-purity 1 -octanol and deionized water (pre-mixed and calibrated for at least 24 h) and measuring the concentration of the compound in each the 1-octanol phase and the water phase by a sufficiently exact method, preferably via LIV / VIS spectroscopy. This method is described in the OECD Guideline for the testing of chemicals, number 107, adopted on July 27th, 1995. Values of Kow for a plurality of substances are known and are easy to be found, for example, in the Dortmund Database (DDB, cf. http: / / www.ddbst.com / ddb-search).

[0071] Regarding suitable solvents, for example, an aliphatic C1 to C10 alcohol is preferably a C1 to C6 mono-ol, more preferably one or more selected from the group consisting of methanol, ethanol and butanol. A C3 to C10 ketone is preferably acetone or methylethyl ketone or a mixture of acetone and methylethyl ketone. A C2 to C10 cyclic ketone is preferably cyclohexanone. A C3 to C10 cyclic ether optionally substituted with one or more C1 to C3 alkyl group(s) is preferably tetrahydrofuran or 2-methyltetrahydrofuran or a mixture of tetrahydrofuran and 2-methyltetrahydrofuran. A C6 to C10 aromatic hydrocarbon, optionally substituted with one or more C1 to C3 alkyl group(s) is preferably one or more selected from the group consisting of benzene, toluene, ethylbenzene, xylene (o, m or p) and mesitylene. A C1 to C10 ester is preferably one or more selected from the group consisting of esters of a C1 to C6 aliphatic mono-ol with a C2 to C5 aliphatic acid. A C5 to C10 cyclic carboxylic ester (lactone) is preferably one or more selected from the group consisting of delta-valerolactone, methylated y-butyrolactone, ethylated y-butyrolactone, propylated y-butyrolactone, and p- propiolactone. A C3 to C6 lactame, optionally substituted with one or more C1 to C3 alkyl group(s), is preferably selected from the group consisting of 2-pyrrolidone, 3-pyrrolidone and mixtures of 2-pyrrolidone, 3-pyrrolidone, each optionally substituted with one or more C1 to C3 alkyl group(s), preferably at the nitrogen atom, more preferably N-methyl-2-pyrrolidone. An imidazolidone, optionally substituted with one or more C1 to C3 alkyl group(s) is preferably 1 ,3-dimethyl-2-imidazolidinone.

[0072] In some preferred embodiments, the optional plasticizer is selected from the group consisting of cyclohexane-1 ,2-dicarboxylic acid dialkylester, wherein the alkyl groups are independently selected from C4-C13 alkyl; cyclohexane-1 ,3-dicarboxylic acid dialkylester, wherein the alkyl groups are independently selected from C4-C13 alkyl; cyclohexane-1 ,4-dicarboxylic acid dialkylester, wherein the alkyl groups are independently selected from C4-C13 alkyl; phthalic acid dialkylester wherein the alkyl groups are independently selected from C4- C13 alkyl; phthalic acid alkylarylester wherein the alkyl group is selected from C4-C13 alkyl and the aryl group is selected from benzyl and phenyl; terephthalic acid dialkylester wherein the alkyl groups are independently selected from C4-C13 alkyl; trimellitic acid trialkylester; benzoic acid alkylester; dibenzoic acid esters of glycols; pentaerythritol esters; saturated monocarboxylic acid alkylester; unsaturated monocarboxylic acid ester; saturated dicarboxylic acid diester; unsaturated dicarboxylic acid diester; aromatic sulfonic acid ester; alkylsulfonic acid ester; glycerol ester; isosorbide ester; phosphoric acid ester; citric acid triester; acetylated citric acid triester; alkylpyrrolidone derivative;

[0073] 2.5-furane dicarboxylic acid dialkylester;

[0074] 2.5-tetrahydrofurane dicarboxylic acid dialkylester; polyester of aliphatic and / or aromatic polycarboxylic acid with at least dialcohol(s); epoxidized plant oil; epoxidized fatty acid mono alkyl ester; and mixture of two or more thereof.

[0075] A cyclohexane-1,2-dicarboxylic acid dialkyl ester has in the range of from 4 to 14 C atoms in the alkyl chain(s). The alkyl chains of the cyclohexane-1,2-dicarboxylic acid dialkyl ester independently of each other have the same or a different number of C atoms. A cyclohexane- 1 ,2-dicarboxylic acid dialkyl ester is preferably selected from the group consisting of di-(2- ethylhexyl)-1,2-cyclohexane dicarboxylate, di-(isononyl)-1 ,2-cyclohexanedicarboxylate, or di- (2-propylheptyl)-1,2-cyclohexane dicarboxylate and mixtures of two or more thereof. A cyclo- hexane-1,3-dicarboxylic acid dialkyl ester has in the range of from 4 to 14 C atoms in the alkyl chain(s). The alkyl chains of the cyclohexane-1,3-dicarboxylic acid dialkyl ester independently of each other have the same or a different number of C atoms. A cyclohexane-1 ,4- dicarboxylic acid dialkyl ester has 4 to 13 C atoms in the alkyl chains. The alkyl chains of the cyclohexane-1 ,4-dicarboxylic acid dialkyl ester independently of each other have the same or a different number of C atoms. A cyclohexane-1 ,4-dicarboxylic acid dialkyl ester is preferably selected from the group consisting of di-(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, di- (isononyl)-l ,4-cyclohexanedicarboxylate, or di-(2-propylheptyl)-1 ,4-cyclohexanedicarboxylate and mixtures of two or more thereof. A phthalic acid dialkyl ester has 4 to 13 C atoms in the alkyl chains. The alkyl chains independently of each other have the same or different numbers of C atoms. A phthalic acid dialkyl ester may be di-isononyl phthalate, dibutyl phthalate, diisobutyl phthalate, or di (2-ethylhexyl) phthalate. A phthalic acid alkylarylester may be butyl benzyl phthalate. A terephthalic acid dialkyl ester has 4 to 13 C atoms in the alkyl chains. The alkyl chains independently of each other have the same or different numbers of C atoms. A trimellitic acid trialkyl ester has 4 to 13 C atoms in the alkyl chains. The alkyl chains of the trimellitic acid trialkyl ester independently of each other have the same or a different number of C atoms. A benzoic acid alkyl ester has 7 to 13 C atoms in the alkyl chain.

[0076] A benzoic acid alkyl ester is preferably selected from the group consisting of isononyl benzoate, isodecyl benzoate, 2-propylheptyl benzoate and mixtures of two or more thereof. A dibenzoic acid 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. A saturated monocarboxylic acid ester is preferably selected from the group consisting of an ester of acetic acid, an ester of butyric acid, an ester of valeric acid, an ester of lactic acid and mixtures of two or more thereof. A saturated monocarboxylic acid ester is in alternative embodiments preferably selected from the group consisting of ester of a monocarboxylic acid with a polyhydric alcohol. For example, valeric acid may be esterified with pentaerythritol. An unsaturated monocarboxylic acid ester is preferably an ester of acrylic acid. An unsaturated dicarboxylic acid diester is preferably an ester of maleic acid. An alkyl sulfonic acid ester has 8 to 22 C atoms in the alkyl chain. An alkyl sulfonic acid ester is preferably a phenyl or cresyl ester of pentadecylsulfonic acid. An isosorbide ester is usually an isosorbide diester esterified with C8 to C13 carboxylic acids. An isosorbide diester has different or identical C8 to C13 alkyl chains. A phosphoric acid 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-ethylhexyldiphenyl phosphate, and mixtures of two or more thereof. In a citric acid triester, the OH group is free or in carboxylated form, for example acetylated form. The alkyl chains of the citric acid triester or the acetylated citric acid triester independently comprise 4 to 8 C atoms. An alkylpyrrolidone derivative has 4 to 18 C atoms in the alkyl chain. A 2,5-furandicarboxylic acid dialkyl ester has 5 to 13 C atoms in the alkyl chains. The alkyl chains of the 2,5-furanedicarboxylic acid dialkyl ester independently have different numbers of C atoms. A 2,5-tetrahydrofuranedicarboxylic acid dialkyl ester has 5 to 13 C atoms in the alkyl chains. The alkyl chains of the 2,5-tetrahydrofuranedicarboxylic acid dialkyl ester independently have a different number of C atoms. A polyester with aromatic or aliphatic polycarboxylic acids is preferably a polyester based on adipic acid with polyhydric alcohols, such as dialkylene glycol polyadipates with 2 to 6 C atoms in the alkylene unit. Examples may include polyester adipates, polyglycol adipates and polyester phthalates.

[0077] In some embodiments, the optional plasticizer comprises at least a cyclohexane-1 ,2-dicar- boxylic acid dialkylester of formula (I)

[0078] , wherein R1and R2are independently selected from the group of branched C4 to C13 alkyl and straight C1 to C13 alkyl, preferably selected from the group consisting of branched C7 to C11 alkyl and straight C7 to C11 alkyl, more preferably R1and R2are independently from each other a branched or straight C9 alkyl residue, more preferably the plasticizer comprises at least 1 ,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH).

[0079] In some preferred embodiments, the optional plasticizer comprises one or more selected from the group consisting of dibutyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, and di (2-ethylhexyl) phthalate.

[0080] In some preferred embodiments, the polymeric material comprises the optional plasticizer in an amount in the range of from 20 to 490 phr. “phr” means “parts per hundred” and indicates the amount of plasticizer per 100 parts of polymeric material.

[0081] In addition to the metal containing additive and the optional plasticizer(s), the polymeric material may comprise further additives, preferably an additive(s) selected from the group consisting of lubricant, filler, colorant (dye and / or optical brightener and / or pigment), flame inhibitor, light stabilizer, blowing agent, polymeric processing agent, impact modifier, antistatic, biostabilizer, or a mixture of two or more thereof, or degradation products of all forementioned further additives resulting from the use-phase of the polymeric material. Stabilizers -aside from the metal cation containing additives - are the usual polyvinyl chloride stabilizers in solid and liquid form, preferably selected from the group consisting of acid-binding layer silicate, carbonate (preferably hydrotalcite) and mixtures of two or more thereof. Lubricants generally serve to reduce adhesion between the disclosed molding composition or the disclosed plastisol and surfaces and are intended, for example, to reduce frictional forces during mixing, plasticizing or molding. All common lubricants used in plastics processing can be used as lubricants in the polymeric material. Lubricants commonly used in plastics processing are, for example, hydrocarbons, such as oils, kerosenes, PE waxes or mixtures thereof, fatty alcohols containing 6 to 20 carbon atoms, ketones, carboxylic acids, such as fatty acids, mon- tanic acids or mixtures thereof, oxidized PE waxes, metal salts of carboxylic acids, carboxylic acid amides, carboxylic acid esters resulting from the esterification of alcohols such as ethanol, fatty alcohols, glycerol, ethanediol or pentaerythritol with long-chain carboxylic acids. The polymeric material preferably contains a lubricant content in the range of from 0.01 to 10 weight-% based on the total weight of the polymeric material being 100 weight-%. Preferably, that the lubricant content is from 0.05 to 5 weight-%, more preferably in the range of from 0.2 to 2 weight-%. Fillers are generally used to positively influence the compressive, tensile and / or flexural strength, the rigidness and / or the heat distortion temperature of the polymeric material. For example, carbon black and / or inorganic fillers are preferably present as fillers in the disclosed polymeric material. Inorganic fillers are preferably selected from the group consisting of natural calcium carbonates, such as chalk, limestone, marbles, synthetic calcium carbonates, dolomite, silicates, silica, sand, diatomaceous earth, aluminosilicates, such as kaolin, mica, feldspar, and any mixture of two or more of the previously mentioned fillers. The polymeric material preferably contains a filler content in the range of from 0.01 to 80 weight- % based on the total weight of the molding compound or plastisol. Preferably, that the content in the range of from fillers is 0.01 to 60 weight-% more preferably 1 to 40 weight-%.

[0082] Thus, the disclosed polymeric material preferably contains a filler content in the range of from 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36 or 39 weight-%. Colorants can be used to adapt the disclosed molding composition or the disclosed plastisol to different applications. Colorants may be, for example, pigments or dyes. Pigments may be, for example, inorganic and / or organic pigments contained in the polymeric material. Inorganic pigments may be cobalt pigments such as CoO / AhOa and / or chromium pigments such as C^Ch. Organic pigments may be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and / or dioxazine pigments. The disclosed molding composition or the disclosed plastisol preferably contains a colorant content in the range of from 0.01 to 10 weight-%, based on the total weight of the polymeric material being 100 weight-%. Preferably, the content in the range of from colorants is 0.05 to 5 weight-% more preferably 0.1 to 3 weight-%. Flame inhibitors may serve to reduce the flammability of the disclosed molding compound or the disclosed plastisol and to reduce smoke formation during combustion. Flame inhibitors that are preferably present in the disclosed polymeric material are preferably selected from the group consisting of antimony trioxide, chlorinated kerosene, phosphate esters, aluminum hydroxide, boron compound and mixtures of two or more of these compounds. The polymeric material preferably contains a flame inhibitor content in the range of from 0.01 to 10 weight-% based on the total weight of the polymeric material being 100 weight-%. It is preferred that the flame inhibitor content is in the range of from 0.2 to 5 weight-% more preferably in the range of from 0.5 to 2 weight-%. Light stabilizers, such as UV absorbers, may serve to protect the disclosed molding composition or the disclosed plastisol from damage due to the influence of light. Light stabilizers are preferably selected from the group consisting of hydroxybenzophenone, hydroxyphenylbenzotria- zole, cyanoacrylate, hindered amine light stabilizer such as derivatives of 2,2,6,6-tetra- methylpiperidine, and mixtures of two or more of these compounds. The polymeric material preferably contains a light stabilizer content in the range of from 0.01 to 7 weight-% based on the total weight of the polymeric material being 100 weight-%. Preferably, the light stabilizer content is in the range of from 0.02 to 4 weight-% more preferably in the range of from 0.05 to 3 weight-%.

[0083] 2ndaspect - Polymer - product-by-process

[0084] A second aspect of the invention is related to a polymer obtained or obtainable from the method according to the first aspect, preferably from (e) and / or (f) and / or (g) according to the method according to the first aspect. All details, embodiments and preferred embodiments disclosed above in the section related to the first aspect apply also to the second aspect of the invention.

[0085] 3rdaspect - Plasticizer - product-by-process

[0086] A third aspect of the invention is related to a plasticizer obtained or obtainable from the method according to the method of the first aspect of the invention, preferably from (h) of the method of the first aspect of the invention. All details, embodiments and preferred embodiments disclosed above in the section related to the first aspect apply also to the third aspect of the invention.

[0087] 4thaspect - Use of re-obtained polymer

[0088] A fourth aspect of the invention is related to the use of the polymer of the second aspect, preferably the polymer obtained or obtainable from the method according to the first aspect, preferably from (e) and / or (f) and / or (g) according to the method according to the first aspect for preparing a polymeric product.

[0089] According to the fourth aspect, the invention also relates to a method for preparing a polymeric product comprising

[0090] (I) providing a polymer of the second aspect;

[0091] (II) preparing a polymeric product from the polymer provided in (I). All details, embodiments and preferred embodiments disclosed above in the sections related to the first aspect of the invention and the second aspect of the invention apply also to the fourth aspect of the invention.

[0092] In (II), preferably a soft polymeric product is prepared by adding at least one plasticizer, wherein the at least one plasticizer is preferably REACH approved. The polymer provided in (I) is preferably obtained or obtainable from the method according to any one of embodiments 1 to 27, preferably from (e) and / or (f) and / or (g) according to embodiment 27.

[0093] 5thaspect - Use of re-obtained plasticizer

[0094] A fifth aspect of the invention is related to the use of the plasticizer of the third aspect, preferably plasticizer obtained or obtainable from the method according to the first aspect, preferably from (h) of the method according to the first aspect, optionally after one or more work-up steps, for preparing a soft polymer. All details, embodiments and preferred embodiments disclosed above in the sections related to the first aspect of the invention and the third aspect of the invention apply also to the fifth aspect of the invention.

[0095] According to the fifth aspect, the invention is also related to a method for preparing a soft polymeric product comprising

[0096] (I) providing a plasticizer of the second aspect of the invention, preferably a plasticizer obtained or obtainable from the method according to the first aspect of the invention, preferably from (h) of the method according to the first aspect of the invention;

[0097] (II) preparing a soft polymeric material from the polymer and the plasticizer provided in (I).

[0098] Preferably, the polymer provided in (I) is a (fresh or recycled) polymer as defined in more detail in the section related to the first aspect of the invention above as TP.1 to TP.38.

[0099] The soft polymeric material obtained as described above in (II) comprises the plasticizer in some embodiments distributed in the polymer or in alternative embodiments, the polymer, preferably in powdered form, is dispersed, optionally with pigments, fillers and additives, such as blowing agents, in a liquid plasticizer (plastisol). The plasticizer is not chemically bonded to the polymer but rather embedded in the polymer or the polymer is dispersed in the (liquid) plasticizer.

[0100] In some alternative preferred embodiments, the polymer obtained or obtainable from the method according to the first aspect, preferably from e) and / or (f) and / or (g) according to the method of the first aspect, is used for preparation of a rigid polymeric product without addition of plasticizer(s).

[0101] In an aspect of said alternative preferred embodiments, the invention is also directed to a method for preparing a rigid polymeric product comprising

[0102] (I) providing a polymer as obtained from the method according to the first aspect, preferably from (e) and / or (f) and / or (g) according to the method of the first aspect;

[0103] (II) preparing a rigid polymeric product from the polymer provided in (I), preferably by shaping, wherein neither in (I) nor in (II) plasticizer(s) are added.

[0104] “Without addition of plasticizer(s)” and “neither in (I) nor in (II) plasticizer(s) are added” means that, even if a certain amount of plasticizer(s) is present, said amount is too low to have an impact on the rigid properties of the rigid polymeric product.

[0105] The rigid polymeric product obtained, i.e. the rigid polymeric material made from the polymer obtained or obtainable from the method according to the first aspect, preferably from (e) and / or (f) and / or (g) according to the method of the first aspect, is used, for example, for the production of plates, tubes, pipes, profiles, blisters, records, windows, window profiles, traffic management, floor covering, or thermoformed sheets.

[0106] 6thaspect of the invention - process for further processing a plasticizer

[0107] A sixth aspect of the invention relates to a process for further processing a plasticizer, preferably the plasticizer of the third aspect of the invention more preferably the plasticizer obtained or obtainable from the method according to the first aspect of the invention, preferably from (h) of the method according to the first aspect of the invention, the process comprising one or more steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification. All details, embodiments and preferred embodiments disclosed above in the section related to the first aspect of the invention, the section related to the second aspect of the invention, the section related to the third aspect of the invention and the section related to the fifth aspect of the invention apply also to the sixth aspect of the invention.

[0108] Regarding the plasticizers, isosorbide esters are excluded regarding transesterification. In some preferred embodiments of the process for further processing, hydrolysis comprises contacting the plasticizer with water and optionally contacting with a base or an acid and / or optionally under electromagnetic radiation, preferably light.

[0109] In some preferred embodiments of the process for further processing, hydrogenation comprises contacting the plasticizer with a hydrogen (H2) containing gas under hydrogenation conditions, preferably hydrogenation conditions allowing for a core hydrogenation of an aromatic ring system, more preferably under conditions as disclosed in WO 99 / 032427 A1.

[0110] In some preferred embodiments of the process for further processing, transesterification comprises contacting the plasticizer with an alcohol having a higher boiling point than the alcohol comprised in the alcoholic part of the plasticizer, optionally in the presence of an acidic or basic catalyst, wherein acidic catalyst preferably comprises a Broenstedt acid as well as a Lewis acid, and a basic catalyst preferably comprises, more preferably is NaHCCh.

[0111] 7thaspect - Polymer

[0112] A seventh aspect of the invention relates to a polymer comprising in the range of from 0.001 to 0.1 weight-% of GVL, based on the total weight of the polymer being 100 weight-%. All details, embodiments and preferred embodiments disclosed above in the sections related to the first to the sixth aspect of the invention apply also to the seventh aspect of the invention.

[0113] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The method of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The method of any one of embodiments 1 , 2, 3 and 4". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0114] 1 . A method for removal of an additive from a polymeric material comprising:

[0115] (a) providing a polymeric material, which comprises a polymer and a metal cation containing additive, and providing a solvent comprising gamma-valerolactone; (b) contacting the polymeric material with the solvent comprising gamma-valerolac- tone, thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, and obtaining an undissolved part of the additive comprising the metal cation;

[0116] (c) filtrating the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b), and a residue comprising the undissolved part of the additive.

[0117] 2. The method of any one of embodiment 1 , wherein the metal cation contained in the additive is a metal cation having a charge of >2, preferably the metal cation contained in the additive is selected from divalent metal cation, trivalent metal cation, tetravalent metal cation and mixtures of two or more thereof, wherein the metal cation comprised in the additive is preferably selected from the group consisting of Sn4+, Zn2+, Ba2+, Cd2+, Ca2+, Pb2+, Mg2+, Al3+and mixtures of two or more of these metal cations, preferably from the group consisting of Cd2+, Pb2 +, Zn2+, Ba2+and mixtures of two or more of these metal cations, more preferably from the group consisting of Cd2+, Pb2 +and mixtures of Cd2+and Pb2 +or from the group consisting of Zn2+, Ba2+and mixtures of Zn2+and Ba2+

[0118] 3. The method of any one of embodiment 1 or 2, wherein the additive, which comprises a metal cation, is selected from the group consisting of organo tin(IV) mercaptide, organo tin(IV) sulfide, organo tin(IV) carboxylate, substituted or unsubstituted barium(ll) phenolate, barium(ll) salt of carboxylic acid, cadmium(ll) salt of carboxylic acid, calcium(ll) salt of carboxylic acid, aluminum(lll) salt of carboxylic acid, zinc(ll) salt of carboxylic acid, substituted or unsubstituted zinc(ll) phenolate, lead(ll) sulfate, lead(ll) phosphite, lead(ll) carbonate, lead(ll) salt of carboxylic acid, magnesium(ll) salt of carboxylic acid, hydroxide carbonate hydrate of two or more of metal cations, and mixtures of two or more of these compounds, preferably from the group consisting of aluminum stearate, barium laurate, barium stearate, cadmium laurate, cadmium stearate, calcium laurate, calcium stearate, lead stearate, dibasic lead stearate, tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phthalate, basic lead carbonate and mixtures of two or more of these compounds.

[0119] 4. The method of any one of embodiments 1 to 3, wherein contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done at a temperature T1 below 190 °C, preferably below 180°C, more preferably below 170°C, more preferably at a temperature T1 in the range of from 90 to < 170°C, more preferably a temperature T1 in the range of from 95 to 165 °C, more preferably a temperature T1 in the range of from 100 to 150 °C.

[0120] 5. The method of any one of embodiments 1 to 4, wherein contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done for a period of time of at least 0.1 h, preferably for a period of time in the range of from 0.1 to 10 h, preferably for a period of time in the range of from 0.1 to 6 h, more preferably for a period of time in the range of from 0.1 to 4 h.

[0121] 6. The method of any one of embodiments 1 to 5, wherein contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done at a pressure in the range of from 800 to 200,000 hPa.

[0122] 7. The method of any one of embodiments 1 to 6, wherein contacting the polymeric material with the solvent comprising gamma-valerolactone in (b) is done with a mass based ratio polymeric material : solvent in the range of 1 :1 to 1 :100 more preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10.

[0123] 8. The method of any one of embodiments 1 to 7, wherein filtration in (c) is done by heated filtration, preferably by heated filtration at a temperature in the range of T1 ± 20°C, more preferably by heated filtration at a temperature in the range of T1 ± 10°C.

[0124] 9. The method of any one of embodiments 1 to 8, wherein filtration in (c) is done at a pressure of >1 ,000 hPa, more preferably at a pressure in the range of from 1 ,000 to 30,000 hPa, preferably in the range of from 1 ,000 to 10,000 hPa, more preferably in the range of from 1 ,000 to 6,000 hPa (heated pressure filtration).

[0125] 10. The method of any one of embodiments 1 to 9, wherein filtration in (c) is done using a filter having a nominal rating of < 30 pm, preferably < 25 pm, more preferably <10 pm, more preferably < 5 pm.

[0126] 11 . The method of any one of embodiments 1 to 10, wherein filtration in (c) is done using a filter comprising an organic material or an inorganic material, preferably a filter comprising an organic material, more preferably a filter comprising a cellulose matrix. 12. The method of any one of embodiments 1 to 11 , wherein (c) comprises

[0127] (c.1a) adding a filteraid to the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, an undissolved part of the additive comprising the metal cation, and filteraid; and (c.2a) filtrating the liquid mixture obtained in (c.1a); or

[0128] (c.1b) providing a filter having deposited thereon filteraid; and

[0129] (c.2b) filtrating the liquid mixture obtained in (b) over the filter provided in (c.1b); thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b) or (c.1a), and a residue comprising the undissolved part of the additive.

[0130] 13. The method of embodiment 12, wherein the filteraid is selected from the group consisting of powdered cellulose, diatomaceous earth, perlite, activated carbon, aluminum oxide, clay, silica, glass wool, absorbend cotton (cotton wool), magnesium silicate, (MgAI)2Si4O (OH) ■ 4 H2O, (MgAQsSisCho ■ 4 H2O, aluminum phyllosilicate clay composed of montmorillonite, (Ca,Na)o,3(AI,Mg)2Si40 (OH)2 n H2O, sodium alumino ortho silicate (Na2O.AI2O3.xSiO2.yH2O), aluminosilicate, sawdust, chitosan, agriculture or industrial waste, mud, fly ash, paper mill waste, AhO3,SiO2, Fe2O3, FesO4, TiO2, ZnO, MgO a composite of two or more of these metal oxides, mesoporouse ball clays (MBCs), ZnFe2O4, MnFe2O4, NiFe2O4, CoFe2O4, CuFe2O4, ion exchanger resin, and mixtures of two or more thereof.

[0131] 14. The method of embodiment 12 or 13, wherein the filteraid in mixture with water and / or organic solvent has a pH value > 7, preferably in the range of from 7 to 11 .

[0132] 15. The method of any one of embodiments 12 to 14, wherein the filteraid is selected from the group consisting of powdered cellulose, diatomaceous earth, perlite, activated carbon, clay, silica, glass wool, absorbend cotton (cotton wool), magnesia silicate, and mixtures of two or more thereof, preferably from the group consisting of powdered cellulose, diatomaceous earth, perlite, and mixtures of two or three thereof, more preferably the filteraid is powdered cellulose, diatomaceous earth, magnesia silicate or a mixture of two or more thereof.

[0133] 16. The method of any one of embodiments 12 to 15, wherein the filteraid is added in (c.1a) in a weight-based ratio with respect to the amount of polymeric material provided in (a) in the range of from 0.5 to 50 weight-%, preferably in the range of from 1 to 20 weight-%.

[0134] 17. The method of any one of embodiments 12 to 15, wherein the filteraid is deposited on the filter, which has a diameter D(f), in (c.1b) as a layer having a thickness LT(f) with 0.01 <LT(f) / D(f) < 2, preferably 0.05 <LT(f) / D(f) < 1.

[0135] 18. The method of any one of embodiments 1 to 17, wherein the polymeric material provided in (a) comprises a polymer, a metal cation containing additive and a plasticizer.

[0136] 19. The method of embodiment 18, wherein liquid mixture obtained in (b) comprises the solvent, dissolved polymer, at least partially dissolved plasticizer and at least partially undissolved additive.

[0137] 20. The method of embodiment 17 or 18, wherein the liquid mixture obtained from filtration in (c) comprises the solvent, dissolved polymer and at least partially dissolved plasticizer.

[0138] 21. The method of any one of embodiments 1 to 20, further comprising:

[0139] (d) precipitating the polymer from the liquid mixture obtained from filtration in (c) by addition of an anti-solvent, thereby obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the at least partially dissolved plasticizer.

[0140] 22. The method of embodiment 21 , wherein step (d) comprises:

[0141] (d.1) adjusting the temperature to a temperature T2, which is below T 1 , preferably a temperature in the range of from 10 °C to 100 °C, more preferably a temperature in the range of from 15 to 90°C, more preferably in the range of from 20 to 80°C;

[0142] (d.2) precipitating the polymer from the liquid mixture obtained from filtration in (c) at T2 by addition of an anti-solvent; thereby obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the dissolved plasticizer.

[0143] 23. The method of embodiment 21 or 22, wherein the anti-solvent used in step (d) or (d.2) is selected from the group consisting of water, C1 to C5 monoalcohol, C1 to C6 dialcohol and mixtures of two or more of these solvents, preferably from the group consisting of water, C1 to C5 monoalcohol, C1 to C5 dialcohol and mixtures of two or more of these solvents, more preferably from the group consisting of water, C1 to C3 monoalcohol and mixtures of two or more of these solvents, more preferably the anti-solvent used in step (d) or (d.2) comprises iso-propanol, more preferably at least 95 weight-% of the anti-solvent used in step (d) or (d.2) consist of iso-propanol. The method of any one of embodiments 21 to 23, wherein the anti-solvent is added in step (d) or (d.2) in a weight-based ratio anti-solvent : polymeric material in the range of from 4:1 to 75:1, preferably in the range of from 5:1 to 50:1 , more preferably in the range of from 5:1 to 20: 1. The method of any one of embodiments 21 to 24, wherein the polymer of the solid residue obtained in (d) or (d.2) comprises <40 %, preferably < 35 % of the amount of metal cation, which had been present in the polymeric material provided in (a) and optionally comprises <5 %, preferably < 1 % of the amount of plasticizer, which had been present in the polymeric material provided in (a). The method of any one of embodiments 1 to 25 further comprising:

[0144] (e) separating the solid residue, which comprises the polymer obtained in (d) or (d.2) from the liquid phase, which comprises the solvent, the anti-solvent and optionally the dissolved plasticizer, thereby obtaining the solid residue, which comprises the polymer and the liquid phase, which comprises the solvent, the antisolvent and optionally the dissolved plasticizer;

[0145] (f) optionally washing the solid residue obtained in (e) with anti-solvent;

[0146] (g) drying the solid residue obtained in (e) or the washed solid residue obtained in (f). The method of any one of embodiments 1 to 26 comprising one or more work-up step(s), wherein the one or more work-up step(s) preferably comprise

[0147] (h) separating solvent and anti-solvent by distillation and / or separating solvent from optionally dissolved plasticizer by distillation, thereby optionally obtaining a, preferably liquid fraction comprising the plasticizer and one or more liquid fraction(s) comprising the solvent and / or the anti-solvent. The method of embodiment 27, further comprising recycling the separated solvent obtained in (h) at least partially to (a) and / or recycling the separated anti-solvent obtained on (h) at least partially to (d). 29. A polymer obtained or obtainable from the method according to any one of embodiments 1 to 28, preferably from (e) and / or (f) and / or (g) according to embodiment 25.

[0148] 30. A plasticizer obtained or obtainable from the method according to any one of embodiments 18 to 27, preferably from (h).

[0149] 31 . Use of the polymer of embodiment 29, preferably the polymer obtained or obtainable from the method according to any one of embodiments 1 to 27, preferably from (e) and / or (f) and / or (g) according to embodiment 27 for preparing a polymeric product.

[0150] 32. A method for preparing a polymeric product comprising

[0151] (I) providing a polymer of embodiment 29;

[0152] (II) preparing a polymeric product from the polymer provided in (I).

[0153] 33. Use of the plasticizer of embodiment 30, preferably plasticizer obtained or obtainable from the method according to any one of embodiments 18 to 27, preferably from (h), optionally after one or more work-up steps, for preparing a soft polymer.

[0154] 34. A method for preparing a soft polymeric product comprising

[0155] (I) providing a plasticizer of embodiment 30, preferably a plasticizer obtained or obtainable from the method according to any one of embodiments 18 to 27, preferably from (h);

[0156] (II) preparing a soft polymeric material from the polymer and the plasticizer provided in (I).

[0157] 35. A process for further processing a plasticizer, preferably the plasticizer of embodiment 30, more preferably the plasticizer obtained or obtainable from the method according to any one of embodiments 18 to 27, preferably from (h), the process comprising one or more work-up steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

[0158] 36. The process for further processing of embodiment 35, wherein hydrolysis comprises contacting the plasticizer with water and optionally contacting with a base or an acid and / or optionally under electromagnetic radiation, preferably light. 37. The process for further processing of embodiment 35, wherein hydrogenation comprises contacting the plasticizer with a hydrogen (H2) containing gas under hydrogenation conditions, preferably hydrogenation conditions allowing for a core hydrogenation of an aromatic ring system more preferably under conditions as disclosed in WO 99 / 032427 A1.

[0159] 38. The process for further processing of embodiment 35, wherein transesterification comprises contacting the plasticizer with an alcohol having a higher boiling point than the alcohol comprised in the alcoholic part of the plasticizer, optionally in the presence of an acidic or basic catalyst, wherein acidic catalyst preferably comprises a Broenstedt acid as well as a Lewis acid, and a basic catalyst preferably comprises, more preferably is NaHCO3.

[0160] 39. A polymer comprising in the range of from 0.001 to 0.1 weight-% of gamma-valerolac- tone, based on the total weight of the polymer being 100 weight-%.

[0161] The present invention is further illustrated by the following reference examples, comparative examples, and examples.

[0162] Examples

[0163] Methods

[0164] Hazen color index:

[0165] The Hazen color index (APHA color number) was determined according to DIN EN ISO 6271 :2016-05 (Pt / Co, APHA, ASTM D1209, D5386).

[0166] GPC:

[0167] Sample preparation

[0168] Approximately 20 mg sample was dissolved in 10 ml eluent (THF) over night. All sample solutions were filtered by a Macherey-Nagel PTFE (0.2 pm) filtered prior to injection. Sealed sample vials were placed into the auto sampler.

[0169] Experimental conditions

[0170] An Agilent 1200 HPLC system, consisting of a isocratic pump, vacuum degasser, auto sampler and a column oven (35°C) was used. As detectors a Differential Refractive Index (DRI) and a variable Ultra Violet (UVW) Detector was used. Data acquisition and data processing of conventionally SEC data were done by WinGPC Unichrom, build 9666, of PSS (Polymer Standard Services). A combination of a Plgel 10p Guard (7,5 x 50 mm) column and 3 PLgel MIXED-B columns (7,5 x 300 mm, 10p) of Agilent were put in series. As an eluent, THF was used as a flow rate of 1 mL / min. Of each sample solution 100pL was injected. The calibration was obtained by narrow molar mass distributed Polystyrene standards (Polymer Standard Services) having a molar mass range of M= 580 till M = 6.870.000 g / mol. Molar masses outside this range were extrapolated. The lowest possible integration limit was set at 25ml (M(1800) ca. ). No lower molar masses could be obtained due to possible polymer additives or solvent impurities. All number average molar mass Mn and all weight average molar mass Mw indicated herein below are related to polyvinylchloride only.

[0171] GC area%:

[0172] The sample was analyzed by gas chromatography (GC), wherein the method detected individual components from a sample dependent on their individual retention times. The concen- tration of the individual component in the sample were given in its percental peak area as GC-area%.

[0173] Chemicals & materials

[0174] Reference Example 1 : General procedure for extraction of additives from PVC

[0175] PVC samples (containing Pb-based and / or Cd-based additives and optionally a plasticizer) were cut / shredded into pieces and placed in a reaction vessel (e.g. flask, tube, reaction vessel). GVL was added (in mass-based ratio polymeric material : GVL 1:1 to 1:100, preferred 1 :1 to 1:10) and the resulting mixture was heated by use of a suitable heating system (e.g. oil bath, heating blocks, mini-plant vessels) to 100-150 °C. After 0.1-4 h, optionally a filteraid was added to the mixture and the mixture was then filtered with variations in filter material. The filtration was carried out at 120°C under a pressure of 1 bar on a pressure suction filter (Druckfilternutsche, heated pressure filtration). After filtration, the filter was optionally washed with hot GVL, especially in case of filter beds (Examples 14-16, see Table 2), resulting in washing solution(s) obtained from the filter. In case of filter beds, the filtration aid was not added to the solution prior to filtration but was rather given onto the pressure suction filter as filter bed having a layer thickness LT(f), the filter having a diameter D(f) with 0.3 < LT(f) / D(f) < 0.5.

[0176] After filtration, any solid residue on the filter was removed and the filtrate, optionally after combination with washing solution(s), was adjusted to have a temperature in the range of from 20 to 80 °C, preferably of 60 °C, and kept at said temperature. iPrOH (in mass-based ratio polymeric material : iPrOH 1 :15) was added to the filtrate, thereby precipitating PVC. The resulting mixture comprising liquid phase and precipitated PVC was filtered at a temperature in the range of from 20 to 30°C, whereby GVL, optionally enriched in plasticizer, and solid PVC were obtained. The solid PVC was washed with a small amount of iPrOH at a temperature in the range of from 20 to 25 °C, using a weight based ratio solid to iPrOH in the range of from 1 :5 to 1 :20. The thus obtained washed solid PVC was dried (for example in a vacuum compartment dryer).

[0177] For the samples containing plasticizer:

[0178] After treatment the GVL enriched with plasticizer was analyzed by GC and the PVC residue (after washing and drying) was further extracted by a conventional extraction method (using methylal) to determine the residual amount of plasticizer still present in the PVC.

[0179] Examples 1 to 16: Extraction of additives from soft PVC

[0180] The analytical data of the starting material (PVC containing Pb-based and / or Cd-based additives and optionally a plasticizer) are given in Table 1 below.

[0181] Table 1

[0182] Analytical data of starting material

[0183] The starting material was treated according to the procedure described in Reference Example 1. The conditions and results are listed in Table 2 below. able 2 xperimental results of examples 1-16

[0184]

[0185]

[0186]

[0187] weight-% based on 100 weight-% starting material.

[0188] For recycling of the used solvent first iPrOH was distilled and then GVL. For the distillation of GVL following parameters were applied: 50-200 °C, 2 hPa to ambient pressure, preferred 70- 110 °C, 5-30 hPa. The obtained GVL had a purity according to GO of > 99 %. For GVL, the Hazen color index was determined before treatment and after distillation as 15. For iPrOH, the Hazen color index was determined after distillation as zero.

[0189] It was found that without filteraid, the best results were obtained with a filter material having a small nominal rating (Examples 1-4) < 20 nm, preferably < 10 nm, more preferably in the range of from 1 to 10 nm.

[0190] Using a filteraid further improved the results and with use of a filteraid, it was found that removal of metal-based additives worked best with basic filteraids (Celite and Macrosorb both having a basic pH value). It was found that the re-obtained PVC showed a decline in weight average molar mass (Mw) when acidic filteraids were used but showed an increase in weight average molar mass (Mw) for neutral or basic filteraids.

[0191] In every case (acidic, neutral or basic filteraids) the number average molar mass (Mn) increased and the dispersity decreased.

[0192] Example 17: Extraction of additives from soft PVC containing Zn salts and

[0193] Ba salts.

[0194] The analytical data of the starting material are given in Table 3 below.

[0195] Table 3

[0196] Analytical data of starting material

[0197] The starting material was treated according to the procedure described in Reference Example

[0198] 1. The conditions and results are listed in Table 4 below. Table 4

[0199] Experimental results of example 17 containing Zn- and Ba-salts

[0200] Table 4 - continuation

[0201] For recycling of the used solvent first iPrOH was distilled and then GVL. For the distillation of GVL following parameters were applied: 50-200 °C, 2 hPa to ambient 20 pressure, preferred 70-110 °C, 5-30 hPa. The obtained GVL had a purity according to GO of > 99 %. For GVL, the Hazen color index was determined before treatment and after distillation as 15. For iso-propa- nol, the Hazen color index was determined after distillation as zero.

[0202] It could be seen that the use of GVL resulted in a considerable removal of metal cations from the PVC since the re-obtained PVC contained less than 33% of the Zn cations and less than 80% of the Ba cations compared to the PVC initially provided.

[0203] Example 18: Extraction of additives from soft PVC

[0204] PVC starting material from post-consumer flooring was treated as described in Reference Example 1. The analytical data of the starting material are given in Table 5 below. The conditions and results are listed in Table 6 below.

[0205] Table 5

[0206] Analytical data of starting material Table 6

[0207] Conditions and results of Example 18

[0208] It could be seen that the use of GVL resulted in a considerable removal of metal cations as well as plasticizer from the PVC.

[0209] Comparative Example 1 : Extraction of additives from soft PVC with different solvents (Procedure according to CN 115784886 A)

[0210] PVC starting material from post-consumer flooring was treated in that 30 g of PVC sample (containing Pb-based and / or Cd-based additives and optionally a plasticizer) were cut / shredded into pieces and placed in a reaction vessel (e.g. flask, tube, reaction vessel). 30 g of n-hexane and 30 g of ethanol were added and the resulting mixture was heated by use of a suitable heating system (e.g. oil bath, heating blocks, mini-plant vessels) to ~ 55 °C (under reflux). After 6 h, the mixture was cooled to room temperature and filtered. The thus obtained solid PVC was dried (for example in a vacuum compartment dryer). The analytical data of the starting material are indicated in Table 5 above. The conditions and results are listed in Table 7 below.

[0211] Table 7

[0212] Conditions and results of Comparative Example 1 Table 7 - continuation

[0213] It could be seen from the comparison of Example 18 and Comparative Example 1 that treatment with n-hexane and ethanol gave a significantly worse result compared to the treatment with GVL in that less plasticizer was removed and more metal cation (Pb) remained in the re-obtained

[0214] PVC.

[0215] Cited Literature

[0216] WO 02 / 14413 A1

[0217] US 4,071 ,479 A

[0218] CN 115784886 A

Claims

Claims1 . A method for removal of an additive from a polymeric material comprising:(a) providing a polymeric material, which comprises a polymer and a metal cation containing additive, and providing a solvent comprising gamma-valerolactone;(b) contacting the polymeric material with the solvent comprising gamma-valerolactone, thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, and obtaining an undissolved part of the additive comprising the metal cation;(c) filtrating the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b), and a residue comprising the undissolved part of the additive.

2. The method of any one of claim 1 , wherein the metal cation contained in the additive is a metal cation having a charge of >2, preferably the metal cation contained in the additive is selected from divalent metal cation, trivalent metal cation, tetravalent metal cation and mixtures of two or more thereof, wherein the metal cation comprised in the additive is preferably selected from the group consisting of Sn4+, Zn2+, Ba2+, Cd2+, Ca2+, Pb2+, Mg2+, Al3+and mixtures of two or more of these metal cations, preferably from the group consisting of Cd2+, Pb2 +, Zn2+, Ba2+and mixtures of two or more of these metal cations, more preferably from the group consisting of Cd2+, Pb2 +and mixtures of Cd2+and Pb2 +or from the group consisting of Zn2+, Ba2+and mixtures of Zn2+and Ba2+; and / or, preferably and, wherein the additive, which comprises a metal cation, is selected from the group consisting of organo tin(IV) mercaptide, organo tin(IV) sulfide, organo tin(IV) carboxylate, substituted or unsubstituted barium(ll) phenolate, barium(ll) salt of carboxylic acid, cadmium(ll) salt of carboxylic acid, calcium(ll) salt of carboxylic acid, aluminum(lll) salt of carboxylic acid, zinc(ll) salt of carboxylic acid, substituted or unsubstituted zinc(ll) phenolate, lead(ll) sulfate, lead(ll) phosphite, lead(ll) carbonate, lead(ll) salt of carboxylic acid, magne- sium(ll) salt of carboxylic acid, hydroxide carbonate hydrate of two or more of metal cations, and mixtures of two or more of these compounds, preferably from the group consisting of aluminum stearate, barium laurate, barium stearate, cadmium laurate, cadmium stearate, calcium laurate, calcium stearate, lead stearate, dibasic lead stearate, tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phthalate, basic lead carbonate and mixtures of two or more of these compounds.

3. The method of claim 1 or 2, wherein filtration in (c) is done using a filter having a nominal rating of < 30 pm, preferably < 25 pm, more preferably <10 pm, more preferably < 5 pm;and / or, preferably and, wherein filtration in (c) is done using a filter comprising an organic material or an inorganic material, preferably a filter comprising an organic material, more preferably a filter comprising a cellulose matrix.

4. The method of any one of claims 1 to 3, wherein (c) comprises(c.1a) adding a filteraid to the liquid mixture obtained in (b), thereby obtaining a liquid mixture, which comprises the solvent, dissolved polymer, an undissolved part of the additive comprising the metal cation, and filteraid; and (c.2a) filtrating the liquid mixture obtained in (c.1a); or (c.1b) providing a filter having deposited thereon filteraid; and (c.2b) filtrating the liquid mixture obtained in (b) over the filter provided in (c.1 b); thereby obtaining a liquid mixture, which comprises the solvent and dissolved polymer, and which is depleted of metal cation compared to the liquid mixture obtained in (b) or (c.1a), and a residue comprising the undissolved part of the additive.

5. The method of claim 4, wherein the filteraid is selected from the group consisting of powdered cellulose, diatomaceous earth, perlite, activated carbon, aluminum oxide, clay, silica, glass wool, absorbend cotton (cotton wool), magnesium silicate, (MgAI)2Si4O (OH) ■ 4 H2O, (MgAQsSisCho ■ 4 H2O, aluminum phyllosilicate clay composed of montmorillonite, (Ca,Na)o,3(AI,Mg)2Si40 (OH)2 n H2O, sodium alumino ortho silicate (Na2O.AI2O3.xSiO2.yH2O), aluminosilicate, sawdust, chitosan, agriculture or industrial waste, mud, fly ash, paper mill waste, AhO3,SiO2, Fe2O3, FesO4, TiO2, ZnO, MgO a composite of two or more of these metal oxides, mesoporouse ball clays (MBCs), ZnFe2O4, MnFe2O4, NiFe2O4, CoFe2O4, CuFe2O4, ion exchanger resin, and mixtures of two or more thereof; wherein preferably, the filteraid in mixture with water and / or organic solvent has a pH value > 7, preferably in the range of from 7 to 11.

6. The method of any one of claims 1 to 5, wherein the polymeric material provided in (a) comprises a polymer, a metal cation containing additive and a plasticizer.

7. The method of any one of claims 1 to 6, further comprising:(d) precipitating the polymer from the liquid mixture obtained from filtration in (c) by addition of an anti-solvent, thereby obtaining a solid residue, which comprises the polymer, and a liquid phase, which comprises the solvent, the anti-solvent, and optionally the at least partially dissolved plasticizer.

8. The method of any one of claims 1 to 7, further comprising:(e) separating the solid residue, which comprises the polymer obtained in (d) or (d.2) from the liquid phase, which comprises the solvent, the anti-solvent and optionally the dissolved plasticizer, thereby obtaining the solid residue, which comprises the polymer and the liquid phase, which comprises the solvent, the anti-solvent and optionally the dissolved plasticizer;(f) optionally washing the solid residue obtained in (e) with anti-solvent;(g) drying the solid residue obtained in (e) or the washed solid residue obtained in (f); the method preferably comprising one or more work-up step(s), wherein the one or more work-up step(s) preferably comprise(h) separating solvent and anti-solvent by distillation and / or separating solvent from optionally dissolved plasticizer by distillation, thereby optionally obtaining a, preferably liquid fraction comprising the plasticizer and one or more liquid fraction(s) comprising the solvent and / or the anti-solvent.

9. A polymer obtained or obtainable from the method according to any one of claims 1 to 8, preferably from (e) and / or (f) and / or (g) according to claim 8.

10. A plasticizer obtained or obtainable from the method according to any one of claims 6 to 8, preferably from (h).

11. Use of the polymer of claim 9, preferably of the polymer obtained or obtainable from the method according to any one of claims 1 to 8, preferably from (e) and / or (f) and / or (g) according to claim 8 for preparing a polymeric product.

12. Use of the plasticizer of claim 10, preferably plasticizer obtained or obtainable from the method according to any one of claims 6 to 8, preferably from (h), optionally after one or more work-up steps, for preparing a soft polymer.

13. A process for further processing a plasticizer, preferably the plasticizer of claim 10, more preferably the plasticizer obtained or obtainable from the method according to any one of claims 6 to 8, preferably from (h), the process comprising one or more work-up steps selected from the group consisting of hydrolysis, hydrogenation, and transesterification.

14. A polymer comprising in the range of from 0.001 to 0.1 weight-% of gamma-valerolactone, based on the total weight of the polymer being 100 weight-%.