Plasticizer compound

Abstract

A compound of general formula (I) wherein R1 and R2 independently of each other are selected from C1-C12 alkyl, is suitable for use as a plasticizer of little volatility, good gelling properties, good compatibility and toxicological acceptability.

Description

[0001] plasticizer compound

[0002] The present invention relates to certain dicarboxylic acid diesters and their use as plasticizers, a plasticizer composition, a molding compound or a plastisol containing the dicarboxylic acid diesters, and a process for the preparation of 4,7-dioxosebacic acid.

[0003] Plasticizers are incorporated into polymers or elastomers to increase their flexibility or processability. Plasticizers are most commonly used in the manufacture of "plasticized" or flexible polyvinyl chloride (PVC) products. Plasticizers can be characterized by their chemical structure. The most important chemical class of plasticizers are esters of aliphatic or aromatic polycarboxylic acids.

[0004] Among the most commonly used aliphatic dicarboxylic acids is adipic acid, which, after esterification with alcohol components to form adipic acid esters (adipates), is used as a plasticizer for polymers, e.g., thermoplastics. Other dicarboxylic acids are known from the literature that can be used as plasticizers after esterification, such as sebacic acid (decanedioic acid), see, for example, US 2339387.

[0005] In general, the known plasticizers are subject to constant optimization, e.g. with regard to their volatility, gelling properties, compatibility and / or toxicological safety.

[0006] The present invention was therefore based on the object of providing plasticizers with low volatility, good gelling properties, good compatibility and toxicological safety.

[0007] The dimethyl and diethyl esters of 4,7-dioxodecanedioic acid are known per se, see, for example, V. Singh et al., Journal of Chemical Research, Synopses 1991, 11, 326-327. Their use as plasticizers has not been described.

[0008] The problem was solved by using a compound of general formula (I) as plasticizer where

[0009] Ri and R2 are independently selected from Ci-Ci2-alkyl, preferably from linear or branched C3-Ci2-alkyl

[0010] Compounds of formula (I) wherein R1 and R2 are independently selected from linear or branched C3-C12-alkyl are materially novel and form a further subject of the invention.

[0011] In the context of the present disclosure, the abbreviation phr (parts per hundred resin) stands for parts by weight per hundred parts by weight of polymer.

[0012] Unless otherwise stated, the percentage by weight refers to the respective total mass.

[0013] A mixture is any combination of two or more components. For example, a mixture can contain two to five or more components. A mixture can also contain any number of components.

[0014] In the compound of general formula (I), R1 and R2 can be independently selected from n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, iso-octyl, 2-octyl, 2-ethylhexyl, n-Nonyl, iso-Nonyl, 2-propylhexyl, n-decyl, iso-Decyl, 2-propylheptyl, n-undecyl, iso-undecyl, n-dodecyl, and iso-dodecyl.

[0015] Preferably, R1 and R2 are independently selected from n-propyl, n-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 2-octyl, 2-ethylhexyl, iso-nonyl, 2-propylheptyl and isodecyl.

[0016] Most preferably, R1 and R2 are independently selected from n-propyl, 2-octyl, 2-ethylhexyl, iso-nonyl and 2-propylheptyl.

[0017] Typically, the alcohols underlying the aforementioned iso radicals, e.g., isooctyl, isononyl, isodecyl, isundecyl, and isododecyl, are obtained not as defined individual compounds, but as mixtures. For the purposes of the present invention, the term "isoalkyl" therefore refers to both a branched alkyl radical and a mixture of a branched alkyl radical with at least one constitutionally isomeric alkyl radical with an identical carbon number. Even if R1 and R2 in a compound of general formula (I) are generally independent of one another, R1 and R2 are preferably identical or constitutionally isomeric.

[0018] For example, a compound of general formula (I) can be:

[0019] - 1.1 Di-(n-propyl)-4,7-dioxodecanoate

[0020] - I.2 Di-(iso-propyl)-4,7-dioxodecanoat

[0021] - I.3 Di-(n-butyl)-4,7-dioxodecanoat

[0022] - I.4 Di-(iso-butyl)-4,7-dioxodecanoat

[0023] - I.5 Di-(n-pentyl)-4,7-dioxodecanoat

[0024] - I.6 Di-(2-methylbutyl)-4,7-dioxodecanoat

[0025] - I.7 Di-(3-methylbutyl)-4,7-dioxodecanoat

[0026] - I.8 Di-(1 ,2-dimethylpropyl)-4,7-dioxodecanoat

[0027] - I.9 Di-(1 ,1-dimethylpropyl)-4,7-dioxodecanoat

[0028] - 1.10 Di-(2,2-dimethylpropyl)-4,7-dioxodecanoat

[0029] - 1.11 Di-(1-ethylpropyl)-4,7-dioxodecanoat

[0030] - 1.12 Di-(n-hexyl)-4,7-dioxodecanoat

[0031] - 1.13 Di-(1-methylpentyl)-4,7-dioxodecanoat

[0032] - 1.14 Di-(2-methylpentyl)-4,7-dioxodecanoat

[0033] - 1.15 Di-(1-ethylbutyl)-4,7-dioxodecanoat

[0034] - 1.16 Di-(2-ethylbutyl)-4,7-dioxodecanoat

[0035] - 1.17 Di-(n-heptyl)-4,7-dioxodecanoat

[0036] - 1.18 Di-(1-methylhexyl)-4,7-dioxodecanoat

[0037] - 1.19 Di-(2-methylhexyl)-4,7-dioxodecanoat

[0038] - I.20 Di-(1-ethylpentyl)-4,7-dioxodecanoat

[0039] - 1.21 Di-(2-ethylpentyl)-4,7-dioxodecanoat

[0040] - I.22 Di-(1-propylbutyl)-4,7-dioxodecanoat

[0041] - I.23 Di-(1-ethyl-2-methylpropyl)-4,7-dioxodecanoat

[0042] - I.24 Di-(n-Octyl, iso-octyl)-4,7-dioxodecanoat

[0043] - I.25 Di-(iso-octyl)-4,7-dioxodecanoat

[0044] - I.26 Di-(2-octyl)-4,7-dioxodecanoat

[0045] - I.27 Di-(2-ethylhexyl)-4,7-dioxodecanoat

[0046] - I.28 Di-(n-nonyl)-4,7-dioxodecanoat

[0047] - I.29 Di-(iso-nonyl)-4,7-dioxodecanoat

[0048] - I.30 Di-(2-propylhexyl)-4,7-dioxodecanoat

[0049] - 1.31 Di-(n-decyl)-4,7-dioxodecanoate

[0050] - I.32 Di-(iso-decyl)-4,7-dioxodecanoate

[0051] - I.33 Di-(2-propylheptyl)-4,7-dioxodecanoate

[0052] - I.34 Di-(n-undecyl)-4,7-dioxodecanoate

[0053] - I.35 Di-(iso-undecyl)-4,7-dioxodecanoate - 1.36 Di-(n-dodecyl)-4,7-dioxodecanoate

[0054] - 1.37 Di-(iso-dodecyl)-4,7-dioxodecanoate

[0055] Use of a compound of general formula (I) as a plasticizer

[0056] In one embodiment, the compound of general formula (I) with independently selected R1 and R2 from Ci-Ci2-alkyl is used as a plasticizer, preferably in a molding compound or a plastisol.

[0057] Plasticizer composition

[0058] A further object of the present invention is a plasticizer composition which contains at least one compound of the general formula (I) as described above and at least one further plasticizer which is different from the compounds of the general formula (I).

[0059] The plasticizer composition can therefore also contain a mixture of compounds of the general formula (I), for example a mixture of compounds of the general formula (I) selected from 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36 and 1.37.

[0060] The content of the at least one compound of general formula (I) in the plasticizer composition is generally at least 10% by weight, preferably 30 to 90% by weight, more preferably 50 to 80% by weight, and the further plasticizer in an amount of 0 to 90% by weight, preferably 10 to 70% by weight, more preferably 20 to 50% by weight, in each case based on the total mass of the plasticizer composition. The content of the at least one compound of general formula (I) in the plasticizer composition can be, for example, 52, 55, 58, 60, 62, 65, 68, 70, 72, 75, 78 or 80% by weight.

[0061] In addition to the compound of general formula (I), the plasticizer composition contains at least one further plasticizer. The further plasticizer is different from the compounds of general formula (I). For example, the further plasticizer can be selected from

[0062] - Phthalic acid dialkyl esters, e.g. with 9 to 13 C atoms in the alkyl chains,

[0063] - trimellitic acid trialkyl esters,

[0064] - Terephthalic acid dialkyl esters, e.g. with 4 to 12 C atoms in the alkyl chains,

[0065] - Benzoic acid alkyl esters,

[0066] - Dibenzoic acid esters, e.g. dibenzoic acid esters of glycols,

[0067] - hydroxybenzoic acid esters, - esters of saturated monocarboxylic acids,

[0068] - Esters of unsaturated monocarboxylic acids,

[0069] - esters of hydroxymonocarboxylic acids,

[0070] - esters of dicarboxylic acids,

[0071] - esters of saturated hydroxydicarboxylic acids,

[0072] - amides and esters of aromatic sulfonic acids,

[0073] - pentaerythritol esters,

[0074] - alkylsulfonic acid esters,

[0075] - glycerol esters,

[0076] - isosorbide esters,

[0077] - phosphoric acid esters,

[0078] - Citric acid diesters and citric acid triesters, e.g. acylated citric acid triesters

[0079] - alkylpyrrolidone derivatives,

[0080] - 2,5-furandicarboxylic acid esters, e.g. 2,5-furandicarboxylic acid dialkyl esters

[0081] - 2,5-tetrahydrofurandicarboxylic acid esters, e.g. 2,5-tetrahydrofurandicarboxylic acid dialkyl esters,

[0082] - epoxidized vegetable oils,

[0083] - epoxidized fatty acid monoalkyl esters,

[0084] - 1,2-cyclohexanedicarboxylic acid dialkyl esters, e.g. with 4 to 13 C atoms in the alkyl chains,

[0085] - 1,3-cyclohexanedicarboxylic acid dialkyl esters, e.g. with 4 to 13 C atoms in the alkyl chains,

[0086] - 1,4-cyclohexanedicarboxylic acid dialkyl esters, e.g. with 4 to 13 C atoms in the alkyl chains,

[0087] - Polyesters made from aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols,

[0088] - other plasticizers, and

[0089] - Mixtures thereof.

[0090] A dialkyl phthalate can have 9 to 13 carbon atoms in the alkyl chains. The alkyl chains can independently have a different number of carbon atoms. A dialkyl phthalate, for example, can be di-isononyl phthalate.

[0091] A trialkyl trimellitate can have 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the trialkyl trimellitate can independently have a different number of carbon atoms.

[0092] An alkyl benzoate can have 10 to 13 carbon atoms in the alkyl chain. An alkyl benzoate can be, for example, isodecyl benzoate or 2-propylheptyl benzoate.

[0093] A dibenzoic acid ester can be, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, or dibutylene glycol dibenzoate. A saturated monocarboxylic acid ester can be, for example, an ester of acetic acid, an ester of butyric acid, an ester of valeric acid, or an ester of lactic acid. A saturated monocarboxylic acid ester can also be an ester of a monocarboxylic acid with a polyhydric alcohol. For example, valeric acid can be esterified with pentaerythritol.

[0094] An unsaturated monocarboxylic acid ester can, for example, be an ester of acrylic acid.

[0095] An unsaturated dicarboxylic acid diester can, for example, be an ester of maleic acid.

[0096] An alkylsulfonic acid ester can have 8 to 22 carbon atoms in the alkyl chain. An alkylsulfonic acid ester can, for example, be a phenyl or cresyl ester of pentadecylsulfonic acid.

[0097] An isosorbide ester is typically an isosorbide diester esterified with Cs to C carboxylic acids. An isosorbide diester can have different or identical Cs to C alkyl chains.

[0098] A phosphoric acid ester can be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, or bis-2(2-ethylhexyl)phenyl phosphate, 2-ethylhexyldiphenyl phosphate.

[0099] In a citric acid triester, the OH group can be present in free or 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 carbon atoms.

[0100] An alkylpyrrolidone derivative can have 4 to 18 C atoms in the alkyl chain.

[0101] A 2,5-furandicarboxylic acid dialkyl ester can have 5 to 13 C atoms in the alkyl chains. The alkyl chains of the 2,5-furandicarboxylic acid dialkyl ester can independently have a different number of C atoms.

[0102] A dialkyl 2,5-tetrahydrofurandicarboxylate can have 5 to 13 carbon atoms in the alkyl chains. The alkyl chains of the dialkyl 2,5-tetrahydrofurandicarboxylate can independently have a different number of carbon atoms.

[0103] A dialkyl cyclohexane-1,2-dicarboxylate typically has 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the dialkyl cyclohexane-1,2-dicarboxylate can independently have a different number of carbon atoms. A dialkyl cyclohexane-1,2-dicarboxylate can be di-(2-ethylhexyl)-1,2-cyclohexanoic acid dicarboxylate, di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate, or di-(2-propylheptyl)-1,2-dicarboxylic acid dicarboxylate.

[0104] A dialkyl cyclohexane-1,3-dicarboxylate can have 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the dialkyl cyclohexane-1,3-dicarboxylate can independently have a different number of carbon atoms.

[0105] A dialkyl cyclohexane-1,4-dicarboxylate can have 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the dialkyl cyclohexane-1,4-dicarboxylate can, independently of one another, have a different number of carbon atoms. A dialkyl cyclohexane-1,4-dicarboxylate can, for example, be di-(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, di-(isononyl)-1,4-cyclohexanoic acid dicarboxylate, or di-(2-propylheptyl)-1,4-dicarboxylic acid dicarboxylate.

[0106] A polyester with aromatic or aliphatic polycarboxylic acids can be a polyester based on adipic acid with polyhydric alcohols, such as dialkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene unit. Examples include polyester adipates, polyglycol adipates, and polyester phthalates.

[0107] Polymers

[0108] Advantageously, a compound of general formula (I) or a plasticizer composition containing it (hereinafter collectively: “plasticizer”) is used as a plasticizer for a polymer or a mixture of polymers.

[0109] A polymer is a plastic. A polymer can be a thermoplastic or an elastomer.

[0110] A thermoplastic can usually be processed thermoplastically.

[0111] An elastomer can be, for example, a rubber. A rubber can be natural rubber or synthetic rubber. Synthetic rubber can be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, and mixtures thereof.

[0112] The plasticizer can therefore be used as a plasticizer for a thermoplastic or a mixture of thermoplastics. The plasticizer can also be used as a plasticizer for an elastomer or a mixture of elastomers. The plasticizer can also be used as a plasticizer for a mixture containing at least one elastomer and at least one thermoplastic. The plasticizer is usually used as a plasticizer for polyvinyl chloride, a polyvinyl chloride copolymer, a mixture of polymers containing polyvinyl chloride, or a plastisol containing polyvinyl chloride.

[0113] A thermoplastic can be, for example:

[0114] - TP.1 : a homo- or copolymer containing in polymerized form at least one

[0115] Contains a monomer selected from C2 to Cw monoolefins, for example ethylene, propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols or their C2 to Cw alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride,

[0116] Tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates or methacrylates with alcohol components of branched or unbranched Ci to Cw alcohols, vinyl aromatics such as styrene, (meth)acrylonitrile, α,β-ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride.

[0117] - TP.2: a polyvinyl ester

[0118] - TP.3: a polycarbonate

[0119] - TP.4: a polyether

[0120] - TP.5: a polyetherketone

[0121] - TP.6: a thermoplastic polyurethane

[0122] - TP.7: a polysulfide

[0123] - TP.8: a polysulfone

[0124] - TP.9: a polyester

[0125] - TP.10: a polyalkylene terephthalate

[0126] - TP.11 : a polyhydroxyalkanoate

[0127] - TP.12: a polybutylene succinate

[0128] - TP.13: a polybutylene succinate adipate

[0129] - TP.14: a polyacrylate with the same or different alcohol residues from the group of C4 to Cs alcohols such as butanol, hexanol, octanol, 2-ethylhexanol

[0130] - TP.15: a polymethyl methacrylate

[0131] - TP.16: a methyl methacrylate-butyl acrylate copolymer

[0132] - TP.17: an acrylonitrile-butadiene-styrene copolymer

[0133] - TP.18: an ethylene-propylene copolymer

[0134] - TP.19: an ethylene-propylene-diene copolymer

[0135] - TP.20: a polystyrene

[0136] - TP.21 : a styrene-acrylonitrile copolymer

[0137] - TP.22: an acrylonitrile-styrene-acrylate

[0138] - TP.23: a styrene-butadiene-methyl methacrylate copolymer

[0139] - TP.24: a styrene-maleic anhydride copolymer

[0140] - TP.25: a styrene-methacrylic acid copolymer

[0141] - TP.26: a polyoxymethylene

[0142] - TP.27: a polyvinyl alcohol - TP.28: a polyvinyl acetate

[0143] - TP.29: a polyvinyl butyral

[0144] - TP.30: a polyvinyl chloride

[0145] - TP.31 : a polycaprolactone

[0146] - TP.32: Polyhydroxybutyric acid

[0147] - TP.33: Polyhydroxyvaleric acid

[0148] - TP.34: Polylactic acid

[0149] - TP.35: Ethylcellulose

[0150] - TP.36: Cellulose acetate

[0151] - TP.37: Cellulose propionate

[0152] - TP.38: Cellulose acetate / butyrate

[0153] Polyvinyl chloride is generally obtained by homopolymerization of vinyl chloride. Polyvinyl chloride can be produced, for example, by suspension polymerization, such as microsuspension polymerization, or by bulk polymerization. The production of polyvinyl chloride by polymerization of vinyl chloride, as well as the production and composition of plasticized polyvinyl chloride, are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2 / 1: Polyvinyl Chloride," 2nd edition, Carl Hanser Verlag, Munich.

[0154] The K value characterizing the molar mass of the polyvinyl chloride is determined according to DIN-EN 1628-2 (November 1999) and for the polyvinyl chloride plasticized with the plasticizer is usually in the range from 57 to 90, preferably 61 to 85, particularly preferably 64 to 80.

[0155] Advantageously, the present plasticizer is characterized by high compatibility with the plastic to be plasticized. Furthermore, the present plasticizer can positively influence the gelling behavior of the plasticized plastics. Furthermore, the present plasticizer can be characterized by low volatility, both during processing and during use of the final products. The plasticizer can also have a beneficial effect on the mechanical properties of the plasticized plastics.

[0156] Good mechanical properties can be reflected, for example, in the high elasticity of plasticized plastics. One measure of the elasticity of plasticized plastics is the Shore A hardness. The lower the Shore A hardness, the higher the elasticity of the plasticized plastics.

[0157] A measure of good gelling properties can be a low dissolution temperature / gelling temperature. The compatibility (permanence) of plasticizers in plasticized plastics characterizes the extent to which plasticizers tend to exude during use of the plasticized plastics and thus the

[0158] The performance properties of the plastics may be impaired.

[0159] Low volatility during processing can, for example, be reflected by low process volatility.

[0160] Low volatility during use of the final product can, for example, be reflected by low film volatility.

[0161] Molding compound and plastisol

[0162] A further subject matter of the present invention is a molding compound or a plastisol, wherein the molding compound or the plastisol contains at least one compound of the general formula (I) or a plasticizer composition as described above, and at least one polymer.

[0163] The plasticizer can therefore be used as a plasticizer in a molding compound or plastisol.

[0164] In general, the term “molding compound” refers to unformed or pre-formed materials that are processed into semi-finished or finished parts by means of mechanical force and elevated temperatures through non-cutting forming.

[0165] In general, a plastisol is a suspension of finely powdered polymer in liquid plasticizer, whereby the dissolution rate of the polymer in the liquid plasticizer is very low at room temperature. When the suspension of finely powdered polymer in liquid plasticizer is heated, a largely homogeneous phase forms between the polymer and plasticizer. The individual isolated plastic aggregates swell and bond (gel) to form a three-dimensional, highly viscous gel. This process is usually referred to as gelling and takes place above a certain minimum temperature. This minimum temperature is generally referred to as the gelling or dissolution temperature. The introduction of the necessary heat can be achieved via the parameters temperature and / or residence time. The faster the gelling process, the lower the temperature (with the same residence time) or the residence time (at the same temperature) can be selected.An indication of the speed of gelation is the dissolution temperature, i.e. the lower this is, the faster the plastisol gels.

[0166] The molding compound or plastisol may also contain a mixture of polymers. In one embodiment of the invention, the polymer is selected from a thermoplastic, an elastomer, and mixtures thereof.

[0167] The molding compound or plastisol containing the plasticizer usually contains at least one thermoplastic. The molding compound or plastisol may also contain a mixture of thermoplastics.

[0168] In one embodiment, the thermoplastic is selected from

[0169] - homo- or copolymers containing at least one monomer in polymerized form, selected from C2-C8 monoolefins such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols and their C2-C10 alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C1-C8 alcohols, vinyl aromatics such as styrene, acrylonitrile, methacrylonitrile, α,β-ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride,

[0170] - Homo- or copolymers of vinyl acetals, polyvinyl esters, polycarbonates, polyesters, polyethers, polyether ketones, thermoplastic polyurethanes, polysulfides, polysulfones, polyether sulfones, polyacrylates, polymethyl methacrylates, polystyrenes, polyvinyl alcohols, polyvinyl acetates, polyvinyl butyrals, polyvinyl chlorides, polycaprolactones, cellulose alkyl esters and mixtures thereof, and the elastomer selected from natural rubber and synthetic rubber such as polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber and mixtures thereof.

[0171] The molding compound or plastisol can, for example, be composed as shown in Table 1.

[0172] Table 1.

[0173]

[0174] Depending on the polymer contained in the molding compound, different amounts of plasticizer may be required to achieve the desired thermoplastic properties. Adjusting the desired thermoplastic properties of the molding compound is generally within the routine work of the person skilled in the art.

[0175] If no polyvinyl chloride is present in the molding compound, the amount of plasticizer in the molding compound is generally 0.5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound is 1.0 to 130 phr. It may be more preferred that the amount of plasticizer in the molding compound is 2.0 to 100 phr. The amount of plasticizer present in the molding compound can be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 phr. If polyvinyl chloride is present in the molding compound, the amount of plasticizer in the molding compound is generally 5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound be 15 to 200 phr. It may be more preferred that the amount of plasticizer in the molding compound be 30 to 150 phr.The amount of plasticizer contained in the molding compound can be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, or 145 phr.

[0176] Typically, the molding compound contains 20 to 90 wt.%, preferably 40 to 90 wt.%, more preferably 45 to 85 wt.% polyvinyl chloride. For example, the molding compound may contain 50, 55, 60, 65, 70, 75, or 80 wt.% polyvinyl chloride.

[0177] Depending on the polymer contained in the plastisol, different amounts of plasticizer may be required to achieve the desired plastisol properties. Adjusting the desired plastisol properties is generally within the routine work of the skilled person.

[0178] If the plastisol contains polyvinyl chloride, the proportion of plasticizer in the plastisol is usually 30 to 400 phr, preferably 50 to 200 phr. The content of plasticizers of the general formula (I) in a plastisol containing polyvinyl chloride is usually at least 10 phr, preferably at least 15 phr, and more preferably at least 20 phr.

[0179] Additives molding compound or plastisol with thermoplastics

[0180] The molding compound containing at least one thermoplastic and the plasticizer, or the plastisol containing at least one thermoplastic and the plasticizer, can expediently additionally contain at least one additive. The additive can be selected from stabilizers, lubricants, fillers, colorants, flame retardants, light stabilizers, blowing agents, polymeric processing agents, impact modifiers, optical brighteners, antistatic agents, biostabilizers, and mixtures thereof.

[0181] The additives described below do not represent a limitation of the molding compound or plastisol, but serve only to explain the molding compound or plastisol.

[0182] Stabilizers can be the usual polyvinyl chloride stabilizers in solid and liquid form, such as Ca / Zn, Ba / Zn, Pb, Sn stabilizers, acid-binding phyllosilicates, carbonates such as hydrotalcite, or mixtures thereof. The molding compound or plastisol can have a stabilizer content of 0.05 to 7 wt.%, preferably 0.1 to 5 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the molding compound or plastisol.

[0183] Lubricants are generally used to reduce the adhesion between the molding compound or plastisol and surfaces and are intended, for example, to reduce frictional forces during mixing, plasticizing or molding.

[0184] All common lubricants used in plastics processing can be used as lubricants in the molding compound or plastisol. Common lubricants used in plastics processing include hydrocarbons such as oils, paraffins, PE waxes, or mixtures thereof; fatty alcohols with 6 to 20 carbon atoms; ketones; carboxylic acids such as fatty acids, montanic acids, or mixtures thereof; oxidized PE waxes; metal salts of carboxylic acids; carboxylic acid amides; and carboxylic acid esters resulting from the esterification of alcohols such as ethanol, fatty alcohols, glycerol, ethanediol, or pentaerythritol with long-chain carboxylic acids.

[0185] The molding compound or plastisol may have a lubricant content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.2 to 2 wt.%, based on the total weight of the molding compound or plastisol.

[0186] Fillers are generally used to positively influence the compressive, tensile and / or flexural strength, hardness and / or heat resistance of the molding compound or plastisol.

[0187] For example, carbon black and / or inorganic fillers may be included in the molding compound or plastisol. Inorganic fillers can be selected from natural calcium carbonates, such as chalk, limestone, marble, synthetic calcium carbonates, dolomite, silicates, silicic acids, sand, diatomaceous earths, aluminum silicates such as kaolin, mica, feldspar, or mixtures of two or more of the aforementioned fillers.

[0188] The molding compound or plastisol may have a filler content of 0.01 to 80 wt.%, preferably 0.01 to 60 wt.%, more preferably 1 to 40 wt.%, based on the total weight of the molding compound or plastisol. Thus, the molding compound or plastisol may have a filler content of 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36, or 39 wt.%.

[0189] Colorants can be used to adapt the molding compound or plastisol to different applications. Colorants can be, for example, pigments or dyes. Pigments can be inorganic and / or organic pigments contained in the molding compound or plastisol. Inorganic pigments can be cobalt pigments such as COO / AI2O3 and / or chromium pigments such as CO2Os. Organic pigments can be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, and / or dioxazine pigments.

[0190] The molding compound or plastisol may have a colorant content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.1 to 3 wt.%, based on the total weight of the molding compound or plastisol.

[0191] Flame inhibitors can be used to reduce the flammability of the molding compound or plastisol and to reduce smoke formation during combustion.

[0192] Flame retardants that may be contained in the molding compound or plastisol may be, for example, antimony trioxide, chlorinated paraffin, phosphate esters, aluminum hydroxide and / or boron compounds.

[0193] The molding compound or plastisol may have a flame retardant content of 0.01 to 10 wt.%, preferably 0.2 to 5 wt.%, more preferably 0.5 to 2 wt.%, based on the total weight of the molding compound or plastisol.

[0194] Light stabilizers, such as UV absorbers, can be used to protect the molding compound or plastisol from damage caused by the influence of light.

[0195] Light stabilizers can be, for example, hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates, hindered amine light stabilizers such as derivatives of 2,2,6,6-tetramethylpiperidine or mixtures of the aforementioned compounds.

[0196] The molding compound or plastisol may have a light stabilizer content of 0.01 to 7 wt.%, preferably 0.02 to 4 wt.%, more preferably 0.05 to 3 wt.%, based on the total weight of the molding compound or plastisol.

[0197] Additives molding compound with elastomers

[0198] The molding compound may contain the plasticizer and at least one elastomer. The molding compound may also contain the plasticizer and a mixture of elastomers.

[0199] As described above, an elastomer can be, for example, a rubber. A rubber can be a natural rubber or a synthetic rubber. Synthetic rubber can be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, and mixtures thereof.

[0200] As a rule, the molding compound contains at least natural rubber and / or at least one synthetic rubber, whereby the contained rubber or the rubber mixture can be vulcanized with sulfur.

[0201] The molding compound usually contains at least one elastomer in a proportion of 20 to 95 wt.%, based on the total weight of the molding compound. It may be preferred for the molding compound to contain at least one elastomer in a proportion of 45 to 90 wt.%. It may also be preferred for the molding compound to contain at least one elastomer in a proportion of 50 to 85 wt. The molding compound may, for example, contain 55, 60, 65, 70, 75, or 80 wt.% of at least one elastomer.

[0202] If the molding compound contains at least one elastomer, especially at least natural rubber or at least one synthetic rubber, the amount of plasticizer in the molding compound is generally 1 to 60 phr. It may be preferred that the amount of plasticizer in the molding compound be 2 to 40 phr, and more preferably 3 to 30 phr. The amount of plasticizer contained in the molding compound can be, for example, 5, 10, 15, 20, or 25 phr.

[0203] The molding compound may also contain a mixture of at least one thermoplastic and at least one elastomer. For example, the molding compound may contain a mixture of polyvinyl chloride and at least one elastomer.

[0204] If the molding compound contains polyvinyl chloride and at least one elastomer, the elastomer content is generally 1 to 50 wt.% based on the total weight of the molding compound. It may be preferred that the elastomer content be 3 to 40 wt.% based on the total weight of the molding compound. It may be more preferred that the elastomer content be 5 to 30 wt.% based on the total weight of the molding compound. The molding compound may contain, for example, 10, 15, 20, or 25 wt.% of elastomer.

[0205] Depending on the composition of the mixture of polyvinyl chloride and at least one elastomer in the molding compound, the amount of plasticizer required to achieve the desired properties can vary greatly. It is within the skill of the art to use appropriate amounts of plasticizer to achieve the desired properties. Typically, the amount of plasticizer in the molding compound containing polyvinyl chloride and at least one elastomer is 0.5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound containing polyvinyl chloride and at least one elastomer is 1 to 150 phr, and more preferably 2 to 120 phr. The amount of plasticizer contained in the molding compound can be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110 or 115 phr.

[0206] The molding compound containing at least one elastomer and the plasticizer may expediently additionally contain at least one additive. The additive may be selected from carbon black, silicon dioxide, phenolic resins, vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, activators, various oils, anti-aging agents, or mixtures of the aforementioned additives.

[0207] Other additives may be substances that the expert would mix into tires or other rubber compounds based on his or her expertise in order to achieve a specific effect.

[0208] Use of the molding compounds

[0209] The molding compound can be used, for example, for the production of molded articles, gloves, films, wallpapers, or heterogeneous flooring, or for textile coating.

[0210] Shaped bodies can be, for example, containers, apparatus or foamed devices.

[0211] Containers can be, for example, housings of electrical appliances, such as kitchen appliances or computer cases, pipes, hoses, such as water or irrigation hoses, industrial rubber hoses, chemical hoses, sheathing for wire or cable, sheathing for tools, bicycle, scooter or wheelbarrow handles, metal coatings or packaging containers.

[0212] Devices can be, for example, tools, furniture such as chairs, shelves, tables, records, profiles such as window profiles, floor profiles for outdoor use or profiles for conveyor belts, components for vehicle construction such as body components, underbody protection or vibration dampers, or erasers.

[0213] Foamed devices can be, for example, upholstery, mattresses, foams or insulation materials.

[0214] Films can be, for example, tarpaulins such as truck tarpaulins, roof tarpaulins, geomembrane tarpaulins, stadium roofs or tent tarpaulins, seals, composite films such as films for laminated safety glass, self-adhesive films, laminating films, shrink films, outdoor floor coverings, adhesive tape films, coatings, swimming pond liners, ornamental pond liners, tablecloths or artificial leather.

[0215] The molding compound can be used to produce molded articles or films that come into direct contact with humans or food.

[0216] Molded articles or films that come into direct contact with humans or food can be, for example, medical devices, hygiene products, food packaging, interior products, baby and children's products, child care articles, sports or leisure products, clothing, fibers or fabrics.

[0217] Medical devices that can be manufactured using the molding compound include, for example, tubes for enteral nutrition or hemodialysis, ventilation tubes, drainage tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or breathing masks.

[0218] Food packaging that can be produced using the molding compound can include, for example, cling film, food tubes, drinking water tubes, containers for storing or freezing food, lid seals, closure caps, crown corks or artificial wine corks.

[0219] Products for the interior that can be manufactured using the molding compound can be, for example, floor coverings, which can be homogeneous or made up of several layers consisting of at least one foamed layer, such as floor coverings, mudguard mats, sports flooring, luxury vinyl tiles (LVT), artificial leather, wall coverings, foamed or non-foamed wallpapers in buildings, paneling or console covers in vehicles.

[0220] Baby and children's products that can be manufactured using the molding compound include toys such as dolls, toy figures or clay, inflatable toys such as balls or rings, anti-slip socks, swimming aids, stroller covers, changing mats, hot water bottles, teething rings or bottles.

[0221] Sports or leisure products that can be manufactured using the molding compound include, for example, exercise balls, exercise mats, seat cushions, massage balls or rollers, shoes, shoe soles, balls, air mattresses, safety goggles, gloves or drinking bottles.

[0222] Clothing that can be manufactured using the molding compound includes latex clothing, protective clothing, rain jackets, or rubber boots. Use of plastisols

[0223] Plastisols are typically formed into the finished product shape at ambient temperature using various processes, such as coating, casting (such as tray casting or rotational casting), dipping, printing (such as screen printing), injection molding, and the like. Gelation then occurs through heating, resulting in a homogeneous, more or less flexible product upon cooling.

[0224] The plastisol can be used for the production of films, wallpapers, seamless hollow bodies, gloves, heterogeneous flooring or for applications in the textile sector, such as textile coatings.

[0225] Films can be, for example, truck tarpaulins, roof tarpaulins, covers in general such as boat covers, stroller covers or stadium roofs, tent tarpaulins, geomembranes, tablecloths, coatings, swimming pond liners, artificial leather or ornamental pond liners.

[0226] Gloves can be, for example, gardening gloves, medical gloves, chemical gloves, protective gloves or disposable gloves.

[0227] Furthermore, the plastisol can be used to produce, for example, seals, lid seals, panels or console covers in vehicles, dolls, toy figures or clay, inflatable toys such as balls or rings, anti-skid socks, swimming aids, changing mats, exercise balls, exercise mats, seat cushions, vibrators, massage balls or rollers, latex clothing, protective clothing, rain jackets or rubber boots.

[0228] The plastisol usually contains polyvinyl chloride.

[0229] Non-PVC applications

[0230] The present disclosure also relates to the use of the plasticizer as a calendering aid or rheology aid. The present disclosure also relates to the use of the plasticizer in surface-active compositions such as flow or film-binding aids, defoamers, antifoams, wetting agents, coalescing agents, or emulsifiers. The plasticizer can also be used in lubricants such as lubricating oils, lubricating greases, or lubricating pastes. Furthermore, the plasticizer can be used as a quenching agent for chemical reactions, as a desensitizer, in pharmaceutical products, in adhesives, in sealants, in inks such as printing inks, in impact modifiers, or as extenders.

[0231] Products containing the plasticizer

[0232] The disclosure relates to molded articles or films containing the plasticizer. Reference is made to the information provided regarding molded articles or films when using molding compounds to produce molded articles or films. The examples of molded articles or films cited therein are to be used to interpret the terms "molded article" or "film" in this section.

[0233] Preparation of compounds of general formula (I)

[0234] Easily accessible starting materials can be used to produce compounds of general formula (I). A particular economic and ecological advantage can be the possibility of producing compounds of general formula (I) from petrochemical and / or renewable raw materials.

[0235] Compounds of general formula (I) can be prepared, for example, by esterification of corresponding dicarboxylic acids with the corresponding aliphatic alcohols. The processes and specific process steps are either known to the person skilled in the art or will be apparent to him through his general technical knowledge.

[0236] This involves the reaction of at least one alcohol component, selected from the alcohols R1-OH and R2-OH, with a corresponding dicarboxylic acid. Suitable derivatives include acid halides and acid anhydrides. An acid halide can be, for example, an acid chloride. The reaction can be carried out in the presence of an esterification catalyst.

[0237] Conventional catalysts can be used as esterification catalysts, e.g., mineral acids such as sulfuric acid or phosphoric acid; organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid; and amphoteric catalysts, particularly titanium, tin(IV), or zirconium compounds such as tetraalkoxytitanium, e.g., tetrabutoxytitanium, or tin(IV) oxide. The water formed during the reaction can be removed by conventional means, e.g., distillation.For example, WO 02 / 038531 describes a process for preparing esters in which a) a mixture consisting essentially of the acid component or an anhydride thereof and the alcohol component is heated to boiling in a reaction zone in the presence of an esterification catalyst, b) the alcohol- and water-containing vapors are separated by rectification into an alcohol-rich fraction and a water-rich fraction, c) the alcohol-rich fraction is recycled to the reaction zone and the water-rich fraction is discharged from the process. The aforementioned catalysts are used as esterification catalysts. The esterification catalyst is used in an effective amount typically in the range of 0.05 to 10 wt. %, preferably 0.1 to 5 wt. %, based on the sum of the acid component (or anhydride) and alcohol component.Further detailed descriptions of the implementation of esterification processes can be found, for example, in US Pat. No. 6,310,235 B1, US Pat. No. 5,324,853 A, DE-A 2612355 (Derwent Abstract No. DW 77-72638 Y), or DE-A 1945359 (Derwent Abstract No. DW 73-27151 U). These documents are incorporated by reference in their entirety.

[0238] In general, the esterification of the corresponding dicarboxylic acid, namely 4,7-dioxodecanedioic acid, can be carried out in the presence of the above-described alcohol components R1-GH and / or R2-OH using an organic acid or mineral acid, especially concentrated sulfuric acid. It may be advantageous to use the alcohol component in at least twice the stoichiometric amount, based on the dicarboxylic acid.

[0239] The esterification can be carried out at ambient pressure or at reduced or elevated pressure. It may be preferred that the esterification be carried out at ambient pressure or at reduced pressure.

[0240] The esterification can be carried out in the absence of an added solvent or in the presence of a solvent.

[0241] If the esterification is carried out in the presence of a solvent, this is preferably a solvent that is inert under the reaction conditions. An inert solvent is generally understood to be a solvent that, under the given reaction conditions, does not react with the reactants, reagents, solvents, or the resulting products. The inert solvent can preferably form an azeotrope with water. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons, or ethers. It may be preferred that the solvent be selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ethers, THF, dioxane, and mixtures thereof.

[0242] The esterification is typically carried out in a temperature range of 50 to 250 °C. If the esterification catalyst is selected from organic acids or mineral acids, the esterification is typically carried out in a temperature range of 50 to 160 °C.

[0243] If the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250 °C.

[0244] The esterification can be carried out in the absence or presence of an inert gas. An inert gas is generally understood to be a gas that, under the given reaction conditions, does not react with the reactants, reagents, solvents, or the resulting products. It may be preferable for the esterification to take place without the addition of an inert gas.

[0245] For example, the alcohol and acid are combined in a 2:1 molar ratio in a stirred flask, along with the esterification catalyst aluminum trimethylsulfonate in a molar ratio of 400:1, based on the acid, without inert gas. The reaction mixture is heated to boiling, preferably between 100 and 140 °C. The water formed during the reaction is azeotropically distilled off together with the alcohol and then separated. The alcohol is returned to the reaction mixture.

[0246] The 4,7-dioxodecanedioic acid and aliphatic alcohols used to prepare the compounds of general formula (I) can either be purchased commercially or prepared according to known synthesis routes, as described, for example, in X.-L. Li et al., Green Chem. 2018, 20, 362-368.

[0247] Production of 4,7-dioxodecanedioic acid

[0248] Preferably, 4,7-dioxodecanedioic acid is prepared according to a further aspect of the present invention. The said process for preparing 4,7-dioxosebacic acid according to formula (II) is characterized by reacting levulinic acid with furfural in the presence of a base to form furfurylidene levulinic acid; reacting the furfurylidene levulinic acid in an alcoholic solvent in the presence of an acidic catalyst to form a reaction product containing 4,7-dioxosebacic acid; evaporating the alcoholic solvent and taking up the residue in water; extracting the aqueous solution with a water-immiscible solvent; and evaporating the water-immiscible solvent to obtain 4,7-dioxosebacic acid. In this way, 4,7-dioxosebacic acid is obtained in higher purity and yield.

[0249] In one embodiment, the resulting 4,7-dioxosebacic acid according to formula (II) is reacted with a C1-C12 alcohol, preferably a C3-C12 alcohol.

[0250] When reacting levulinic acid with furfural, the levulinic acid is preferably initially introduced as an aqueous solution to which the base is added. The base can be selected from hydroxides, bicarbonates, carbonates, carboxylates or mixtures thereof in the form of their alkali or alkaline earth compounds. Alkali hydroxides, such as sodium hydroxide, or alkali carbonates, such as sodium carbonate, are preferably used. The base is usually added at room temperature. A solution of furfural in an alcoholic solvent is preferably metered into the aqueous solution of levulinic acid and base. The alcoholic solvent can be selected from methanol, ethanol, propanols, and tert-butanol, preferably ethanol. The metered addition preferably takes place at elevated temperature, e.g., at a temperature in the range from 40 to 100°C. Conventional methods known to those skilled in the art are suitable for isolation.For example, the resulting furfurylidene levulinic acid can be precipitated by adding an acid, e.g., hydrochloric acid, and filtered off. The resulting solid can be purified by further measures, such as washing, recrystallization, or chromatography.

[0251] When reacting furfurylidene levulinic acid, it is initially introduced into an alcoholic solvent. The alcoholic solvent can be selected from methanol, ethanol, propanols, and tert-butanol, preferably ethanol. An acid is added, preferably at an elevated temperature, e.g., at a temperature in the range from 40 to 100°C. The acidic catalyst can be selected from mineral acids, such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid, preferably hydrochloric acid. After evaporation of the alcoholic solvent, the residue is taken up in water. The aqueous solution is preferably admixed with activated carbon and treated at an elevated temperature, e.g., at a temperature in the range from 40 to 100°C, and then filtered. The aqueous solution is extracted with a water-immiscible solvent.The water-immiscible solvent can be selected from methyl isobutyl ketone, methyl tert-butyl ether, hexane, heptane, tetrahydropyran, benzene, toluene, and xylene, preferably methyl tert-butyl ether. All methods known to the person skilled in the art are suitable for extraction, e.g., continuous extraction using a perforator. After the extraction is complete, the water-immiscible solvent is evaporated off, yielding 4,7-dioxosebacic acid. In a preferred embodiment, 4,7-dioxosebacic acid according to formula (II) is produced from renewable raw materials.

[0252] Furfural can be obtained, for example, by the action of sulfuric acid on pentose-containing plant materials, such as corn cobs or bagasse, or during pulp production by the magnesium bisulfite process.

[0253] Levulinic acid can be obtained from hexose of biomass or by hydrolysis of cellulose.

[0254] Transesterification

[0255] The preparation of the compounds of general formula (I) can also be carried out by transesterification. Transesterification processes and specific process measures are either known to the person skilled in the art or are apparent from his general technical knowledge. The starting materials used are generally compounds of general formula (I) in which R 1 and R 2 independently of one another represent C 1 to C 2 -alkyl. This includes, for example, the reaction of corresponding carboxylic acid dialkyl esters, for example 4,7-

[0256] Dioxodecanedioic acid dimethyl ester or 4,7-dioxodecanedioic acid diethyl ester or 4,7-dioxodecanedioic acid ethyl methyl ester or mixtures thereof, with at least one alcohol component selected from the alcohols R1-OH and R2-OH, where R1 and R2 are C3 to C12 alkyl, in the presence of a suitable transesterification catalyst.

[0257] Examples of suitable transesterification catalysts include the conventional catalysts commonly used for transesterification reactions, which are also often used in esterification reactions. These include, for example:Mineral acids, such as sulfuric acid or phosphoric acid; organic sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid; or special metal catalysts from the group of tin (IV) catalysts, for example dialkyltin dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides; from the group of titanium catalysts, monomeric or polymeric titanates or titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titanate; from the group of zirconium catalysts, zirconates or zirconium chelates such as tetrapropyl zirconate, tetrabutyl zirconate, triethanolamine zirconate; and lithium catalysts such as lithium salts, lithium alkoxides; or aluminum(III), chromium(III), iron(III), cobalt(II), nickel(II) and zinc(II) acetylacetonate.

[0258] The amount of transesterification catalyst used can generally be from 0.001 to 10 wt.%, preferably from 0.05 to 5 wt.%. The reaction mixture is generally heated to its boiling point, so that the reaction temperature is in a temperature range of 20 to 200°C, depending on the reactants. The transesterification can be carried out at ambient pressure or at reduced or elevated pressure. It may be preferred that the transesterification be carried out at a pressure of 0.001 to 200 bar, more preferably 0.01 to 5 bar.

[0259] The lower-boiling alcohol split off during the transesterification can be continuously distilled off to shift the equilibrium of the transesterification reaction. The distillation column required for this is usually directly connected to the transesterification reactor. For example, the distillation column can be installed directly next to the transesterification reactor. If several transesterification reactors are used in series, each of these reactors can be equipped with a distillation column, or the evaporated alcohol mixture can be fed to a distillation column via one or more collecting lines, preferably from the last boilers in the transesterification reactor cascade. The higher-boiling alcohol recovered during this distillation is preferably recycled back into the transesterification.

[0260] When using an amphoteric catalyst, its removal is generally achieved by hydrolysis and subsequent removal of the resulting metal oxide, e.g., by filtration. It may be preferred that, after the reaction, the catalyst be hydrolyzed by washing with water, and the precipitated metal oxide be filtered off. The filtrate can be subjected to further processing to isolate and / or purify the product. It may be preferred that the product be removed by distillation.

[0261] The transesterification of the di-(Ci-C2)-alkyl esters of corresponding dicarboxylic acids, for example 4,7-dioxodecanedioic acid dimethyl ester, with at least one alcohol component selected from the alcohols R1-GH and R2-OH can preferably be carried out in the presence of at least one titanium(IV) alkoxide. Preferred titanium(IV) alkoxides are tetrapropoxytitanium, tetrabutoxytitanium, or mixtures thereof. It may be preferred that the alcohol component be used in at least twice the stoichiometric amount, based on the di-(Ci-C2-alkyl) esters used.

[0262] The transesterification can be carried out in the absence or presence of an added solvent. It may be preferable to carry out the transesterification in the presence of an inert solvent. Suitable solvents are those previously mentioned for the esterification. These include, in particular, toluene and THF.

[0263] The temperature during transesterification is usually in the range of 20 to 200 °C.

[0264] The transesterification can be carried out in the absence or presence of an inert gas. An inert gas is generally understood to be a gas that, under the given reaction conditions, does not react with the reactants, reagents, solvents, or the resulting products. It may be preferable to carry out the transesterification without adding an inert gas.

[0265] Preferred C3 to C12 alkanols used to prepare the compounds (I) present in the plasticizer composition according to the invention can be straight-chain or branched or consist of mixtures of straight-chain and branched C3 to C12 alkanols. These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-octanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol, or isododecanol. It may be preferred that C7 to C8 alkanols such as 2-ethylhexanol, 2-octanol, isononanol and 2-propylheptanol are used, and more preferably that 2-ethylhexanol, 2-octanol or 2-propylheptanol is used.

[0266] Heptanol

[0267] The heptanols used to prepare the compounds of general formula (I) can be straight-chain or branched, or consist of mixtures of straight-chain and branched heptanols. It may be preferred to use mixtures of branched heptanols, also referred to as isoheptanol, which are prepared by the rhodium- or preferably cobalt-catalyzed hydroformylation of dimerpropene, obtainable e.g. by the Dimersol® process, and subsequent hydrogenation of the resulting isoheptanals to form an isoheptanol mixture. Depending on its preparation, the isoheptanol mixture obtained in this way consists of several isomers. Essentially straight-chain heptanols can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-hexene and subsequent hydrogenation of the resulting n-heptanal to n-heptanol. The hydroformylation of 1-hexene orDimer propene can be prepared by processes known per se: In the hydroformylation with rhodium catalysts homogeneously dissolved in the reaction medium, both uncomplexed rhodium carbonyls, which are formed in situ under the conditions of the hydroformylation reaction in the hydroformylation reaction mixture under the action of synthesis gas, e.g. from rhodium salts, and complex rhodium carbonyl compounds, in particular complexes with organic phosphines, such as triphenylphosphine, or organophosphites, preferably chelating biphosphites, as described, for example, in US-A 5288918, can be used as catalyst. In the cobalt-catalyzed hydroformylation of these olefins, cobalt carbonyl compounds which are homogeneously soluble in the reaction mixture and are formed in situ from cobalt salts under the conditions of the hydroformylation reaction under the action of synthesis gas.If the cobalt-catalyzed hydroformylation is carried out in the presence of trialkyl- or triarylphosphines, the desired heptanols are formed directly as the hydroformylation product, thus eliminating the need for further hydrogenation of the aldehyde function. Suitable processes for the cobalt-catalyzed hydroformylation of 1-hexene or the hexene isomer mixtures include, for example, the industrially established processes described in Falbe, New Syntheses with Carbon Monoxide, Springer, Berlin, 1980, pages 162-168, such as the Ruhrchemie process, the BASF process, the Kuhlmann process, or the Shell process.While the Ruhrchemie, BASF, and Kuhlmann processes use non-ligand-modified cobalt carbonyl compounds as catalysts, yielding hexanal mixtures, the Shell process (DE-A 1593368) uses phosphine- or phosphite-ligand-modified cobalt carbonyl compounds as catalysts, which, due to their additional high hydrogenation activity, lead directly to the hexanol mixtures. Advantageous embodiments for carrying out the hydroformylation with non-ligand-modified cobalt carbonyl complexes are described in detail, for example, in DE-A 2139630, DE-A 2244373, DE-A 2404855, and WO 01014297.

[0268] For the rhodium-catalyzed hydroformylation of 1-hexene or the hexene isomer mixtures, the industrially established rhodium low-pressure hydroformylation process with triphenylphosphine ligand-modified

[0269] Rhodium carbonyl compounds can be used, as is the subject of US-A 4,148,830, for example. It may be advantageous to use non-ligand-modified rhodium carbonyl compounds as catalysts for the rhodium-catalyzed hydroformylation of long-chain olefins, such as the hexene isomer mixtures obtained by the abovementioned processes. In contrast to the low-pressure process, a higher pressure of 80 to 400 bar must be set. The implementation of such high-pressure rhodium hydroformylation processes is described, for example, in EP-A 695734, EP-B 880494, and EP-B 1047655.

[0270] The isoheptanal mixtures obtained after hydroformylation of the hexene isomer mixtures can, for example, be catalytically hydrogenated in a conventional manner to give isoheptanol mixtures. It may be preferred to use heterogeneous catalysts containing, as the catalytically active component, metals and / or metal oxides of transition groups VI to VIII and I of the Periodic Table of the Elements, in particular chromium, molybdenum, manganese, rhenium, iron, cobalt, nickel, and / or copper, optionally deposited on a support material such as Al2O3, SiO2, and / or TiO2. Such catalysts are described, for example, in DE-A 3228881, DE-A 2628987, and DE-A 2445303.Furthermore, it may be preferred that the hydrogenation of the isoheptanals is carried out with an excess of hydrogen of 1.5 to 20% above the amount of hydrogen stoichiometrically required for the hydrogenation of the isoheptanals, at temperatures of 50 to 200 °C and at a hydrogen pressure of 25 to 350 bar, and to avoid side reactions, a small amount of water, for example in the form of an aqueous solution of an alkali metal hydroxide or carbonate according to the teaching of WO 01087809, is added to the hydrogenation feed according to DE-A 2628987. Octanol.

[0271] 2-Ethylhexanol, which for many years was the plasticizer alcohol produced in the largest quantities, can be obtained, for example, via the aldol condensation of n-butyraldehyde to 2-ethylhexenal and its subsequent hydrogenation to 2-ethylhexanol (see Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A 10, pp. 137 - 140, VCH Verlagsgesellschaft GmbH, Weinheim 1987).

[0272] Essentially straight-chain octanols can be obtained, for example, by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptene followed by hydrogenation of the resulting n-octanal to n-octanol. The 1-heptene required for this can be obtained, for example, from the Fischer-Tropsch synthesis of hydrocarbons.

[0273] In contrast to 2-ethylhexanol or n-octanol, the alcohol isooctanol is not a single chemical compound due to its method of production, but rather an isomeric mixture of differently branched Cs alcohols, for example 2,3-dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol,

[0274] 3-Methyl-1-heptanol and 5-methyl-1-heptanol, which can be present in isooctanol in varying proportions depending on the production conditions and processes used. Isooctanol is typically produced by codimerizing propene with butenes, such as n-butenes, followed by hydroformylation of the resulting mixture of heptene isomers. The octanal isomer mixture obtained in the hydroformylation can then be hydrogenated to isooctanol in a conventional manner.

[0275] The codimerization of propene with butenes to form isomeric heptenes can be achieved, for example, using the homogeneously catalyzed Dimersol® process (e.g., Chauvin et al.; Chem. Ind.; May 1974, pp. 375-378), in which a soluble nickel-phosphine complex in the presence of an ethylaluminum chloride compound, such as ethylaluminum dichloride, serves as the catalyst. Phosphine ligands for the nickel complex catalyst include tributylphosphine, triisopropylphosphine, tricyclohexylphosphine, and / or tribenzylphosphine. The reaction generally takes place at temperatures from 0 to 80 °C, whereby it may be advantageous to set a pressure at which the olefins are dissolved in the liquid reaction mixture (for example Cornils; Hermann: Applied Homogeneous Catalysis with Organometallic Compounds; 2nd edition; Vol. 1 ; pp. 254 - 259, Wiley-VCH, Weinheim 2002).

[0276] As an alternative to the Dimersol® process, which uses nickel catalysts homogeneously dissolved in the reaction medium, the codimerization of propene with butenes can also be carried out using heterogeneous NiO catalysts deposited on a support, resulting in similar heptene isomer distributions as in the homogeneously catalyzed process. Such catalysts are used, for example, in the so-called Octol® process (Hydrocarbon Processing, February 1986, pp. 31-33). A highly suitable specific nickel heterogeneous catalyst for olefin dimerization or codimerization is disclosed, for example, in WO 9514647.

[0277] Instead of nickel-based catalysts, Bronsted-azide heterogeneous catalysts can also be used for the codimerization of propene with butenes, generally yielding more highly branched heptenes than in nickel-catalyzed processes. Examples of suitable catalysts are solid phosphoric acid catalysts, such as phosphoric acid-impregnated kieselguhr or diatomaceous earth, as used, for example, by the PolyGas® process for olefin dimerization or oligomerization (e.g., Chitnis et al.; Hydrocarbon Engineering 10, No. 6 - June 2005). Bronsted-azide catalysts that are very suitable for the codimerization of propene and butenes to heptenes are usually zeolites, which are used, for example, in the EMOGAS® process, which has been further developed based on the PolyGas® process.

[0278] The 1-heptene and the heptene isomer mixtures are converted into n-octanal and octanal isomer mixtures by rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, according to the known processes explained above in connection with the preparation of n-heptanal and heptanal isomer mixtures. These are then hydrogenated to the corresponding octanols, for example, using one of the catalysts mentioned above in connection with the preparation of n-heptanol and isoheptanol.

[0279] 2-octanol

[0280] 2-Octanol is commercially available and is produced by the basic treatment of castor oil at high temperatures with simultaneous production of sebacic acid (US 2015 / 0299093 AI, High temperature fusion of castor oil with caustic soda: a critical study, Nanavati, DD Journal of Scientific Volume 35 Issue 3 Pages 163-8 (1976)).

[0281] Nonanol

[0282] The nonanols used to prepare the compounds of general formula (I) contained in the plasticizer composition can be straight-chain or branched, or composed of mixtures of straight-chain and branched nonanols. It may be preferred to use mixtures of branched nonanols, also referred to as isononanols, as the alcohol component. Essentially straight-chain nonanol can be obtained, for example, by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-octene and subsequent hydrogenation of the resulting n-nonanal. The starting olefin 1-octene can be obtained, for example, via ethylene oligomerization using a nickel complex catalyst that is homogeneously soluble in the reaction medium, i.e., 1,4-butanediol, and has, for example, diphenylphosphinoacetic acid or 2-diphenylphosphinobenzoic acid as the ligand.This process is also known as the Shell Higher Olefins Process or SHOP process (for example, Weisermel, Arpe: Industrial Organic Chemistry; 5th edition; p. 96; Wiley-VCH, Weinheim 1998).

[0283] Isononanol is not a single chemical compound, but rather a mixture of variably branched isomeric Cg alcohols, which can have varying degrees of branching depending on the method of their preparation, particularly the starting materials used. Isononanols are generally produced by dimerizing butenes to form isooctene mixtures, followed by hydroformylation of the isooctene mixtures, and hydrogenation of the resulting isononanal mixtures to form isononanol mixtures, as explained, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A1, pp. 291-292, VCH Verlagsgesellschaft GmbH, Weinheim 1995.

[0284] Isobutene, cis- and trans-2-butene, as well as 1-butene, or mixtures of these butene isomers, can be used as starting materials for the production of isononanols. The dimerization of pure isobutene, catalyzed primarily by liquid, e.g., sulfuric or phosphoric acid, or solid, e.g., phosphoric acid or zeolite supported on diatomaceous earth, SiO2, or Al2O3, or Bronsted acids, predominantly yields the highly branched 2,4,4-trimethylpentene, also known as diisobutylene, which, after hydroformylation and hydrogenation of the aldehyde, yields highly branched isononanols.

[0285] Isononanols with a lower degree of branching may be preferred. Such slightly branched isononanol mixtures are prepared from the linear butenes 1-butene, cis- and / or trans-2-butene, which may optionally contain even smaller amounts of isobutene, for example via the above-described route of butene dimerization, hydroformylation of the isooctene, and hydrogenation of the resulting isononanal mixtures. It may be preferred to use raffinate II as the raw material.Raffinate II can generally be obtained from the C4 cut of a cracker, for example a steam cracker, which, after elimination of allenes, acetylenes and dienes, in particular 1,3-butadiene, by its partial hydrogenation to linear butenes or its separation by extractive distillation, for example by means of N-methylpyrrolidone, and subsequent Bronsted acid-catalyzed removal of the isobutene contained therein by its reaction with methanol or isobutanol according to industrially established processes to form the fuel additive methyl tert-butyl ether (MTBE) or the isobutyl tert-butyl ether used to obtain pure isobutene.

[0286] In addition to 1-butene and cis- and trans-2-butene, raffinate II may also contain n- and iso-butane and residual amounts of up to 5 wt.% of isobutene.

[0287] The dimerization of the linear butenes or of the butene mixture contained in the raffinate II can be carried out, for example, by means of the common, industrially practiced processes as explained above in connection with the production of isoheptene mixtures, for example by means of heterogeneous, Bronsted-acidic catalysts as used, for example, in the PolyGas® or EMOGAS® process, by means of the Dimersol® process using nickel complex catalysts homogeneously dissolved in the reaction medium or by means of heterogeneous, nickel(II) oxide-containing catalysts according to the Octol® process or, for example, the process according to WO 9514647. The isooctene mixtures obtained are converted into isononanal mixtures by means of the known processes explained above in connection with the production of heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation.These are then hydrogenated to the suitable isononanol mixtures, for example using one of the catalysts mentioned above in connection with isoheptanol production.

[0288] The isononanol isomer mixtures produced in this way can be characterized by their isoindex, which can be calculated from the degree of branching of the individual isomeric isononanol components in the isononanol mixture multiplied by their percentage in the isononanol mixture. For example, n-nonanol contributes 0, methyloctanols (one branch) contribute 1, and dimethylheptanols (two branches) contribute 2 to the isoindex of an isononanol mixture. The higher the linearity, the lower the isoindex of the respective isononanol mixture. Accordingly, the isoindex of an isononanol mixture can be determined by gas chromatographic separation of the isononanol mixture into its individual isomers and the concomitant quantification of their percentage content in the isononanol mixture, determined using standard methods of gas chromatographic analysis.To increase the volatility and improve the gas chromatographic separation of the isomeric nonanols, they are advantageously trimethylsilylated prior to gas chromatographic analysis using standard methods, for example, by reaction with N-methyl-N-trimethylsilyltrifluoroacetamide. To achieve the best possible separation of the individual components in gas chromatographic analysis, capillary columns with polydimethylsiloxane as the stationary phase are typically used. Such capillary columns are commercially available, and only a few routine experiments are required by the expert to select the product optimally suited for this separation task from the wide range available commercially.The diisononyl esters of the general formula (I) used in the plasticizer composition are generally esterified with isononanols having an isoindex of 0.8 to 2, preferably of 1.0 to 1.8 and particularly preferably of 1.1 to 1.5, which can be prepared by the processes mentioned above.

[0289] Possible compositions of isononanol mixtures which can be used to prepare the compounds of the general formula (I) according to the disclosure are given below only by way of example, it being noted that the proportions of the isomers listed in detail in the isononanol mixture may vary depending on the composition of the starting material, for example raffinate II, whose composition of butenes may vary depending on the production process, and on fluctuations in the production conditions used, for example the age of the catalysts used and the temperature and pressure conditions which must be adapted thereto.

[0290] For example, an isononanol mixture produced by cobalt-catalyzed hydroformylation and subsequent hydrogenation from an isooctene mixture produced using raffinate II as raw material by means of the catalyst and process according to WO 9514647 may have the following composition:

[0291] 1.73 to 3.73 wt.%, preferably 1.93 to 3.53 wt.%, particularly preferably 2.23 to 3.23 wt.% 3-ethyl-6-methyl-hexanol;

[0292] 0.38 to 1.38 wt.%, preferably 0.48 to 1.28 wt.%, particularly preferably 0.58 to 1.18 wt.% 2,6-dimethylheptanol;

[0293] 2.78 to 4.78 wt.%, preferably 2.98 to 4.58 wt.%, particularly preferably 3.28 to 4.28 wt.% 3,5-dimethylheptanol;

[0294] 6.30 to 16.30 wt.%, preferably 7.30 to 15.30 wt.%, particularly preferably

[0295] 8.30 to 14.30 wt.% 3,6-dimethylheptanol;

[0296] 5.74 to 11.74 wt.%, preferably 6.24 to 11.24 wt.%, particularly preferably

[0297] 6.74 to 10.74 wt% 4,6-dimethylheptanol;

[0298] 1.64 to 3.64 wt.%, preferably 1.84 to 3.44 wt.%, particularly preferably 2.14 to 3.14 wt.% 3,4,5-trimethylhexanol;

[0299] 1.47 to 5.47 wt.%, preferably 1.97 to 4.97 wt.%, particularly preferably 2.47 to 4.47 wt.% of 3,4,5-trimethylhexanol, 3-methyl-4-ethylhexanol and 3-ethyl-4-methylhexanol;

[0300] 4.00 to 10.00 wt.%, preferably 4.50 to 9.50 wt.%, particularly preferably 5.00 to 9.00 wt.% 3,4-dimethylheptanol;

[0301] 0.99 to 2.99 wt.%, preferably 1.19 to 2.79 wt.%, particularly preferably 1.49 to 2.49 wt.% of 4-ethyl-5-methylhexanol and 3-ethylheptanol; 2.45 to 8.45 wt.%, preferably 2.95 to 7.95 wt.%, particularly preferably 3.45 to 7.45 wt.% of 4,5-dimethylheptanol and 3-methyloctanol;

[0302] 1.21 to 5.21 wt.%, preferably 1.71 to 4.71 wt.%, particularly preferably 2.21 to 4.21 wt.% 4,5-dimethylheptanol;

[0303] 1.55 to 5.55 wt.%, preferably 2.05 to 5.05 wt.%, particularly preferably 2.55 to 4.55 wt.% 5,6-dimethylheptanol;

[0304] 1.63 to 3.63 wt.%, preferably 1.83 to 3.43 wt.%, particularly preferably 2.13 to 3.13 wt.% 4-methyloctanol;

[0305] 0.98 to 2.98 wt.%, preferably 1.18 to 2.78 wt.%, particularly preferably 1.48 to 2.48 wt.% 5-methyloctanol;

[0306] 0.70 to 2.70 wt.%, preferably 0.90 to 2.50 wt.%, particularly preferably 1.20 to 2.20 wt.% 3,6,6-trimethylhexanol;

[0307] 1.96 to 3.96 wt.%, preferably 2.16 to 3.76 wt.%, particularly preferably 2.46 to 3.46 wt.% 7-methyloctanol;

[0308] 1.24 to 3.24 wt.%, preferably 1.44 to 3.04 wt.%, particularly preferably 1.74 to 2.74 wt.% 6-methyloctanol;

[0309] 0.1 to 3 wt.%, preferably 0.2 to 2 wt.%, particularly preferably 0.3 to 1 wt.% n-nonanol;

[0310] 25 to 35% by weight, preferably 28 to 33% by weight, particularly preferably 29 to 32% by weight of other alcohols having 9 and 10 carbon atoms; with the proviso that the total of the said components amounts to 100% by weight.

[0311] According to the above, an isononanol mixture produced by cobalt-catalyzed hydroformylation and subsequent hydrogenation using an ethylene-containing butene mixture as raw material by means of the PolyGas® or EMOGAS® process can vary within the range of the following compositions, depending on the raw material composition and variations in the reaction conditions used:

[0312] 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0 wt.% n-nonanol;

[0313] 12.8 to 28.8 wt.%, preferably 14.8 to 26.8 wt.%, particularly preferably 15.8 to 25.8 wt.% 6-methyloctanol;

[0314] 12.5 to 28.8 wt.%, preferably 14.5 to 26.5 wt.%, particularly preferably 15.5 to 25.5 wt.% 4-methyloctanol;

[0315] 3.3 to 7.3 wt.%, preferably 3.8 to 6.8 wt.%, particularly preferably 4.3 to 6.3 wt.% 2-methyloctanol;

[0316] 5.7 to 11.7 wt.%, preferably 6.3 to 11.3 wt.%, particularly preferably 6.7 to

[0317] 10.7 wt% 3-ethylheptanol;

[0318] 1.9 to 3.9 wt.%, preferably 2.1 to 3.7 wt.%, particularly preferably 2.4 to 3.4 wt.% of 2-ethylheptanol; 1.7 to 3.7 wt.%, preferably 1.9 to 3.5 wt.%, particularly preferably 2.2 to 3.2 wt.% of 2-propylhexanol;

[0319] 3.2 to 9.2 wt.%, preferably 3.7 to 8.7 wt.%, particularly preferably 4.2 to 8.2 wt.% 3,5-dimethylheptanol;

[0320] 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0 wt.% 2,5-dimethylheptanol;

[0321] 1.8 to 3.8 wt.%, preferably 2.0 to 3.6 wt.%, particularly preferably 2.3 to 3.3 wt.% of 2,3-dimethylheptanol;

[0322] 0.6 to 2.6% by weight, preferably 0.8 to 2.4% by weight, particularly preferably 1.1 to 2.1% by weight of 3-ethyl-4-methylhexanol;

[0323] 2.0 to 4.0 wt.%, preferably 2.2 to 3.8 wt.%, particularly preferably 2.5 to 3.5 wt.% 2-ethyl-4-methylhexanol;

[0324] 0.5 to 6.5% by weight, preferably 1.5 to 6% by weight, particularly preferably 1.5 to 5.5% by weight of other alcohols having 9 carbon atoms; with the proviso that the total of the said components amounts to 100% by weight.

[0325] Decanol

[0326] Isodecanol, which is used for the synthesis of the diisodecyl esters of the general formula (I) contained in the plasticizer composition, is generally not a uniform chemical compound, but a complex mixture of differently branched isomeric decanols.

[0327] These are generally produced by nickel- or Bronsted acid-catalyzed trimerization of propylene, for example, by the PolyGas® or EMOGAS® process described above, followed by hydroformylation of the resulting isonone isomer mixture using homogeneous rhodium or cobalt carbonyl catalysts, preferably using cobalt carbonyl catalysts, and hydrogenation of the resulting isodecanal isomer mixture, e.g., using the catalysts and processes mentioned above in connection with the production of Cy-Cg alcohols (Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A1, p. 293, VCH Verlagsgesellschaft GmbH, Weinheim 1985). The isodecanol produced in this way is generally highly branched.

[0328] The 2-propylheptanol used to synthesize the di-(2-propylheptyl) esters of general formula (I) contained in the plasticizer composition can be pure 2-propylheptanol or propylheptanol isomer mixtures, such as those generally formed in the industrial production of 2-propylheptanol and commonly also referred to as 2-propylheptanol. Pure 2-propylheptanol can be obtained, for example, by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the resulting 2-propylheptenal, for example, according to US-A 2,921,089. In general, commercially available 2-propylheptanol contains, in addition to the main component 2-propylheptanol, one or more of the 2-propylheptanol isomers 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropyl-heptanol, 2-isopropyl-4-methylhexanol, 2-isopropyl-5-methylhexanol and / or 2-propyl-4,4-dimethylpentanol.The presence of other isomers of 2-propylheptanol, for example 2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methylheptanol and / or 2-ethyl-2,5-dimethylhexanol in 2-propylheptanol is possible. Due to the low formation rates of the aldehydic precursors of these isomers during the aldol condensation, these are present, if at all, only in trace amounts in 2-propylheptanol and play practically no role in the plasticizing properties of the compounds produced from such 2-propylheptanol isomer mixtures.

[0329] Various hydrocarbon sources can be used as starting materials for the production of 2-propylheptanol, for example, 1-butene, 2-butene, raffinate I (an alkane / alkene mixture obtained from the C4 fraction of a cracker after removal of allenes, acetylenes, and dienes, which contains significant amounts of isobutene in addition to 1- and 2-butene), or raffinate II, which is obtained from raffinate I by separation of isobutene and contains only small amounts of isobutene as olefin components, apart from 1- and 2-butene. Of course, mixtures of raffinate I and raffinate II can also be used as raw materials for 2-propylheptanol production.These olefins or olefin mixtures can be hydroformylated using conventional methods using cobalt or rhodium catalysts, whereby a mixture of n- and iso-valeraldehyde (the term iso-valeraldehyde refers to the compound 2-methylbutanal) is formed from 1-butene, the n / iso ratio of which can vary within relatively wide limits depending on the catalyst used and the hydroformylation conditions. For example, when using a homogeneous rhodium catalyst (Rh / TPP) modified with triphenylphosphine, n- and iso-valeraldehyde are formed from 1-butene in an n / iso ratio of generally 10:1 to 20:1, whereas when using rhodium hydroformylation catalysts modified with phosphite ligands, for example according to US-A 5288918 or WO 05028407, or with phosphoamidite ligands, for example according to WO 0283695, almost exclusively n-valeraldehyde is formed.While the Rh / TPP catalyst system converts 2-butene only very slowly during hydroformylation, so that most of the 2-butene can be recovered from the hydroformylation mixture, the hydroformylation of 2-butene is successful with the aforementioned phosphite ligand- or phosphoramidite ligand-modified rhodium catalysts, predominantly forming n-valeraldehyde. In contrast, isobutene contained in the olefinic raw material is hydroformylated, albeit at different rates, by virtually all catalyst systems to 3-methylbutanal and, depending on the catalyst, to a lesser extent to pivalaldehyde. The Cs-aldehydes obtained, depending on the starting materials and catalysts used, i.e.n-Valeraldehyde, optionally in a mixture with isovaleraldehyde, 3-methylbutanal, and / or pivalaldehyde, can, if desired, be completely or partially separated into the individual components by distillation before the aldol condensation, thus also providing the possibility of influencing and controlling the isomer composition of the Cw-alcohol component of the ester mixtures according to the disclosure. Likewise, it is possible to feed the Cs-aldehyde mixture, as formed in the hydroformylation, to the aldol condensation without prior separation of individual isomers.In the aldol condensation, which can be carried out using a basic catalyst such as an aqueous solution of sodium or potassium hydroxide, for example, according to the processes described in EP-A 366089, US-A 4426524, or US-A 5434313, the use of n-valeraldehyde results in 2-propylheptenal as the sole condensation product. Whereas, when a mixture of isomeric Cs-aldehydes is used, an isomer mixture is formed from the products of the homoaldol condensation of identical aldehyde molecules and the cross-aldol condensation of different valeraldehyde isomers. Of course, the aldol condensation can be controlled by the targeted conversion of individual isomers so that a single aldol condensation isomer is predominantly or completely formed.The aldol condensation products in question can then be hydrogenated to the corresponding alcohols or alcohol mixtures using conventional hydrogenation catalysts, for example those mentioned above for the hydrogenation of aldehydes, usually after prior separation, usually by distillation, from the reaction mixture and, if desired, purification by distillation.

[0330] As already mentioned, the compounds of general formula (I) contained in the plasticizer composition can be esterified with pure 2-propylheptanol. However, these esters are generally prepared using mixtures of 2-propylheptanol with the aforementioned propylheptanol isomers, in which the 2-propylheptanol content is at least 50% by weight. It may be preferred that the 2-propylheptanol content be 60 to 98% by weight, more preferably 80 to 95% by weight, and particularly preferably 85 to 95% by weight.

[0331] Suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those consisting of 60 to 98 wt.% 2-propylheptanol, 1 to 15 wt.% 2-propyl-4-methylhexanol, 0.01 to 20 wt.% 2-propyl-5-methylhexanol, and 0.01 to 24 wt.% 2-isopropylheptanol, where the sum of the proportions of the individual components does not exceed 100 wt.%. It may be preferred that the proportions of the individual components add up to 100 wt.%.

[0332] Other suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those of 75 to 95 wt.% 2-propylheptanol, 2 to 15 wt.% 2-propyl-4-methylhexanol, 1 to 20 wt.% 2-propyl-5-methylhexanol, 0.1 to 4 wt.% 2-isopropylheptanol, 0.1 to 2 wt.% 2-isopropyl-4-methylhexanol, and 0.1 to 2 wt.% 2-isopropyl-5-methylhexanol, where the sum of the proportions of the individual components does not exceed 100 wt.%. It may be preferred that the proportions of the individual components add up to 100 wt.%.

[0333] It may be preferred that mixtures of 2-propylheptanol with the propylheptanol isomers comprise those containing 85 to 95 wt.% 2-propylheptanol, 5 to 12 wt.% 2-propyl-4-methylhexanol, 0.1 to 2 wt.% 2-propyl-5-methylhexanol, and 0.01 to 1 wt.% 2-isopropylheptanol, where the sum of the proportions of the individual components does not exceed 100 wt.%. It may be preferred that the proportions of the individual components add up to 100 wt.%.

[0334] When using the above-mentioned 2-propylheptanol isomer mixtures instead of pure 2-propylheptanol to prepare the compounds of general formula (I), the isomer composition of the alkyl ester groups or alkyl ether groups practically corresponds to the composition of the propylheptanol isomer mixtures used for the esterification.

[0335] Undecanol

[0336] The undecanols used to produce the compounds of general formula (I) contained in the plasticizer composition can be straight-chain or branched, or composed of mixtures of straight-chain and branched undecanols. It may be preferred to use mixtures of branched undecanols, also known as iso-decanol, as the alcohol component.

[0337] Essentially straight-chain undecanol can be obtained, for example, by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-decene and subsequent hydrogenation of the resulting n-undecanal. The starting olefin, 1-decene, is prepared, for example, by the SHOP process mentioned above for the production of 1-octene.

[0338] To produce branched isoundecanol, the 1-decene obtained in the SHOP process can be subjected to skeletal isomerization, e.g., using acidic zeolitic molecular sieves, as described in WO 9823566, to form mixtures of isomeric decenes, the rhodium- or preferably cobalt-catalyzed hydroformylation of which and subsequent hydrogenation of the resulting isoundecanal mixtures also leads to the production of the isoundecanols used in the disclosed compounds of general formula (I). The hydroformylation of 1-decene or isoundecanal mixtures using rhodium or cobalt catalysis can be carried out as previously described in connection with the synthesis of C7 to C8 alcohols. The same applies to the hydrogenation of n-undecanal or isoundecanal mixtures to n-undecanol or isoundecanol, respectively.

[0339] After purification of the hydrogenation effluent by distillation, the C7 to Cn-alkyl alcohols thus obtained or mixtures thereof can be used, as described above, to prepare the diester compounds of the general formula (I) according to the disclosure.

[0340] Dodecanol

[0341] The dodecanols used to produce the compounds of general formula (I) contained in the plasticizer composition can be straight-chain or branched, or composed of mixtures of straight-chain and branched dodecanols. It may be preferred to use mixtures of branched dodecanols, also known as isododecanol, as the alcohol component.

[0342] Essentially straight-chain dodecanol can be obtained, for example, via the Alfol® or Epal® process. These processes involve the oxidation and hydrolysis of straight-chain trialkylaluminum compounds, which are synthesized stepwise from triethylaluminum through several ethylation reactions using Ziegler-Natta catalysts. The resulting mixtures of largely straight-chain alkyl alcohols of varying chain lengths can be used to obtain the desired n-dodecanol after distillation of the C12-alkyl alcohol fraction.

[0343] Alternatively, n-dodecanol can also be produced by hydrogenation of natural fatty acid methyl esters, for example from coconut oil.

[0344] Branched isododecanol can be obtained analogously to the known processes for the codimerization and / or oligomerization of olefins, as described, for example, in WO 0063151, with subsequent hydroformylation and hydrogenation of the isoundecene mixtures, as described, for example, in DE-A 4339713. After distillative purification of the hydrogenation effluent, the isododecanols thus obtained or mixtures thereof can be used, as described above, to prepare the diester compounds of the general formula (I) according to the disclosure. Examples

[0345] The invention is explained in more detail with reference to the figures and examples described below. These figures and examples should not be construed as limiting the invention.

[0346] The plasticizers according to the invention exhibit a partially significant reduction in the dissolution temperature compared to the comparative examples. This allows for improved incorporation of the plasticizer into PVC at lower temperatures. The film volatility of the plasticizers according to the invention is significantly lower than that of comparable plasticizers from the comparative examples. This results in better retention of the plasticizer in the soft PVC during processing. In addition, the plasticizers according to the invention exhibit better compatibility with soft PVC. This is noticeable in the lower weight loss in the compatibility test, but above all in the significantly better visual assessment. A smaller coating, or no coating, formed on the films with the plasticizers according to the invention compared to the comparative examples.

[0347] An Agilent 6890 series gas chromatograph was used for gas chromatography, with an Optima 5 Accent column (length = 30 m, inner diameter = 0.25 mm, outer diameter = 0.40 mm, film thickness = 0.5 μm) from Macherey & Nagel (order no. 726354.30). A split / splitless injector with a Topaz Split Precision Liner Whool from Restek (# 23305) was used as the injector. The injection conditions were: injector temperature = 280 °C, injection volume = 1 μL, split 1:50, split flow 150 mL / min, septum purge 3.0 mL / min (measured at an oven temperature of 80 °C). The carrier gas was nitrogen at 28 PSI = 3.0 mL / min (measured at an oven temperature of 80 °C). The temperature program was: Start: 60 °C, dwell time 1: 5 min, temperature ramp 1: 8 °C / min, end temperature 1: 240 °C, dwell time 2: 0 min, temperature ramp 2: 30 °C / min, end temperature 2: 300 °C, dwell time 3: 10 min, total running time: 59.5 min.Detection was performed using FID with 300 mL / min air, 30 mL / min hydrogen and 30 mL / min make-up gas (nitrogen) at 320 °C.

[0348] In the examples, the starting materials are used as shown in Table 2. Table 2.

[0349] Di-2-ethylhexylsebacic acid ester is commercially available from TCI Europe NV, Belgium.

[0350] Preparation of di-n-propylsebacic acid ester

[0351] A 1.0 L four-necked flask was charged with sebacic acid (300 g, 1.48 mol, 1.2 eq., Sigma Aldrich), tripropyl orthoformate (235 g, 1.24 mmol, 1.0 eq., Sigma Aldrich), propanol (100 mL), and methanesulfonic acid (6.53 g, 2.2 wt%). Under a gentle nitrogen stream, the reaction mixture was heated to 98°C and refluxed. After 4.5 hours, the reaction mixture was transferred to a 2 L flask, and more n-propanol was added (850 mL in total). After a further 16 hours of reaction, excess n-propanol was distilled off (65 °C, 2 mbar). Toluene (250 mL) and water (250 mL) were added to the crude product, and an aqueous 50 wt% NaOH solution (37 g) was added to the mixture. The organic phase was extracted first with water (4 x 250 mL) and then with a saturated NaCl solution (200 mL). The organic phase was dried over sodium sulfate, and the mixture was filtered through a pressure filter (2 L Pall filter holder, filter plate K100).The crude product was heated to 165 °C to distill off excess toluene, and then a nitrogen stream (initially 20 L / h at 165–198 °C for 1 h, then >25 L / h at 200 °C for 15 min) was passed through the product to obtain a highly pure product. 274 g of product were obtained (928 mmol, 65% yield). Analysis: GC area %: 98.87%. Preparation of 4,7-dioxosebacic acid.

[0352] The inventive two-step synthesis of 4,7-dioxosebacic acid starting from levulinic acid and furfural via furfurylidene levulinic acid is shown in the following scheme together with the isolation of difurfurylidene levulinic acid.

[0353] HCl (aq.)

[0354] Ethanol

[0355] LevOH

[0356] O Base Furfurylidenelevulinic acid 4,7-diketosebacic acid

[0357] Ethanol

[0358] Furfural

[0359] Aldol condensation to furfurylidene levulinic acid

[0360] Sodium carbonate (240 g, 2.26 mol) was added to a solution of levulinic acid (98%, 186 g, 1.57 mol) in water (1000 mL) at room temperature. The reaction mixture was then heated to reflux, and a solution of furfural (98%, 78.4 g, 0.80 mol) in ethanol (160 mL) was added continuously over 1 h. After the addition was complete, the reaction mixture was stirred under reflux for a further 1 h. The reaction mixture was then cooled to 10 °C and neutralized with hydrochloric acid (10%, 905 g). The resulting suspension was then filtered. The resulting filter cake was heated once with water (130 mL) to reflux for 30 min, and the suspension was filtered again after cooling to 5 °C. The filtrate was concentrated to half its volume using a rotary evaporator and cooled again to 5 °C, resulting in the precipitation of further solid, which was isolated by filtration.After drying the two combined filter cakes, furfurylidene levulinic acid (60.6 g, 302 mmol, 38%) was obtained as a solid.

[0361] Aldol condensation to furfurylidene levulinic acid & isolation of difurfurylidene levulinic acid

[0362] Sodium carbonate (71.7 g, 677 mmol) and magnesium oxide (25.3 g, 627 mmol) were added to a solution of levulinic acid (98%, 145 g, 1.22 mol) in water (800 mL) at room temperature. The reaction mixture was then heated to reflux, and a solution of furfural (98%, 98.0 g, 1.00 mol) in ethanol (160 mL) was added continuously over 1 h. After the addition was complete, the reaction mixture was stirred under reflux for a further 1 h. The reaction mixture was then brought to room temperature and filtered. The filter cake was discarded. The filtrate was cooled to 10 °C and neutralized with hydrochloric acid (10%, 240 g). The resulting suspension was then also filtered. The resulting filter cake was heated once with water (1500 mL) for 30 min at reflux and the suspension was filtered again after cooling to 5 °C.The filtrate was concentrated to half its volume using a rotary evaporator and cooled again to 5 °C, resulting in the precipitation of further solid, which was isolated by filtration. After drying, the two combined filter cakes were washed with MTBE (200 mL). Difurfurylidenelevulinic acid (19.7 g, 72.4 mmol, 15%) was isolated immediately, and furfurylidenelevulinic acid (73.7 g, 380 mmol, 38%) was isolated as a solid after complete removal of the solvent.

[0363] Acid-catalyzed ring opening to 4,7-dioxosebacic acid

[0364] Hydrochloric acid (32%, 105 g, 0.92 mol) was added to a stirred solution of

[0365] Furfurylidene levulinic acid (97%, 30.0 g, 0.15 mol) in ethanol (250 mL) was added continuously at reflux over 30 min. After the addition was complete, the reaction mixture was stirred under reflux for 6 h. The reaction mixture was then cooled to room temperature, and all volatile components were completely removed using a rotary evaporator. The resulting residue was treated with water (500 mL) and activated carbon (3.00 g), and the mixture was heated to boiling for 15 min. The solution was then filtered. The resulting solution was then diluted with water (700 mL) and continuously extracted using methyl tert-butyl ether (1300 mL) in a perforator. After complete removal of the solvent, 4,7-dioxosebacic acid (27.5 g, 114 mmol, 76%) was obtained as a solid.

[0366] Preparation of the connection 1.1

[0367] A 2.0 L four-necked flask was charged with 4,7-dioxosebacic acid (83.1 g, 361 mmol, 1.2 eq., previously prepared), tripropyl orthoformate (59.0 g, 301 mmol, 1.0 eq., Sigma Aldrich), propanol (450 mL), toluene (450 mL), and methanesulfonic acid (1.66 g, 2.0 wt%). Under a gentle nitrogen stream, the reaction mixture was heated to 88 °C and refluxed. After 5.5 hours of reaction, excess n-propanol and toluene were distilled off (70 °C, 2 mbar). Toluene (250 mL) was added to the crude product, and the mixture was treated with an aqueous 2.0 wt% NaOH solution (140 mL). The organic phase was first extracted with water (3 x 250 mL) and then with a saturated NaCl solution (150 mL). The organic phase was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure (70 °C, 2 mbar).To remove potential byproducts, the product was poured hot and stored overnight in a vacuum oven (110 °C, 20 mbar). A second batch (4,7-dioxosebacic acid (31.2 g, 135 mmol, 1.2 eq., previously prepared), tripropyl orthoformate (22.1 g, 113 mmol, 1.0 eq., Sigma Aldrich), propanol (150 mL), toluene (150 mL), and methanesulfonic acid (623 mg, 2.0 wt%)) was synthesized according to the same procedure. The products from both batches were combined, yielding a total of 120 g (382 mmol, 77% yield). Analysis: GC area %: 94.68%.

[0368] Preparation of the connection 1.26

[0369] A 1.6 L reactor vessel was charged with 4,7-dioxosebacic acid (110 g, 478 mmol, 1.0 eq., previously prepared), 2-octanol (187 g, 1.43 mol, 3.0 eq.), xylene (150 mL, BASF), and Tyzor TPT-20B (0.15 g, 0.05 wt%). The reaction mixture was heated to 155–187 °C under a gentle nitrogen stream (xylene was distilled off after 5 h, allowing the reaction temperature to be steadily increased) to both keep the reaction mixture boiling and continuously distill off the water formed. After 7.0 hours of reaction time, no more water was formed. The excess 2-octanol and xylene were then distilled off (189 °C, 13 mbar). The reaction mixture was quenched with a 2.0 wt% NaOH aqueous solution (75 mL). After stirring for 5 min at room temperature, water (450 mL) and xylene (450 mL) were added to the reaction mixture.For better phase separation, the mixture was treated with saturated NaCl solution and then filtered through a pressure filter (2 L Pall filter holder, filter plate AKS 7 with activated carbon). The now clearer two-phase mixture was treated with an aqueous 2.0 wt% NaOH solution (40 mL). Next, the organic phase was washed with an aqueous 2.0 wt% NaOH solution (50 mL), then with water (4 x 250 mL), and finally with a saturated NaCl solution (2 x 250 mL). The organic phase was dried over Na2SO4 and the mixture was filtered through a pressure filter (2 L Pall filter holder, filter plate K100). The crude product was heated to 176 °C to distill off the excess xylene and then steam distilled (189 °C, N2 flow: 20-25 L / h, 1 h) to remove residues of xylene and 2-octanol.Finally, a nitrogen stream (>25 L / h) was passed through the product (196 °C, 10 min) to obtain a highly pure product. 98 g of the product were obtained (216 mmol, 45% yield). Analysis: GC area %: 89.5%.

[0370] Preparation of the connection 1.27 A 1.6 L reactor vessel was charged with 4,7-dioxosebacic acid (105 g, 456 mmol, 1.0 eq., previously prepared), 2-ethylhexanol (178 g, 1.37 mol, 3.0 eq., BASF), xylene (150 mL, BASF), and Tyzor TPT-20B (0.15 g, 0.05 wt%). The reaction mixture was heated to 151–169 °C under a gentle nitrogen stream (xylene was distilled off after 2 h, allowing the reaction temperature to be steadily increased) to maintain the reaction mixture at boiling and to continuously distill off the water formed. After 6.50 hours of reaction time, no more water was formed. The reaction mixture was quenched with an aqueous 2.0 wt% NaOH solution (20 mL). After stirring for 5 minutes at room temperature, water (200 mL), xylene (300 mL) and saturated NaCl solution (200 mL) were added to the reaction mixture and the organic phase was separated by extraction.The organic phase was washed with water (3 x 250 mL) and saturated NaCl solution, dried over NaSO4, and then filtered through a pressure filter (2 L Pall filter holder, AKS 7 filter plate with activated carbon). Steam distillation (185 °C, N flow: 20-25 L / h, 45 min) was then performed to remove excess xylene and 2-ethylhexanol. Finally, a nitrogen flow (>25 L / h) was passed through the product (193 °C, 10 min) to obtain a highly pure product. (If residues of low-boiling products were still present in the product, a second steam distillation was performed (1 h).) 121 g of product was obtained (266 mmol, 58% yield). Analysis: GC area %: 95.4%.

[0371] Preparation of the connection 1.33

[0372] A 1.6 L reactor vessel was charged with 4,7-dioxosebacic acid (120 g, 521 mmol, 1.0 eq., previously prepared), 2-propylheptanol (248 g, 1.56 mol, 3.0 eq., BASF), xylene (200 mL, BASF), and Tyzor TPT-20B (0.25 g, 0.07 wt%). Under a gentle nitrogen stream, the reaction mixture was heated to 146–170 °C (xylene was distilled off after 2 h and 3.15 h, allowing the reaction temperature to be steadily increased) to both keep the reaction mixture boiling and continuously distill off the water formed. After 6.25 hours of reaction time, no more water was formed. The reaction mixture was then quenched with an aqueous 2.0 wt% NaOH solution (80 mL). After stirring for 5 minutes at room temperature, water (250 mL) and xylene (200 mL) were added to the reaction mixture, and the mixture was filtered through a pressure filter (2 L Pall filter holder, AKS 7 filter plate with activated carbon).The phases were then separated by extraction, the organic phase was washed with water (4 x 250 mL) and saturated NaCl solution, and dried over NaSO4. The crude product was heated to 170 °C to distill off the excess xylene. Steam distillation (189 °C, N flow: 20-25 L / h, 1 h) was then performed to remove residual xylene and 2-propylheptanol. Finally, a nitrogen stream was passed through the product (193 °C, 10 min) to obtain a highly pure product. 163 g of the product was obtained (319 mmol, 61% yield). Analysis: GC area %: 94.4%.

[0373] The following Table 3 shows the properties of the compounds described above.

[0374] Table 3. Comparative example 1] Solid 2] not determined

[0375] Application-related tests:

[0376] II. a) Determination of the dissolution temperature of the plasticizer compositions according to the disclosure:

[0377] To determine the dissolution temperature of the disclosed plasticizer compositions, approximately 10 grams of a mixture was prepared according to the following recipe (see Table 4). The mixture was stirred with a pipette, and then approximately 30 drops of the homogeneous mixture were immediately added to the plate-on-plate measuring system.

[0378] Table 4.

[0379] The viscosity measurements were carried out using a heated oscillation and rotation rheometer MCR 302 from Anton Paar in a rotation test.

[0380] Measuring system: plate / plate d=50 mm

[0381] Shear rate D: 10 (1 / s)

[0382] Gap width: 0.25 mm

[0383] Starting temperature: 30 °C

[0384] Temperature profile: 30 - 180 °C

[0385] Temperature increase: 5 °C / min

[0386] Value recording: every 3 seconds

[0387] The measurement was performed in two ramps. The first ramp, lasting 120 s at D=10 (1 / s) and 30 °C, served to temper the sample. The second ramp, at D=10 (1 / s) and a continuous temperature increase of 5 °C min, was the actual measurement. The measurement was aborted manually after the viscosity maximum was exceeded. The temperature at which the viscosity maximum was reached was determined as the result of the measurement. These measurements were performed four times in total, and the arithmetic mean of all four measurements was considered the final result. ll.b) Production and testing of soft PVC films produced using plasticizer compositions according to the invention

[0388] Recipe: see Table 5 below.

[0389] Table 5.

[0390] 150 g of PVC (homopolymer suspension PVC, brand name Inovyn® 271 PC), 90 g of plasticizer composition, and 3 g of Ba / Zn stabilizer, brand name Baerostab® UBZ 760 XLP RF, were mixed with a hand mixer at room temperature. The mixture was then plasticized on an oil-heated laboratory mixing mill (Collin, automatic mill type W250M, diameter: 252 mm, width: 450 mm) and processed into a rolled sheet. The temperature of both rolls was 180 °C each; the speeds were 15 rpm (front roll) and 12 rpm (rear roll); the rolling time was 5 minutes. The roll gap was set to 0.5 mm. This produced a rolled sheet with a thickness of 0.53 mm. The cooled rolled sheet was then pressed at a temperature of 190 °C and a pressure of 150 bar within 180 s on a press of the type "Laborplattenpresse 400 P" from Collin to form a soft PVC film with a thickness of 0.50 mm.While maintaining the pressing pressure, the press film was cooled to approximately 40 °C within 10 minutes.

[0391] II. c) Determination of the Shore A hardness of films with the plasticizer compositions according to the disclosure

[0392] The measurement is based on DIN EN ISO 868, Oct. 2003: A total of 22 pieces of 49 x 49 mm foil are punched from the rolled sheets produced as under ll.b). A suitable punching die is used to ensure the foil size is the same for each sheet. These are placed in a press frame (dimensions 400 x 400 mm; thickness 10 mm) without air bubbles, which contains a total of 16 cavities for the production of Shore A test specimens. Each cavity has internal dimensions of 50 x 50 mm. After loading the frame, the specimens are pressed between two highly polished, chrome-plated brass press plates measuring 400 x 400 x 2 mm on a Collin "Laboratory Plate Press 400 P" press. The test specimens are pressed at 185 °C and 200 bar for a total of 15 minutes. The cooled test specimens are then conditioned for 7 days in a climate-controlled room at 23 °C and approximately 50% humidity prior to measurement. A Hildebrand HDD-2 durometer is used to measure Shore A hardness.10 measurements are taken on a test specimen after 15 s penetration time.

[0393] Il.d) Determination of film volatility of films with the plasticizer compositions according to the disclosure

[0394] To determine film volatility, four individual films (150 x 100 mm) were cut from the pressed films described under II. b), perforated, and weighed. The films were hung on a rotating star wheel in a Heraeus Type 5042 E drying oven set to 130 °C. The air in the oven was changed 18 times per hour. This corresponds to 800 L / h of fresh air. After 24 hours in the oven, the films were removed and reweighed. The weight loss in percent indicates the film volatility of the plasticizer compositions.

[0395] Il.e) Determination of the compatibility (permanence) of films with the plasticizer compositions according to the disclosure

[0396] To determine compatibility, 10 test specimens (films) measuring 75 x 110 x 0.5 mm were cut from the pressed films described under II. b). The films were perforated along their wide sides, labeled, and weighed. The test specimens thus produced were then placed on a metal frame made of stainless material in a glass basin. To avoid mutual interference, only test specimens with the same composition may be stored in a glass basin. The glass basins are filled with demineralized water to a level of approximately 3 cm. Care must be taken to ensure that the test specimens are a further 2 cm above the water surface and do not touch the water. The subsequently hermetically sealed glass containers are then placed in an oven with internal temperature control. The test is carried out at 70 °C and 100% relative humidity for a total of 28 days.At intervals of 1, 3, 7, 14, and 28 days, two samples were taken each and conditioned in air for 1 hour while hanging freely. The films were then cleaned with methanol in a fume hood. The films were then dried while hanging freely in a drying cabinet (natural convection) for 16 hours at 80°C. After removal from the drying cabinet, the films were conditioned while hanging freely in the laboratory for 1 hour and then weighed. The test result was given in each case as the arithmetic mean of the weight changes compared to the samples before placement in the heating cabinet. A visual assessment was also carried out. The following evaluation criteria were used:

[0397] 0 = dry touch, the film is smooth and dry (best compatibility)

[0398] 1 = blunt grip, the film is still dry, a small amount of plasticizer is present on the surface, resulting in a blunt grip. Fingerprints are visible.

[0399] 2 = sticky feel, plasticizer has already noticeably leaked out on the surface,

[0400] Fingerprints are easily and clearly visible

[0401] 3 = weak, dry coating; visible to the naked eye

[0402] 4 = weak, liquid or greasy coating

[0403] 5 = heavy dry coating

[0404] 6 = heavy greasy coating ll.f) Determination of the HCI residual stability of films with the plasticizer compositions according to the disclosure

[0405] The determination of residual HCl stability is carried out according to DIN EN 60811-405 (VDE 0473-811-405): A metal block thermostat from Liebisch Labortechnik is used as the test device at a test temperature of 200 °C. A triplicate determination is always performed. Approximately 50 mg of the rolled foil is weighed, cut to a length of 3 cm, and placed in the lower part of the glass tube. A strip of indicator paper (litmus paper) approximately 10 mm long is placed at the upper end of the glass tube, leaving approximately 2 mm protruding. The prepared glass tubes are placed in the metal block, and the time until a color change to red occurs is recorded. The arithmetic mean is calculated from the three measured values ​​of the three samples.

[0406] I lg) Determination of the cold fracture temperature of films with the plasticizer compositions according to the disclosure

[0407] The cold fracture temperature test is carried out on test specimens obtained from the pressed films produced under II. b). The test is carried out in accordance with the draft of DIN 53372 from 1981. The dimensions and number of test specimens are in accordance with the specifications of the DIN standard (length 60 mm, width 15 mm, thickness exactly 0.50 mm). The test specimens must be stored at room temperature for at least four days before testing. The key difference between this test design and the draft of DIN 53372 is that the hammers do not impact the test specimen loops in a free vertical fall. Instead, the hammers are attached to a shaft and, after the impact weights are triggered, fall in a circular arc from the same height (= distance from the test specimen) onto the test loops. In this case, six identical test specimens in a row are tested simultaneously.The freezer is set to an expected starting temperature, and the sample carrier (bomb) with the test specimens is inserted. To condition the test specimens, they are held at room temperature for 1 hour per test temperature. For evaluation, only those test loops that have completely broken into two or more pieces are considered defective. To determine the cold fracture temperature, at least one row of six test specimens must be considered completely broken, and at least one row of six must be considered completely intact. The temperature interval for each test is 5 °C. The cold fracture temperature is calculated according to the formula in the draft of DIN standard 53372 (1981).

[0408] II. h) Determination of the tensile test properties of films with the plasticizer compositions according to the disclosure

[0409] This test is used to determine the parameters elongation at break, stress at break and 100% modulus. For this purpose, type 2 test specimens according to DIN EN ISO 527-3 are measured on the Zwick / Z 2.5 tensile testing machine. The test specimens are 150 mm long, 15 mm wide and approximately 0.50 mm thick. The test specimens are punched out of the pressed films described under II. b) using a punch. Before the test, the test specimens are conditioned for 7 days in a climatic chamber under standard climate. It must be ensured that exactly 7 days elapse between the production of the pressed films and the performance of the tensile test. Conditioning takes place at 23 °C + / - 1.0 °C and 50% + / - 5 RH according to DIN EN ISO 291. The tensile tests are carried out according to DIN EN ISO 527, Part 1-3. Each measurement consists of testing 10 individual test specimens. The measuring length of 100 mm is determined by the free clamping length of the specimen between the clamping jaws. The test speed is 100 mm / min.The average thickness is determined from five individual values ​​within the measuring length. Strain and 100% modulus are measured by changing the crosshead travel.

[0410] The results of the application tests are shown in Tables 6 and 7.

[0411] Table 6.

[0412] * Comparison example

[0413] Table 7.

[0414] Comparison example

Claims

Patent claims 1 . Use of a compound of general formula (I) as a plasticizer where Ri and R2 are independently selected from Ci-Ci2-alkyl.

2. Compound of general formula (I) where Ri and R2 are independently selected from linear or branched C3-Ci2-alkyl 3. A compound according to claim 2, wherein R1 and R2 are independently selected from n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-Methyl pentyl, 1-Ethylbutyl, 2-Ethylbutyl, 1-Ethyl-2-methyl propyl, n-Heptyl, 1-Methylhexyl, 2-Methyl hexyl, 1-Ethylpentyl, 2-Ethylpentyl, 1-Propylbutyl, n-Octyl, iso-Octyl, 2-Octyl, 2-Ethylhexyl, n-Nonyl, iso-Nonyl, 2-Propylhexyl, n-Decyl, iso-Decyl, 2-propylheptyl, n-undecyl, iso-undecyl, n-dodecyl, and iso-dodecyl.

4. A compound according to claim 3, wherein R1 and R2 are independently selected from n-propyl, n-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-Methylbutyl, 2-octyl, 2-ethylhexyl, iso-nonyl, 2-propylheptyl and isodecyl, in particular n-propyl, 2-octyl, 2-ethylhexyl, iso-nonyl and 2-propylheptyl.

5. A compound according to any one of claims 2 to 4, wherein Ri and R2 are the same or constitutionally isomeric.

6. Plasticizer composition containing at least one compound of general formula (I) where Ri and R2 are independently selected from linear or branched Ci-Ci2-alkyl, and at least one further plasticizer which is different from the compounds of the general formula (I).

7. Plasticizer composition according to claim 6, wherein the further plasticizer is selected from - Phthalic acid dialkyl esters, - trimellitic acid trialkyl esters, - terephthalic acid dialkyl esters, - Benzoic acid alkyl esters, - dibenzoic acid esters, - hydroxybenzoic acid esters, - esters of saturated monocarboxylic acids, - Esters of unsaturated monocarboxylic acids, - esters of hydroxymonocarboxylic acids, - esters of dicarboxylic acids, - esters of saturated hydroxydicarboxylic acids, - amides and esters of aromatic sulfonic acids, - pentaerythritol esters, - alkylsulfonic acid esters, - glycerol esters, - isosorbide esters, - phosphoric acid esters, - citric acid diesters and citric acid triesters, - alkylpyrrolidone derivatives, - 2,5-furandicarboxylic acid esters, - 2,5-tetrahydrofurandicarboxylic acid esters, - epoxidized vegetable oils, - epoxidized fatty acid monoalkyl esters, - 1,2-cyclohexanedicarboxylic acid dialkyl esters, - 1,3-cyclohexanedicarboxylic acid dialkyl esters, - 1,4-cyclohexanedicarboxylic acid dialkyl esters, - Polyesters made from aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols, - other plasticizers, and - Mixtures thereof.

8. Plasticizer composition according to claim 6 or 7, containing the compound of general formula (I) in an amount of at least 10 wt.%, preferably 30 to 90 wt.%, more preferably 50 to 80 wt.%, and the further plasticizer in an amount of 0 to 90 wt.%, preferably 10 to 70 wt.%, more preferably 20 to 50 wt.%, in each case based on the total mass of the plasticizer composition.

9. Moulding compound or plastisol containing at least one compound of general formula (I) where Ri and R2 are independently selected from linear or branched Ci-Ci2-alkyl, and at least one polymer.

10. A molding compound or plastisol according to claim 9, wherein the polymer is selected from a thermoplastic, an elastomer, and mixtures thereof.

11. Moulding compound or plastisol according to claim 10, wherein the thermoplastic is selected from - homo- or copolymers containing at least one monomer in polymerized form, selected from C2-C8 monoolefins such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols and their C2-C8 alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C1-C8 alcohols, vinyl aromatics such as styrene, acrylonitrile, methacrylonitrile, α,β-ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride, - Homo- or copolymers of vinyl acetals, polyvinyl esters, polycarbonates, polyesters, polyethers, polyether ketones, thermoplastic polyurethanes, polysulfides, polysulfones, polyether sulfones, polyacrylates, polymethyl methacrylates, polystyrenes, polyvinyl alcohols, polyvinyl acetates, polyvinyl butyrals, polyvinyl chlorides, polycaprolactones, cellulose alkyl esters and mixtures thereof, and the elastomer is selected from natural rubber and synthetic rubber such as polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber and mixtures thereof.

12. Molding compound or plastisol according to one of claims 9 to 11, additionally containing at least one additive selected from stabilizers, lubricants, fillers, colorants, flame inhibitors, light stabilizers, blowing agents, polymeric processing agents, impact modifiers, optical brighteners, antistatic agents, biostabilizers, silicon dioxide, phenolic resins, vulcanizing agents, crosslinking agents, vulcanization accelerators, crosslinking accelerators, activators, oils, ageing inhibitors and mixtures thereof.

13. Use of the molding compound or plastisol according to any one of claims 9 to 12 for the production of molded articles, gloves, films, wallpapers, or heterogeneous flooring, or for textile coating.

14. Process for the preparation of 4,7-dioxosebacic acid according to formula (II) wherein levulinic acid is reacted with furfural in the presence of a base to form furfurylidene levulinic acid; the furfurylidene levulinic acid is reacted in an alcoholic solvent in the presence of an acidic catalyst to form a reaction product containing 4,7-dioxosebacic acid; the alcoholic solvent is evaporated and the residue is taken up in water; the aqueous solution is extracted with a water-immiscible solvent; and the water-immiscible solvent is evaporated to obtain 4,7-dioxosebacic acid.

15. The process according to claim 14, wherein 4,7-dioxosebacic acid according to formula (II) is reacted with a Ci-Ci2 alcohol.

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