Plasticizer composition

Abstract

A plasticizer composition, containing a) at least one compound of the general formula (I), wherein R1 and R2 independently of each other are selected from among C5-C8 cycloalkyl, which is unsubstitute

Description

[0001] Plasticizer composition

[0002] The present invention relates to a plasticizer composition comprising certain dicarboxylic acid diesters and diesters selected from 1,2-cyclohexanedicarboxylic acid esters and terephthalic acid esters, their use as plasticizers for polymers, and a molding compound or a plastisol comprising the plasticizer composition.

[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 the esters of aliphatic or aromatic polycarboxylic acids. 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.

[0004] It is desirable that the plasticizers have a high compatibility with the plasticized plastic, i.e. that they do not leach out of the plasticized plastic or only leach relatively slowly, and / or are largely toxicologically harmless.

[0005] In addition to PVC, plasticizers are also commonly used in other plastics. These include polyvinyl butyral (PVB), styrene homopolymers or copolymers, polyacrylates, polysulfides, polylactic acid (PLA), or thermoplastic polyurethanes (TPU).

[0006] The prior art discloses various plasticizers for plastics, for example for PVC.

[0007] Particularly in the production and processing of PVC plastisols, for example for the production of PVC coatings, it is desirable, among other things, to have a plasticizer with a low gelling temperature as a fast gelator ("fast fuser"). In addition, a high storage stability of the plastisol is also desired, i.e. the non-gelled plastisol should show no or only a slight increase in viscosity over time at ambient temperature. These properties should be achieved, if possible, by adding a suitable plasticizer with fast gelling properties, whereby the use of further viscosity-reducing additives and / or solvents should be unnecessary.

[0008] However, rapid gelling agents generally exhibit poor compatibility with the polymers they contain. Furthermore, they are often highly volatile, both during processing and during use of the final products. Furthermore, the addition of rapid gelling agents often has a detrimental effect on the mechanical properties of the final products. To achieve the desired plasticizer properties, it is therefore also known to use plasticizer mixtures, e.g., at least one plasticizer that imparts good thermoplastic properties but gels less well, in combination with at least one rapid gelling agent. However, these properties cannot be achieved with just any combination of a plasticizer and a rapid gelling agent.

[0009] EP 1 354 867 B1 discloses mixtures of isononyl benzoates in combination with alkyl phthalates and / or dialkyl adipic acids and / or alkyl cyclohexanedicarboxylates, which can be used as plasticizers for PVC.

[0010] The synthesis and use of certain 4-oxoheptanedioic acid esters as plasticizers is described in US Pat. No. 2,665,303. It states that the C4 to C12 diesters are low-viscosity to low-melting compounds. The diesters are synthesized by direct esterification of the acid or by reacting the dilactones with the corresponding alcohols. The resulting esters are characterized by high plasticizer efficiency and good cold-break properties. No statement is made regarding the other properties of the corresponding soft PVC compounds.

[0011] Gavat et al., Revista de Chimie-Romania 1955, 6, 516-520, describe various synthetic routes to esters of 4-oxopimelic acid starting from furfuryl alcohols. A use as a plasticizer in PVC is mentioned, but no data are disclosed.

[0012] Moshkin, in: Voprosy Ispol'zovan. Pentozansoderzhashchego Syr'ya, Trudy Vsesoyuz. Soveshchaniya, Riga 1958, 225-254 describes the synthesis of 4-oxopimelic acid ester from furfuryl alcohol. The use of di-2-ethylhexyl ester in PVC is described.

[0013] In general, the known plasticizers are subject to constant optimization, e.g. with regard to their volatility, cold fracture temperature, compatibility and / or toxicological safety.

[0014] The present invention was therefore based on the object of providing plasticizers for plastics, for example for PVC, which impart good mechanical properties to the plasticized plastics. The plasticizer composition should also have good gelling properties and high compatibility with the plastics to be plasticized, exhibit low volatility during use of the end products, and be toxicologically safe. This object was achieved by a plasticizer composition comprising a) at least one compound of the general formula (I) where R1 and R2 are independently selected from Cs-Cs-cycloalkyl which is unsubstituted or carries one or more Ci-Cio-alkyl substituents, and n1 and n2 are independently 1, 2 or 3; and b) at least one compound of the general formula (II) where R 3 and R 4are independently selected from branched or unbranched C4-Ci2-alkyl, and Y is selected from (Ya) and (Yb)

[0015] (Ya) (Yb) where # indicates points of contact.

[0016] 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.

[0017] Unless otherwise stated, the percentage by weight refers to the total mass. 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.

[0018] In a preferred embodiment of the invention, n1 and n2 are 1. In this case, the compounds of general formula (I) are diesters of 4-oxoheptanedioic acid.

[0019] In the compound of general formula (I), R1 and R2 are independently selected from Cs-Cs-cycloalkyl, which is unsubstituted or bears one or more Cs-Cw-alkyl substituents. Substituted Cs-Cs-cycloalkyl may, depending on the ring size, bear one or more Cs-Cw-alkyl substituents, e.g., 1, 2, 3, 4, 5, or 6 Cs-Cw-alkyl substituents, preferably 1 or 2 Cs-Cw-alkyl substituents. The Ci-Cw-alkyl substituents are each independently selected from straight-chain and branched Ci-Cio-alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the structural isomers thereof.

[0020] Preferably, R1 and R2 are independently selected from cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, cyclohexyl,

[0021] 2-Methylcyclohexyl, 3-Methylcyclohexyl, 2,3-Dimethylcylclohexyl, 2,4-Dimethylcyclohexyl, 2,5-Dimethylcyclohexyl, 2,6-Dimethylcyclohexyl, 3,4-Dimethylcyclohexyl, 3,5-Dimethylcyclohexyl, Cycloheptyl, 2-Methylcycloheptyl,

[0022] 3-Methylcycloheptyl, 4-Methylcycloheptyl, 2,3-Dimethylcycloheptyl, 2,4-Dimethylcycloheptyl,

[0023] 2.5-Dimethylcycloheptyl, 2,6-Dimethylcycloheptyl, 2,7-Dimethylcycloheptyl, 3,4-Dimethylcycloheptyl,

[0024] 3.5-Dimethylcycloheptyl, 3,6-Dimethylcycloheptyl, 4,5-Dimethylcycloheptyl, Cyclooctyl, 2-Methylcyclooctyl, 3-Methylcyclooctyl, 4-Methylcyclooctyl, 5-Methylcyclooctyl, 2,3-Dimethylcyclooctyl, 2,4-Dimethylcyclooctyl,

[0025] 2.5-Dimethylcyclooctyl, 2,6-Dimethylcyclooctyl, 2,7-Dimethylcyclooctyl, und 2,8-Dimethylcyclooctyl.

[0026] Stärker bevorzugt sind Ri und R2 unabhängig voneinander ausgewählt sind unter Cyclopentyl, Cyclohexyl, Cycloheptyl und Cyclooctyl.

[0027] Even if Ri and R2 are generally independent of each other in a compound of general formula (I), Ri and R2 are preferably the same.

[0028] For example, a compound of general formula (I) can be:

[0029] - 1.1 Dicyclopentyl-4-oxoheptanoate

[0030] - I.2 Dicyclohexyl-4-oxoheptanoate

[0031] - I.3 Dicycloheptyl-4-oxoheptanoate

[0032] - I.4 Dicyclooctyl 4-oxoheptanoate The plasticizer composition may also contain a mixture of compounds of general formula (I), for example a mixture of compounds of general formula (I) selected from 1.1, 1.2, I.3, and I.4.

[0033] The plasticizer composition according to the invention comprises, in addition to a compound of the general formula (I) or a mixture of compounds of the general formula (I), at least one compound of the general formula (II) where R 3 and R4 are independently selected from branched or unbranched C4-Ci2-alkyl, and Y is selected from (Ya) and (Yb) where # indicates attachment points, that is, the positions to which-COOR 3 and -COOR 4 are bound.

[0034] If in compounds of the general formula (II) Y stands for (Ya), the compounds of the general formula (II) are 1,2-cyclohexanedicarboxylic acid dialkyl esters (II,a)

[0035] If in compounds of the general formula (II) Y stands for (Yb), the compounds of the general formula (II) are T ereph th al acid d I al ky lester (II ,b)

[0036] The term "C4-C12-alkyl" in compounds of general formula (II) includes unbranched or branched alkyl groups having 4 to 12 carbon atoms. These include, for example, n-butyl, isobutyl, 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, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2-propylheptyl, n-Undecyl, iso-decyl, n-dodecyl, isododecyl, and the structural isomers thereof.

[0037] Preferred are R 3 and R 4in compounds of the general formula (II) independently selected from branched or unbranched C7-Ci2-alkyl, such as n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isundecyl, n-dodecyl, isododecyl, and the structural isomers thereof.

[0038] More preferred are R 3 and R 4 in compounds of the general formula (II) independently selected from branched or unbranched Cs-Cn-alkyl, such as n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl, isundecyl, and the structural isomers thereof.

[0039] Even if R3 and R4 in a compound of general formula (II) are generally independent of each other, R3 and R4 are preferably the same.

[0040] Particularly preferably, R3 and R4 both represent 2-ethylhexyl or both represent isononyl.

[0041] The plasticizer composition may also contain a mixture of compounds of general formula (II).

[0042] Typically, the alcohols underlying the above-mentioned iso-radicals, e.g., iso-octyl, iso-nonyl, iso-decyl, iso-undecyl, iso-dodecyl, are obtained not as defined individual compounds, but as mixtures. In the context of the present invention, the term "iso-alkyl" 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.

[0043] In compounds of the general formula (II. a) R 3 and R 4be independently selected from branched and unbranched C2-C12-alkyl. In compounds of the general formula (II.a), R3 and R4 are preferably identical. Particularly preferably, in compounds of the general formula (II.a), R3 and R4 are identical and both represent isononyl. A particularly preferred compound of the general formula (II.a) is di-(isononyl)-1,2-cyclohexanedicarboxylate.

[0044] In compounds of the general formula (II. b) R 3 and R 4 preferably be selected independently from branched and unbranched C2-C12-alkyl, preferably from 2-ethylhexyl, isononyl, and 2-propylheptyl. Preferably, in compounds of the general formula (II.b), R5 and R4 are identical. Particularly preferably, in compounds of the general formula (II.b), R3 and R4 are identical and both represent 2-ethylhexyl. A particularly preferred compound of the general formula (II.b) is di-(2-ethylhexyl) terephthalate.

[0045] The plasticizer composition contains the at least one compound of the general formula (I) in an amount of 5 to 60 wt.%, preferably 7 to 40 wt.%, more preferably 9 to 30 wt.%, based on the total mass of the compounds of the general formula (I) and (II).

[0046] Use of the plasticizer composition as a plasticizer for polymers

[0047] In one embodiment, the plasticizer composition is used as a plasticizer for polymers, preferably for thermoplastics and elastomers, more preferably in a molding compound or a plastisol.

[0048] Special embodiments

[0049] By adjusting the proportions of the amounts of the general compounds (I) and (II) in the plasticizer composition according to the invention, the plasticizer properties can be tailored to the respective intended use. For use in specific applications, it may be helpful to additionally add at least one further plasticizer different from compounds (I) and (II) to the plasticizer composition according to the invention. For this reason, the plasticizer composition according to the invention may optionally contain at least one further plasticizer different from compounds (I) and (II).

[0050] For example, the additional plasticizer can be selected from

[0051] - Phthalic acid dialkyl esters, e.g. with 9 to 13 C atoms in the alkyl chains,

[0052] - trimellitic acid trialkyl esters, - benzoic acid alkyl esters,

[0053] - Dibenzoic acid esters, e.g. dibenzoic acid esters of glycols,

[0054] - hydroxybenzoic acid esters,

[0055] - esters of saturated monocarboxylic acids,

[0056] - Esters of unsaturated monocarboxylic acids,

[0057] - esters of hydroxymonocarboxylic acids,

[0058] - esters of dicarboxylic acids,

[0059] - esters of saturated hydroxydicarboxylic acids,

[0060] - amides and esters of aromatic sulfonic acids,

[0061] - pentaerythritol esters,

[0062] - alkylsulfonic acid esters,

[0063] - glycerol esters,

[0064] - isosorbide esters,

[0065] - phosphoric acid esters,

[0066] - Citric acid diesters and citric acid triesters, e.g. acylated citric acid triesters

[0067] - alkylpyrrolidone derivatives,

[0068] - 2,5-furandicarboxylic acid esters, e.g. 2,5-furandicarboxylic acid dialkyl esters

[0069] - 2,5-tetrahydrofurandicarboxylic acid esters, e.g. 2,5-tetrahydrofurandicarboxylic acid dialkyl esters,

[0070] - epoxidized vegetable oils,

[0071] - epoxidized fatty acid monoalkyl esters,

[0072] - 1,3-cyclohexanedicarboxylic acid dialkyl esters, e.g. with 4 to 13 C atoms in the alkyl chains,

[0073] - 1,4-cyclohexanedicarboxylic acid dialkyl esters, e.g. with 4 to 13 C atoms in the alkyl chains,

[0074] - Polyesters made from aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols,

[0075] - other plasticizers, and

[0076] - Mixtures thereof.

[0077] 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 can, for example, be di-isononyl phthalate.

[0078] 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.

[0079] An alkyl benzoate can have 9 to 13 carbon atoms in the alkyl chain. An alkyl benzoate can be, for example, isodecyl benzoate or 2-propylheptyl benzoate. A dibenzoate can be, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, or dibutylene glycol dibenzoate.

[0080] A saturated monocarboxylic acid ester can, for example, be 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.

[0081] An unsaturated monocarboxylic acid ester can, for example, be an ester of acrylic acid.

[0082] An unsaturated dicarboxylic acid diester can, for example, be an ester of maleic acid.

[0083] 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.

[0084] 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.

[0085] A phosphoric acid ester can be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecy diphenyl phosphate, or bis-2(2-ethyl hexyl)phenyl phosphate, 2-ethyl hexyldiphenyl phosphate.

[0086] 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.

[0087] An alkylpyrrolidone derivative can have 4 to 18 C atoms in the alkyl chain.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] A dialkyl cyclohexane-1,4-dicarboxylate can have 4 to 13 C 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 C 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.

[0093] 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.

[0094] Polymers

[0095] The plasticizer composition (hereinafter also referred to as "plasticizer") is advantageously used as a plasticizer for a polymer or a mixture of polymers.

[0096] A polymer is a plastic. A polymer can be a thermoplastic or an elastomer.

[0097] A thermoplastic can usually be processed thermoplastically.

[0098] 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.

[0099] 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, preferably containing polyvinyl chloride.

[0100] A thermoplastic can be, for example:

[0101] - TP.1: a homo- or copolymer which contains, in polymerized form, at least one 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, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates or methacrylates with alcohol components of branched or unbranched C1 to Cw alcohols, vinyl aromatics such as styrene, (meth)acrylonitrile, α,β-ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride.

[0102] - TP.2: a polyvinyl ester

[0103] - TP.3: a polycarbonate

[0104] - TP.4: a polyether

[0105] - TP.5: a polyetherketone

[0106] - TP.6: a thermoplastic polyurethane

[0107] - TP.7: a polysulfide

[0108] - TP.8: a polysulfone

[0109] - TP.9: a polyester

[0110] - TP.10: a polyalkylene terephthalate

[0111] - TP.11 : a polyhydroxyalkanoate

[0112] - TP.12: a polybutylene succinate

[0113] - TP.13: a polybutylene succinate adipate

[0114] - TP.14: a polyacrylate with identical or different alcohol residues from the group of C4 to Cs-

[0115] Alcohols such as butanol, hexanol, octanol, 2-ethylhexanol

[0116] - TP.15: a polymethyl methacrylate

[0117] - TP.16: a methyl methacrylate-butyl acrylate copolymer

[0118] - TP.17: an acrylonitrile-butadiene-styrene copolymer

[0119] - TP.18: an ethylene-propylene copolymer

[0120] - TP.19: an ethylene-propylene-diene copolymer

[0121] - TP.20: a polystyrene

[0122] - TP.21 : a styrene-acrylonitrile copolymer

[0123] - TP.22: an acrylonitrile-styrene-acrylate

[0124] - TP.23: a styrene-butadiene-methyl methacrylate copolymer

[0125] - TP.24: a styrene-maleic anhydride copolymer

[0126] - TP.25: a styrene-methacrylic acid copolymer

[0127] - TP.26: a polyoxymethylene - TP.27: a polyvinyl alcohol

[0128] - TP.28: a polyvinyl acetate

[0129] - TP.29: a polyvinyl butyral

[0130] - TP.30: a polyvinyl chloride

[0131] - TP.31 : a polycaprolactone

[0132] - TP.32: Polyhydroxybutyric acid

[0133] - TP.33: Polyhydroxyvaleric acid

[0134] - TP.34: Polylactic acid

[0135] - TP.35: Ethylcellulose

[0136] - TP.36: Cellulose acetate

[0137] - TP.37: Cellulose propionate

[0138] - TP.38: Cellulose acetate / butyrate

[0139] Generally, polyvinyl chloride is 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] A measure of good gelling properties can be a low dissolution / gelling temperature. The compatibility (permanence) of plasticizers in plasticized plastics characterizes the extent to which plasticizers tend to bleed out during use of the plasticized plastics, thereby impairing the performance properties of the plastics.

[0144] Low volatility during processing can, for example, be reflected by low process volatility.

[0145] Low volatility during use of the final product can, for example, be reflected by low film volatility.

[0146] Molding compound and plastisol

[0147] A further subject matter of the present invention is a molding compound or a plastisol, wherein the molding compound or the plastisol contains the plasticizer composition as described above and at least one polymer.

[0148] The plasticizer can therefore be used as a plasticizer in a molding compound or plastisol.

[0149] In general, the term "molding compound" refers to unformed or preformed materials that are processed into semi-finished or finished parts by means of mechanical force and elevated temperatures through non-cutting forming.

[0150] 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.

[0151] The molding compound or plastisol may also contain a mixture of polymers.

[0152] In one embodiment of the invention, the polymer is selected from a thermoplastic, an elastomer, and mixtures thereof. 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.

[0153] In one embodiment, the thermoplastic is selected from

[0154] - homo- or copolymers containing at least one monomer in polymerized form, selected from C2-C10-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,

[0155] - 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.

[0156] The molding compound or plastisol can, for example, be composed as shown in Table 1.

[0157] Table 1.

[0158] 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.

[0159] If no polyvinyl chloride is present in the molding compound, the amount of plasticizer in the molding compound is typically 0.5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound be 1.0 to 130 phr. It may be more preferred that the amount of plasticizer in the molding compound be 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.

[0160] If polyvinyl chloride is present in the molding compound, the amount of plasticizer in the molding compound is typically 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 present in the molding compound may 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.

[0161] 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.

[0162] 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.

[0163] If the plastisol contains polyvinyl chloride, the plasticizer content in the plastisol is typically 30 to 400 phr, preferably 50 to 200 phr. The plasticizer content in a plastisol containing polyvinyl chloride is usually at least 10 phr, preferably at least 15 phr, and more preferably at least 20 phr.

[0164] Additives molding compound or plastisol with thermoplastics

[0165] 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.

[0166] 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.

[0167] Stabilizers can be the usual polyvinyl chloride stabilizers in solid and liquid form, such as Ca / Zn, Ba / Zn, Pb, Sn stabilizers, acid-binding layered silicates, carbonates such as hydrotalcite or mixtures thereof.

[0168] The molding compound or plastisol may 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.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] For example, carbon black and / or inorganic fillers may be present in the molding compound or plastisol as fillers. 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. The molding compound or plastisol can 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. The molding compound or plastisol can have a filler content of 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36 or 39 wt.%.

[0174] Colorants can be used to adapt the molding compound or plastisol to different applications. Colorants can be pigments or dyes, for example.

[0175] Pigments that can be contained in the molding compound or plastisol include, for example, inorganic and / or organic pigments. Inorganic pigments can be cobalt pigments such as COO / Al2O3 and / or chromium pigments such as Cr2O3. Organic pigments can be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, and / or dioxazine pigments.

[0176] 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.

[0177] Flame inhibitors can be used to reduce the flammability of the molding compound or plastisol and to reduce smoke formation during combustion.

[0178] 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.

[0179] 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.

[0180] Light stabilizers, such as UV absorbers, can be used to protect the molding compound or plastisol from damage caused by the influence of light.

[0181] 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.

[0182] The molding compound or plastisol may contain light stabilizers in a range 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. Additives molding compound with elastomers

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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 routine practice for the skilled person to use appropriate amounts of plasticizer to achieve the desired properties.

[0191] 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 may 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.

[0192] 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.

[0193] 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.

[0194] Use of the molding compounds

[0195] The molding compound can be used, for example, for the production of molded articles, gloves, films, wallpapers, or heterogeneous flooring, or for textile coating.

[0196] Shaped bodies can be, for example, containers, apparatus or foamed devices.

[0197] 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.

[0198] 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.

[0199] Foamed devices can be, for example, upholstery, mattresses, foams or insulation materials.

[0200] 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.

[0201] The molding compound can be used to produce molded articles or films that come into direct contact with humans or food.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] Clothing that can be manufactured using the molding compound includes latex clothing, protective clothing, rain jackets, or rubber boots. Use of plastisols

[0209] 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.

[0210] 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.

[0211] 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.

[0212] Gloves can be, for example, gardening gloves, medical gloves, chemical gloves, protective gloves or disposable gloves.

[0213] 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.

[0214] The plastisol usually contains polyvinyl chloride.

[0215] Non-PVC applications

[0216] 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, a desensitizer, in pharmaceutical products, in adhesives, in sealants, in inks, such as printing inks, in impact modifiers, or in suspension agents. Products containing the plasticizer

[0217] 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.

[0218] Preparation of compounds of general formula (I)

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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, which is usually 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.

[0223] In general, the esterification of the corresponding dicarboxylic acid, e.g., 4-oxoheptanedioic 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.

[0224] 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.

[0225] The esterification can be carried out in the absence of an added solvent or in the presence of a solvent.

[0226] 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.

[0227] Esterification is usually carried out in a temperature range of 50 to 250 °C.

[0228] If the esterification catalyst is selected from organic acids or mineral acids, the esterification is usually carried out in a temperature range of 50 to 160 °C.

[0229] If the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250 °C.

[0230] The esterification can take place in the absence or in the presence of an inert gas. An inert gas is generally understood to be a gas which, under the given reaction conditions, does not react with the reactants, reagents, solvents or the resulting products involved in the reaction. It may be preferred for the esterification to take place without the addition of an inert gas. For example, the alcohol and the acid are combined in a molar ratio of 2:1 in a stirred flask together 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 from 100 to 140 °C. The water formed during the reaction is distilled off azeotropically together with the alcohol and then separated off. The alcohol is returned to the reaction mixture.

[0231] The dicarboxylic acid and aliphatic alcohols used to prepare the compounds of general formula (I) can either be purchased commercially or prepared according to synthesis routes known from the literature.

[0232] Transesterification

[0233] 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 will be apparent to him from his general specialist 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 -C 2 -alkyl. This includes, for example, the reaction of corresponding carboxylic acid dialkyl esters, for example dimethyl 4-oxoheptanedioate or diethyl 4-oxoheptanedioate or ethyl methyl 4-oxoheptanedioate or mixtures thereof, with at least one alcohol component selected from the alcohols R 1 -OH and R 2 -OH, where R 1 and R 2 represent C 10 -C 13 -alkyl, where at least some of the radicals R 1 and / or R 2 are branched, in the presence of a suitable transesterification catalyst.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] The transesterification of the di-(Ci-C2)-alkyl esters of corresponding dicarboxylic acids, for example 4-oxoheptanedioic 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.

[0239] 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.

[0240] The temperature during transesterification is usually in the range of 20 to 200 °C.

[0241] 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. The aliphatic dicarboxylic acids and cycloaliphatic alcohols used to prepare the compounds of general formula (I) can either be purchased commercially or prepared using synthesis routes known from the literature.

[0242] Michael Tuttle Musser, in "Cyclohexanol and Cyclohexanone" in "Ullmann's Encyclopedia of Industrial Chemistry" (2011) (DOI: 10.1002 / 14356007. a08_217.pub2), discloses technical synthesis routes for the large-scale production of cyclohexanol. Cyclohexanol can be obtained either by hydrogenation of phenol in the gas phase or by catalyzed oxidation of cyclohexane with the aid of transition metal catalysts in the liquid phase using atmospheric oxygen. Cyclohexanol can be obtained more selectively and in higher yields by using boric acid in the liquid phase and oxidizing it with atmospheric oxygen. This latter process proceeds via the intermediate stage of a peroxyboric acid ester of cyclohexanol. Furthermore, a process starting from benzene has also been realized on an industrial scale. In this process, benzene is hydrogenated step by step and cyclohexene is separated from the secondary components, such as unreacted benzene and cyclohexane.In a catalyzed step, cyclohexene is then converted into cyclohexanol very selectively and in high yields (up to 95% over all steps).

[0243] Preparation of compounds of general formula (II)

[0244] The compounds of general formulas (II), (II. a) and (II. b) can either be purchased commercially or prepared by methods known in the art.

[0245] For example, the diesters can be obtained by esterification or transesterification of the diacids or suitable derivatives thereof with the corresponding alcohols. Conventional methods are known to those skilled in the art. The esterification can be carried out by conventional methods known to those skilled in the art.

[0246] Compounds of the general formula (II. a)

[0247] As a rule, 1,2-cyclohexanedicarboxylic acid esters are usually obtained by ring hydrogenation of the corresponding phthalic acid esters. The ring hydrogenation can be carried out according to the process described in WO 99 / 32427. A particularly suitable ring hydrogenation process is also described, for example, in WO 2011 / 082991 A2.

[0248] Likewise, 1,2-cyclohexanedicarboxylic acid esters can be prepared in a reaction sequence comprising a Diels-Alder reaction followed by hydrogenation and esterification, or subsequent esterification and hydrogenation. Suitable processes are known to those skilled in the art, for example from WO 02 / 066412. Furthermore, 1,2-cyclohexanedicarboxylic acid esters can be obtained by esterification of 1,2-cyclohexanedicarboxylic acid or suitable derivatives thereof with the corresponding alcohols. The esterification can be carried out by conventional processes known to those skilled in the art.

[0249] The processes for preparing compounds of general formula (II.a) have in common that starting from phthalic acid, 1,2-cyclohexanedicarboxylic acid, or suitable derivatives thereof, an esterification or transesterification is carried out, using the corresponding C4-C12 alkanols as starting materials. These alcohols are generally not pure substances, but rather mixtures of isomers, the composition and degree of purity of which depend on the specific process used to prepare them.

[0250] Preferred C4-C12-alkanols used to prepare the compounds (II.a) present in the plasticizer composition according to the invention can be straight-chain or branched, or consist of mixtures of straight-chain and branched C4-C12-alkanols. These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isononanol, n-dodecanol, or isododecanol. Particular preference is given to C2-C12-alkanols, in particular 2-ethylhexanol, isononanol, and 2-propylheptanol, especially isononanol.

[0251] Compounds of formula (II. a) are commercially available. A suitable commercially available plasticizer of formula (II. a) is, for example, di-(1,2-isononyl cyclohexanoate), which is marketed under the brand name Hexamoll® DINCH by BASF SE, Ludwigshafen, Germany.

[0252] Compounds of formula (II. b)

[0253] As a rule, the dialkyl terephthalates are obtained by esterification of terephthalic acid or suitable derivatives thereof with the corresponding alcohols. The esterification can be carried out by conventional methods known to those skilled in the art, as described, for example, in WO 2009 / 095126.

[0254] The processes for preparing the compounds of formula (II.b) have in common that, starting from terephthalic acid or suitable derivatives thereof, an esterification or transesterification is carried out, using the corresponding C4-C12 alkanols as starting materials. These alcohols are generally not pure substances, but rather mixtures of isomers whose composition and degree of purity depend on the particular process used to prepare them. C7-C12 alkanols are preferably used as starting materials.

[0255] Preferred C4-C12 alkanols used to prepare the compounds (II.b) present in the plasticizer composition according to the invention can be straight-chain or branched, or consist of mixtures of straight-chain and branched C4-C12 alkanols. These include n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, iso-decanol, n-dodecanol, or isododecanol. Particularly preferred are Cz-Ci2-alkanols, in particular 2-ethylhexanol, isononanol and 2-propylheptanol, especially 2-ethylhexanol.

[0256] Compounds of formula (II. b) are commercially available. A suitable commercially available plasticizer of formula (II. b) is, for example, di-(2-ethylhexyl) terephthalate (DOTP), which is marketed under the brand name Eastman 168™ by Eastman Chemical BV, Capelle aan den Ijssel, Netherlands, and under the brand name Palatinol® DOTP by BASF Corp., Florham Park, NJ, USA.

[0257] Alkanols

[0258] In the context of the present application, with regard to the alkanols mentioned below, the term "isoalcohol" is to be understood as a mixture of structural isomers, unless otherwise stated.

[0259] Heptanol

[0260] The heptanols used to prepare the compounds of general formula (II) can be straight-chain or branched or consist of mixtures of straight-chain and branched heptanols. Preference is given to using mixtures of branched heptanols, also known 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 give 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 give 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 in DE-A 2139630, DE-A 2244373, DE-A 2404855, and WO 01014297.

[0261] For the rhodium-catalyzed hydroformylation of 1-hexene or the hexene isomer mixtures, the industrially established rhodium low-pressure hydroformylation process using triphenylphosphine ligand-modified rhodium carbonyl compounds, as is the subject of US-A 4,148,830, can be used. For the rhodium-catalyzed hydroformylation of long-chain olefins, such as the hexene isomer mixtures obtained by the above-mentioned processes, non-ligand-modified rhodium carbonyl compounds can advantageously serve as catalysts; in contrast to the low-pressure process, a higher pressure of 80 to 400 bar must be set. The implementation of such rhodium high-pressure hydroformylation processes is described, for example, in EP-A 695734, EP-B 880494, and EP-B 1047655.

[0262] The isoheptanal mixtures obtained after hydroformylation of the hexene isomer mixtures are catalytically hydrogenated to isoheptanol mixtures in a conventional manner. Heterogeneous catalysts are preferably used for this purpose, which contain, 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 T02. Such catalysts are described, for example, in DE-A 3228881, DE-A 2628987, and DE-A 2445303.The hydrogenation of the isoheptanals is particularly advantageously 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 in order to avoid side reactions, a small amount of water, advantageously 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.

[0263] Octanol

[0264] 2-Ethylhexanol, which for many years was the plasticizer alcohol produced in the largest quantities, can be obtained by 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).

[0265] Essentially straight-chain octanols can be obtained by rhodium- or, preferably, cobalt-catalyzed hydroformylation of 1-heptene followed by hydrogenation of the resulting n-octanal to n-octanol. The required 1-heptene can be obtained from the Fischer-Tropsch synthesis of hydrocarbons.

[0266] 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 isomer mixture of differently branched C8 alcohols, for example 2,3-dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 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, preferably 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.

[0267] The codimerization of propene with butenes to form isomeric heptenes can be advantageously carried out using the homogeneously catalyzed Dimersol® process (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 can include tributylphosphine, triisopropylphosphine, tricyclohexylphosphine, and / or tribenzylphosphine. The reaction takes place at temperatures of 0 to 80 °C, whereby a pressure is advantageously set at which the olefins are dissolved in the liquid reaction mixture (Cornils; Hermann: Applied Homogeneous Catalysis with Organometallic Compounds; 2nd edition; Vol. 1; pp. 254 - 259, Wiley-VCH, Weinheim 2002).

[0268] 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.

[0269] 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 by the PolyGasO process for olefin di- or oligomerization (Chitnis et al.; Hydrocarbon Engineering 10, No. 6 - June 2005). Bronsted-azide catalysts, which are very well suited for the codimerization of propene and butenes to heptenes, are zeolites, which are used in the EMOGASO process, which is based on the PolyGasO process.

[0270] 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.

[0271] Nonanol

[0272] Essentially straight-chain nonanol can be obtained 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, by ethylene oligomerization using a nickel complex catalyst that is homogeneously soluble in the reaction medium—1,4-butanediol—with, for example, diphenylphosphinoacetic acid or 2-diphenylphosphinobenzoic acid as ligands. This process is also known as the Shell Higher Olefins Process or SHOP process (see Weisermel, Arpe: Industrial Organic Chemistry; 5th edition; p. 96; Wiley-VCH, Weinheim 1998).

[0273] Isononanol, which is used to synthesize the diisononyl esters of general formula (II) contained in the plasticizer composition according to the invention, is not a single chemical compound, but rather a mixture of differently branched isomeric Cg alcohols, which can have different degrees of branching depending on the method of their preparation, in particular the starting materials used. In general, isononanols are prepared by dimerizing butenes to form isooctene mixtures, subsequent hydroformylation of the isooctene mixtures, and hydrogenation of the resulting isononanal mixtures to form isononanol mixtures, as explained in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A1, pp. 291-292, VCH Verlagsgesellschaft GmbH, Weinheim 1995.

[0274] 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, which is catalyzed primarily by liquid, e.g., sulfuric or phosphoric acid, or solid, e.g., phosphoric acid supported on diatomaceous earth, SiO2, or Al2O3 as a support material, or zeolites 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. Isononanols with a lower degree of branching are 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, via the route described above of butene dimerization, hydroformylation of the isooctene and hydrogenation of the resulting isononanal mixtures. A preferred raw material is the so-called raffinate II, which is 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-catalysed 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 isobutyl tert-butyl ether, which is used to obtain pure isobutene.

[0275] Raffinate II contains, in addition to 1-butene and cis- and trans-2-butene, n- and iso-butane and residual amounts of up to 5 wt.% of isobutene.

[0276] The dimerization of the linear butenes or of the butene mixture contained in the raffinate II can be carried out 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 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 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, for example,hydrogenated to the suitable isononanol mixtures using one of the catalysts mentioned above in connection with isoheptanol production.

[0277] 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 preferably 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.

[0278] The diisononyl esters of the general formula (II) used in the plasticizer composition according to the invention 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.

[0279] Possible compositions of isononanol mixtures which can be used to prepare the compounds of the general formula (II) used according to the invention 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 production conditions, 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.

[0280] For example, an isononanol mixture prepared 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:

[0281] 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;

[0282] 0.38 to 1.38 wt.%, preferably 0.48 to 1.28 wt.%, particularly preferably 0.58 to 1.18 wt.% 2,6-dimethylheptanol;

[0283] 2.78 to 4.78 wt.%, preferably 2.98 to 4.58 wt.%, particularly preferably 3.28 to 4.28 wt.% 3,5-dimethylheptanol;

[0284] 6.30 to 16.30 wt.%, preferably 7.30 to 15.30 wt.%, particularly preferably 8.30 to 14.30 wt.% 3,6-dimethylheptanol;

[0285] 5.74 to 11.74 wt.%, preferably 6.24 to 11.24 wt.%, particularly preferably 6.74 to 10.74 wt.% 4,6-dimethylheptanol;

[0286] 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;

[0287] 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; 4.00 to 10.00 wt.%, preferably 4.50 to 9.50 wt.%, particularly preferably 5.00 to 9.00 wt.% of 3,4-dimethylheptanol;

[0288] 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;

[0289] 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;

[0290] 1.21 to 5.21 wt.%, preferably 1.71 to 4.71 wt.%, particularly preferably 2.21 to 4.21 wt.% 4,5-dimethylheptanol;

[0291] 1.55 to 5.55 wt.%, preferably 2.05 to 5.05 wt.%, particularly preferably 2.55 to 4.55 wt.% 5,6-dimethylheptanol;

[0292] 1.63 to 3.63 wt.%, preferably 1.83 to 3.43 wt.%, particularly preferably 2.13 to 3.13 wt.% 4-methyloctanol;

[0293] 0.98 to 2.98 wt.%, preferably 1.18 to 2.78 wt.%, particularly preferably 1.48 to 2.48 wt.% 5-methyloctanol;

[0294] 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;

[0295] 1.96 to 3.96 wt.%, preferably 2.16 to 3.76 wt.%, particularly preferably 2.46 to 3.46 wt.% 7-methyloctanol;

[0296] 1.24 to 3.24 wt.%, preferably 1.44 to 3.04 wt.%, particularly preferably 1.74 to 2.74 wt.% 6-methyloctanol;

[0297] 0.1 to 3% by weight, preferably 0.2 to 2% by weight, particularly preferably 0.3 to 1% by weight of n-nonanol; 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 components mentioned amounts to 100% by weight.

[0298] 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 following compositions, depending on the raw material composition and variations in the reaction conditions used:

[0299] 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0 wt.% n-nonanol;

[0300] 12.8 to 28.8 wt.%, preferably 14.8 to 26.8 wt.%, particularly preferably 15.8 to 25.8 wt.% 6-methyloctanol;

[0301] 12.5 to 28.8 wt.%, preferably 14.5 to 26.5 wt.%, particularly preferably 15.5 to 25.5 wt.% 4-methyloctanol;

[0302] 3.3 to 7.3 wt.%, preferably 3.8 to 6.8 wt.%, particularly preferably 4.3 to 6.3 wt.% of 2-methyloctanol; 5.7 to 11.7 wt.%, preferably 6.3 to 11.3 wt.%, particularly preferably 6.7 to 10.7 wt.% of 3-ethylheptanol;

[0303] 1.9 to 3.9 wt.%, preferably 2.1 to 3.7 wt.%, particularly preferably 2.4 to 3.4 wt.% 2-ethylheptanol;

[0304] 1.7 to 3.7 wt.%, preferably 1.9 to 3.5 wt.%, particularly preferably 2.2 to 3.2 wt.% 2-propylhexanol;

[0305] 3.2 to 9.2 wt.%, preferably 3.7 to 8.7 wt.%, particularly preferably 4.2 to 8.2 wt.% 3,5-dimethylheptanol;

[0306] 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0 wt.% 2,5-dimethylheptanol;

[0307] 1.8 to 3.8 wt.%, preferably 2.0 to 3.6 wt.%, particularly preferably 2.3 to 3.3 wt.% 2,3-dimethylheptanol;

[0308] 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;

[0309] 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;

[0310] 0.5 to 6.5 wt.%, preferably 1.5 to 6 wt.%, particularly preferably 1.5 to 5.5 wt.% of other alcohols having 9 carbon atoms; with the proviso that the total of the said components amounts to 100 wt.%.

[0311] Decanol

[0312] Isodecanol is generally not a single chemical compound, but rather a complex mixture of differently branched isomeric decanols.

[0313] 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 Cz-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.

[0314] 2-Propylheptanol can be pure 2-propylheptanol or propylheptanol isomer mixtures, such as those generally formed during the industrial production of 2-propylheptanol and commonly 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 Pat. No. 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-dimethyl-pentanol.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 prepared from such 2-propylheptanol isomer mixtures.

[0315] 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 with 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 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 feedstock is hydroformylated by virtually all catalyst systems, albeit at varying rates, to 3-methylbutanal and, depending on the catalyst, to a lesser extent to pivalaldehyde.

[0316] The Cs-aldehydes obtained, depending on the starting materials and catalysts used, i.e., n-valeraldehyde optionally mixed 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 C5 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 formed predominantly or entirely.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.

[0317] As already mentioned, the compounds of general formula (II) 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.

[0318] 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.%.

[0319] 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.%.

[0320] 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.%.

[0321] 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.

[0322] Undecanol

[0323] The undecanols can be branched or composed of mixtures of straight-chain and branched undecanols. It may be preferred to use mixtures of branched undecanols, also known as isoundecanol, as the alcohol component.

[0324] 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 produced, for example, by the SHOP process mentioned above for the production of 1-octene.

[0325] 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 isoundecane mixtures using rhodium or cobalt catalysis can be carried out as previously described in connection with the synthesis of C2 to C8 alcohols. The same applies to the hydrogenation of n-undecanal or isoundecanal mixtures to n-undecanol or isoundecanol, respectively.

[0326] After purification of the hydrogenation output by distillation, the C2 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.

[0327] Dodecanol

[0328] The dodecanols can be branched or composed of mixtures of straight-chain and branched dodecanols. 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 via 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.

[0329] Alternatively, n-dodecanol can also be produced by hydrogenation of natural fatty acid methyl esters, for example from coconut oil.

[0330] 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.

[0331] Examples and figures

[0332] Fig. 1 shows the gelling behavior of various plastisols with plasticizers according to the disclosure.

[0333] Compositions and comparative plasticizer compositions of the general formula (II. a).

[0334] Fig. 2 shows the gelling behavior of various plastisols with plasticizers according to the disclosure.

[0335] Compositions and comparative plasticizer compositions of the general formula (II. b).

[0336] 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.

[0337] An Agilent 6890 series gas chromatograph was used for gas chromatography, and an Optima 5 Amin 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) was used as the column. A split / splitless column with a Topaz Split Precision Liner Whool from Restek (# 23305) served as the injector. The injection conditions were: injector temperature = 280 °C, injection volume = 1 DL, 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.

[0338] In the examples, the starting materials are used as shown in Table 2.

[0339] Table 2.

[0340] Unless otherwise stated, all proportions are based on weight.

[0341] Synthesis of compound 1.2 (Dicyclohexyl 4-oxo-pimelate)

[0342] A 1.6 L reactor vessel was charged with diethyl 4-oxopimelate (296 g, 1.28 mol, 1.0 eq., BLDpharm), cyclohexanol (384 g, 3.83 mol, 3.0 eq., BASF), and Tyzor TPT-20B (0.34 g, 0.05 wt. %, Dorf Ketal). The reaction mixture was heated to 157-192 °C under a nitrogen stream. After 16 hours of reaction, no more ethanol was formed. The excess cyclohexanol was then distilled off (max. 185 °C,

[0343] 9 mbar). The reaction temperature was brought to 80 °C, and the reaction mixture was quenched with an aqueous 2.0 wt% NaOH solution (1.7 g). After stirring at 80 °C for 20 minutes, water (16 mL) was added to the reaction mixture to agglomerate the precipitated titanium dioxide. The water was immediately distilled off (max. 123 °C, 4 mbar), and the crude product was filtered through a pressure filter (2 L Pall filter holder, AK 100). To obtain a highly pure product, steam distillation was performed (max. 210 °C, duration: 5 h), and finally, a nitrogen stream was passed through the product (200 °C,

[0344] 10 min) and the product was filtered through a pressure filter (2 L Pall filter holder, AKS 7 with activated carbon, 1 bar). 215 g of the product was obtained (635 mmol, 50% yield).

[0345] Analysis: GC area%: 98.75

[0346] The following Table 3 shows the properties of the compound as described above together with comparative examples not according to the invention.

[0347] Table 3.

[0348] Application-related tests:

[0349] II. a) Determination of the dissolution temperature of the plasticizer compositions according to the disclosure:

[0350] To determine the dissolution temperature of the disclosed plasticizer compositions, approximately 10 grams of a mixture were 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.

[0351] Table 4.

[0352] 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 is determined as the result of the measurement. These measurements were performed four times in total, and the arithmetic mean of all four measurements was used as the final result.

[0353] As can be seen from Table 3, 4-oxoheptanedioic acid dicyclohexyl ester (compound I.2) exhibits a significantly lower dissolution temperature for PVC than the plasticizers isononyl benzoate (Vestinol INB), isodecyl benzoate (Jayflex MB10), diisononyl phthalate (Palatinol® N), di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH), and di-(2-ethylhexyl) terephthalate (Palatinol DOTP). II.b) Determination of the gelling behavior of plastisols with the disclosed plasticizer compositions

[0354] To investigate the gelling behavior of plastisols based on the disclosed plasticizer compositions, plastisols containing PVC and a mixture of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 4-oxoheptanedioic acid di-cyclohexyl ester (compound 1.2) or di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) with 4-oxoheptanedioic acid di-cyclohexyl ester (compound 1.2) in different proportions (Palatinol DOTP to 4-oxoheptanedioic acid di-cyclohexyl ester 91 / 9, or Hexamoll DINCH to 4-oxoheptanedioic acid di-cyclohexyl ester 78 / 22) were prepared according to the following recipe:

[0355] Table 5.

[0356] For comparison, plastisols were also produced which, in addition to PVC, exclusively contained the plasticizers di-(2-ethylhexyl) terephthalate (Palatinol DOTP), diisononyl phthalate (Palatinol® N) or di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH), or plastisols with 73 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 27 wt.% of the gelling agent isononyl benzoate (Vestinol® INB), a plastisol with 64 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 36 wt.% of the gelling agent isodecyl benzoate (Jayflex® MB 10), a plastisol with 45 wt.% of the plasticizer di-(isononyl)-1 ,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) with 55 wt.% of the gelling agent isononyl benzoate (Vestinol® INB) and a plastisol with 33 wt.% of the plasticizer di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) with 67 wt.% of the gelling agent isodecyl benzoate (Jayflex® MB 10). Table 6.

[0357] The plastisols were produced by weighing the two PVC types together in a PVC-free device. The liquid components were weighed into a second PVC-free device. Using a dissolver (Jahnke & Kunkel, IKA-Werk, type RE-166 A, 60-6000 rpm, dissolver disk diameter = 40 mm), the PVC was stirred into the liquid components at 400 rpm. After the mixture was homogenized, the speed was increased to 2500 rpm and homogenized for 150 s. The plastisol was transferred from the PVC-free device to a suitable device, such as a steel bowl, and placed under vacuum to remove the air contained in the plastisol. The plastisol was then brought back to ambient pressure. The rheological measurements began 30 minutes after homogenization for all plastisols.

[0358] The viscosity measurements were carried out using a heated oscillation and rotation rheometer MCR 302 from Anton Paar in an oscillation test.

[0359] Measuring system: plate / plate d=50 mm

[0360] Amplitude 0: 1%

[0361] Frequency: 1 Hz

[0362] Gap width: 1 mm

[0363] Starting temperature: 20 °C

[0364] Temperature profile: 20 - 200 °C

[0365] Temperature increase: 10 °C / min

[0366] Measuring points: 201

[0367] Measurement point duration: 0.09 min

[0368] The measurement was carried out in two ramps. The first ramp served to temper the sample. At 20 °C, the plastisol was gently sheared for 2 min at 0=1%. The temperature program started with the second ramp. During the measurement, the storage modulus and the loss modulus were recorded. The complex viscosity h* is calculated from the quotient of these two values. The temperature at which the viscosity maximum was reached is considered the gelling temperature of the plastisol. As shown in Fig. 1, the plastisols with the plasticizer composition according to the disclosure gelled more effectively than the plastisol containing only the plasticizer di-(isononyl)-

[0369] I,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) at significantly lower temperatures. Even with a composition of 78 wt.% di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) and 22 wt.% dicyclohexyl 4-oxoheptanedioate (compound I.2), a gelling temperature of 150 °C is achieved, which corresponds to the gelling temperature of the plasticizer Palatinol® N and is sufficient for many plastisol applications. By further increasing the proportion of dicyclohexyl 4-oxoheptanedioate in the disclosed plasticizer compositions, the gelling temperature of the plastisols can be further reduced.

[0370] As shown in Fig. 2, a composition of 91 wt.% di-(2-ethylhexyl) terephthalate (Palatinol DOTP) and 9 wt.% dicyclohexyl 4-oxoheptanedioate (compound I.2) already achieves a gelling temperature of 150 °C, which corresponds to the gelling temperature of the plasticizer Palatinol® N and is sufficient for many plastisol applications. By further increasing the proportion of dicyclohexyl 4-oxoheptanedioate in the disclosed plasticizer compositions, the gelling temperature of the plastisols can be further reduced.

[0371] Both figures include two comparative examples with gelling agents. A plastisol consisting of 73 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 27 wt.% of the gelling agent isononyl benzoate (Vestinol® INB) and a plastisol consisting of 64 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 36 wt.% of the gelling agent isodecyl benzoate (Jayflex® MB 10). In both cases, the gelling temperature of 150 °C is also reached, which corresponds to the gelling temperature of diisononyl phthalate.

[0372] For the plasticizer compositions containing the gelling agents isononyl benzoate (Vestinol® INB) and isodecyl benzoate (Jayflex® MB 10), significantly higher proportions of isononyl benzoate (27 wt.%) and isodecyl benzoate (36 wt.%) are required to achieve a gelling temperature of 150 °C for the plastisols. Therefore, 4-oxoheptanedioic acid dicyclohexyl ester has a significantly better gelling effect than the gelling agents isononyl benzoate (Vestinol® INB) and isodecyl benzoate (Jayflex® MB 10) and is therefore suitable as a gelling agent.

[0373] II. c) Production and testing of soft PVC films produced using plasticizer compositions according to the invention

[0374] Recipe: see Table 7 below. Table 7.

[0375] *Comparison example

[0376] The plastisols of formulations I*, II*, III*, V, and VI were prepared as described under II.b). Films with a thickness of 0.5 mm were produced from the resulting plastisols by gelling the plastisols in a Mathis oven.

[0377] Settings on the Mathisofen:

[0378] Exhaust air: flap fully open

[0379] Fresh air: open

[0380] Recirculation: maximum position

[0381] Upper air / lower air: Upper air position 1

[0382] A new relay paper was clamped into the clamping device on the Mathis oven. The oven was preheated to 190 °C and the gel time was set to 120 s. To adjust the gap, the gap between the paper and the doctor blade was set to 0.1 mm using the thickness gauge. The thickness gauge was set to 0.1 mm. The gap was then adjusted to a value of 0.7 mm on the dial gauge.

[0383] The plastisol was applied to the paper and smoothed with a squeegee. The clamping device was then moved into the oven using the start button. After 120 seconds, the clamping device was removed from the oven. The plastisol had gelled, and the resulting 0.5 mm thick film could be peeled off.

[0384] II. d) Films of formulation IV* were produced as follows: 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 resulted in a rolled sheet with a thickness of 0.53 mm. The cooled rolled sheet was then subjected to a temperature of 190 °C and a pressure of 150 bar for 180 seconds on a "Laborplattenpresse 400 P" press from the company.Collin pressed the film into a 0.50 mm thick soft PVC film. While maintaining the same pressure, the film was cooled to approximately 40 °C within 10 minutes.

[0385] II. e) Determination of the Shore A hardness of films with the plasticizer compositions according to the disclosure

[0386] 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 press foils produced as under II. d) or the foils produced under II. c). A suitable punching die must be used to ensure the foils are the same size in each case. These are placed, free of air bubbles, into a press frame (dimensions 400 x 400 mm; thickness 10 mm) containing 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 chamber at 23 °C and approximately 50% humidity prior to testing.A Hildebrand HDD-2 durometer is used to measure Shore A hardness. Ten readings are taken on a test specimen after a 15-second penetration time.

[0387] II. f) Determination of film volatility of films with the plasticizer compositions according to the disclosure

[0388] To determine film volatility, four individual films (150 x 100 mm) were cut from the pressed films produced under II. d) and the films produced under II. c), 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.

[0389] II. g) Determination of the compatibility (permanence) of films with the plasticizer compositions according to the disclosure

[0390] To determine compatibility, 10 test specimens (films) measuring 75 x 110 x 0.5 mm were cut from the pressed films produced under II. d) and the films produced under II. c). The films were perforated on the wide side, labeled, and weighed. The test specimens produced in this way 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 glass vessels are then hermetically sealed and placed in an oven with internal temperature control. The test is carried out at 70 °C and 100% rel.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 the air for 1 hour while hanging freely. The films were then cleaned with methanol in a fume hood. The films were then dried in a drying cabinet (natural convection) at 80°C while hanging freely for 16 hours. After removal from the drying cabinet, the films were conditioned in the laboratory for 1 hour while hanging freely and then weighed. The test result was given in each case as the arithmetic mean of the weight changes compared to the samples before being placed in the heating cabinet.

[0391] In addition to the gravimetric evaluation, the films are visually assessed using the following assessment table:

[0392] 0 = dry touch, the film is smooth and dry (best compatibility)

[0393] 1 = blunt touch, the film is still dry, a small amount of plasticizer is on the

[0394] surface and results in a blunt grip. Finger marks are visible

[0395] 2 = sticky feel, plasticizer has already noticeably leaked out on the surface, fingerprints are easily and clearly visible

[0396] 3 = weak, dry coating; visible to the naked eye

[0397] 4 = weak, liquid or greasy coating

[0398] 5 = heavy dry coating

[0399] 6 = heavy greasy coating II. h) Determination of the HCI residual stability of films with the plasticizer compositions according to the disclosure

[0400] 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 carried out. Approximately 50 mg of the films prepared under II. c) or II. d) are 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 so that approximately 2 mm protrudes. The glass tubes prepared in this way 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.

[0401] II. i) Determination of the cold fracture temperature of films with the plasticizer compositions according to the disclosure

[0402] The cold fracture temperature test is carried out on test specimens obtained from the films produced under II. c) or II. d). 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 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 specimen carrier (bomb) with the test specimens is inserted. To condition the test specimens, they are kept at the same temperature for 1 hour per test temperature. For evaluation, only those test loops that have broken completely into two or more pieces are considered defective. To determine the cold fracture temperature, at least one row of six test specimens must be assessed as completely broken and one row of six as completely intact. The temperature interval for the tests to be carried out is 5 °C in each case. The cold fracture temperature is calculated according to the formula in the draft of DIN standard 53372 (1981). ll.j) Determination of the tensile test properties of films with the plasticizer compositions as disclosed. This test is used to determine the parameters elongation at break, stress at break and 100% modulus. For this purpose, type 2 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 films described under II. c) or II. d) using a punching die. Before testing, the test specimens are conditioned for 7 days in a climate chamber under standard climate conditions. 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, Parts 1-3. Each measurement consists of the testing of 10 individual test specimens. The measuring length of 100 mm results from the free clamping length of the test specimen between the clamping jaws. The test speed is 100 mm / min. Within the measuring length, the average thickness is determined from 5 individual values. The strain and the 100% modulus are measured by changing the traverse path.

[0403] The results of the application tests are shown in Tables 8 and 9.

[0404] As shown in Tables 8 and 9, the properties of the plasticizer compositions according to the invention are comparable to the properties of the previously known non-inventive plasticizers. The addition of appropriate amounts of the plasticizer according to the invention, 4-oxoheptanedioic acid di-1,2-cyclohexyl ester, leads to only a slight change in the properties of the plasticizer composition according to the invention in PVC due to the small amounts required to achieve the gelling properties of diisononyl phthalate.

[0405] Table 8.

[0406] * Comparison example

[0407] Table 9.

[0408] Comparison example

Claims

1. A plasticiser composition comprising a) at least one compound of the general formula (I)oO 0(I)whereinRi and R2 are independently selected from Cs-C(8) cycloalkyl which is unsubstituted or bears one or more Ci-C(w) alkyl substituents, and n1 and n2 independently of one another are 1,2 or 3;andb) at least one compound of the general formula (II)(II)whereinR3 and R4 are independently selected from C4-Ci2-alkyl, andY is selected from (Y.a) and (Y.b)(Y.a)(Y.b)wherein # indicates points of attachment.

2. The plasticiser composition according to claim 1, wherein n1 and n2 are 1.

3. The plasticiser composition according to claim 1 or 2, wherein Ri and R2 are independentlyselected fromcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2,5-dimethylcyclopentyl,cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl,cycloheptyl, 2-methylcycloheptyl, 3-methylcycloheptyl, 4-methylcycloheptyl, 2,3-dimethylcycloheptyl, 2,4-dimethylcycloheptyl, 2,5-dimethylcycloheptyl, 2,6-dimethylcycloheptyl, 2,7-dimethylcycloheptyl, 3,4-dimethylcycloheptyl, 3,5-dimethylcycloheptyl, 3,6-dimethylcycloheptyl, 4,5-dimethylcycloheptylcyclooctyl, 2-methylcyclooctyl, 3-methylcyclooctyl, 4-methylcyclooctyl, 5-methylcyclooctyl, 2,3-dimethylcyclooctyl, 2,4-dimethylcyclooctyl, 2,5-dimethylcyclooctyl, 2,6-dimethylcyclooctyl, 2,7-dimethylcyclooctyl, and 2,8-dimethylcyclooctyl.

4. The plasticiser composition according to claim 3, wherein Ri and R2 are independently selected from cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

5. The plasticiser composition according to any one of the preceding claims, wherein Ri and R2 are the same.

6. The plasticiser composition according to any one of the preceding claims, wherein Y is (Y.a) and R3 and R4 are independently selected from branched and unbranched C7-C12-alkyl.

7. The plasticiser composition according to any one of the preceding claims, wherein Y is (Y.b) and preferably R3and R4are independently selected from branched and unbranched C7-Ci2-alkyl.

8. The plasticiser composition according to any one of the preceding claims, wherein R3 and R4 are both 2-ethylhexyl or both isononyl.

9. Plasticiser composition according to any one of the preceding claims, containing the at least one compound of the general formula (I) in an amount of 5 to 60% by weight, preferably 7 to 40% by weight, based on the total mass of the compounds of the general formula (I) and (II).

10. The plasticiser composition according to any one of the preceding claims, comprising at least one further plasticiser which is different from the compounds of the general formula (I) and (II).

11. The plasticiser composition according to claim 10, wherein the further plasticiser is selected from- phthalic acid dialkyl esters,- trimellitic acid trialkyl esters,- benzoic acid alkyl esters,- dibenzoic acid esters,- hydroxy benzoic acid esters,- esters of saturated monocarboxylic acids,- esters of unsaturated monocarboxylic acids,- esters of hydroxy monocarboxylic acids,- esters of dicarboxylic acids,- esters of saturated hydroxy dicarboxylic acids,- amides and esters of aromatic sulphonic acids,- pentaerythritol esters,- alkyl sulphonic 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-tetrahydrofuran dicarboxylic acid esters,- epoxidised vegetable oils,- epoxidised fatty acid monoalkyl esters,- 1,3-cyclohexanedicarboxylic acid dialkyl esters,- 1,4-cyclohexanedicarboxylic acid dialkyl esters,- polyesters of aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols,- other plasticisers, and- mixtures thereof.

12. A moulding composition or plastisol comprising the plasticiser composition according to any one of claims 1 to 11, and at least one polymer preferably selected from a thermoplastic, an elastomer, and mixtures thereof.

13. The moulding composition or plastisol according to claim 12, whereinthe thermoplastic is selected from- homo- or copolymers containing at least one monomer in polymerised form, selected from C2-Cw-monoolefins such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols and their Cz-Cio-alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of Ci-Cwalcohols, vinylaromatics such as styrene, acrylonitrile, methacrylonitrile, a,p-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, polyethersulfones, polyacrylates, polymethyl methacrylates, polystyrenes, polyvinyl alcohols, polyvinyl acetates, polyvinyl butyrals, polyvinyl chlorides, polycaprolactones, cellulose alkyl esters and mixtures thereof,andthe 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.

14. Moulding compound or plastisol according to claim 12 or 13, additionally containing at least one additive selected from stabilisers, lubricants, fillers, colourants, flame inhibitors, light stabilisers, blowing agents, polymer processing agents, impact improvers, optical brighteners, antistatic agents, bio-stabilisers, silicon dioxide, phenolic resins, vulcanisingagents, cross-linking agents, vulcanisation accelerators, cross-linking accelerators, activators, oils, anti-ageing agents and mixtures thereof.

15. Use of the moulding composition or plastisol according to any one of claims 12 to 14 for the 5 manufacture of moulded articles, gloves, films, wallpaper or heterogeneous flooring, or fortextile coating.

16. Use of the plasticiser composition according to any one of claims 1 to 11 as a plasticiser for polymers, preferably for thermoplastics and elastomers.

017. Use according to claim 16 as a plasticiser in a moulding compound ora plastisol.

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