EP3491053A1

EP3491053A1 - Plasticizer composition

Info

Publication number: EP3491053A1
Application number: EP17742454.6A
Authority: EP
Inventors: Matthias Pfeiffer; Boris Breitscheidel; Axel Grimm; Herbert Morgenstern
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-08-01
Filing date: 2017-07-27
Publication date: 2019-06-05
Also published as: RU2019105688A3; CA3032594A1; WO2018024596A1; US20190161598A1; RU2019105688A; CN109563305A

Abstract

Disclosed is a plasticizer composition containing a) at least one compound of general formula (I), where R^1a, R^1b and R^1c independently represent C₃-C₅ alkyl, b) at least one compound of general formula (II), where R^2a and R^2b independently represent C₈ alkyl.

Description

Plasticizer composition

BACKGROUND OF THE INVENTION The present invention relates to a plasticizer composition containing at least one trimellitic acid trialkyl ester and at least one terephthalic acid tartyl ester, molding compositions containing at least one polymer and such plasticizer composition, plastisols containing at least one polymer and such plasticizer composition, and the use of these softener compositions, molding compositions and plastisols.

STATE OF THE ART

Polyvinyl chloride (PVC) is one of the most widely produced plastics in terms of quantity. PVC is usually a hard and brittle plastic up to about 80 ° C, which is used as rigid PVC (PVC-U) by adding heat stabilizers and other additives. The addition of plasticizers can yield soft PVC (PVC-P), which can be used for many applications where rigid PVC is unsuitable. In general, the use of plasticizers serves to lower the processing temperature of plastics and to increase their elasticity.

In addition to PVC, plasticizers are commonly used in other plastics. Other plastics may be, for example, polyvinyl butyral (PVB), homopolymers or copolymers of styrene, polyacrylates, polysulfides or thermoplastic polyurethanes (TPU).

Typical plasticizers for plastics are, for example, ortho-phthalic acid esters, such as di-2-ethylhexyl phthalate, diisononyl phthalate or diisodecyl phthalate. Short-chain ortho-phthalates, however, increasingly come under pressure because of their toxicological properties.

It is desirable that plasticizers in addition to a high compatibility with the plastic to be softened, that is, they do not occur or only relatively slowly from the plastic to be plasticized, are also toxicologically largely harmless. A toxicologically largely harmless plasticizer, which has gained some industrial relevance, especially for PVC, is di-2-ethylhexyl terephthalate (DEHT or DOTP).

The object of the present invention is therefore to provide a plasticizer composition for plastics, for example PVC, based on DOTP, which has a high compatibility with the plastics to be plasticized and is toxicologically harmless. In addition, the plasticizer composition should soften the plasticized with it Give good mechanical properties to plastics and show low volatility, both during processing and during use.

This object is achieved by a plasticizer composition comprising a) at least one compound of the general formula (I),

(I)

wherein

R ^1a R ^1b and R ^{1c are} independently C3 to Cs alkyl

at least one compound of the general formula (II),

wherein

R ^2a and R ^{2b are} independently Cs-alkyl, An object of the disclosure is the use of the disclosed plasticizer composition as a plasticizer for plastics.

Also subject of the disclosure is the use of the disclosed plasticizer composition as plasticizer for plastisols.

Also subject matter of the disclosure is a molding composition containing at least one polymer and the disclosed plasticizer composition. Further, a plastisol is the subject of the disclosure containing at least one polymer and the disclosed softener composition.

Also, the use of a molding composition containing at least one polymer and the disclosed plasticizer composition for the production of moldings and films is the subject of the present disclosure.

Also, the use of a plastisol containing at least one polymer and the disclosed plasticizer composition for making molded articles and films is the subject of the present disclosure.

Also, molded articles and films containing the disclosed plasticizer composition are the subject of the present disclosure.

DESCRIPTION OF THE INVENTION

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. The weight percentage refers to the total weight if nothing else is stated.

A mixture is any mixture of two or more, for example a mixture may contain two to five or more. A mixture can also contain an arbitrarily large number.

In the context of the present disclosure, a gelling aid is a plasticizer

or a mixture of different plasticizers, which is characterized in that the dissolution temperature of the plasticizer or the mixture of different plasticizers according to DIN 53408 (Jun 1967) is not more than 125 ° C.

A compound of general formula (I) may be: .1 is 1, 2,4-benzenetricarboxylic acid tr ^■ (n-propyl) ester

.2 1, 2,4-benzenetricarboxylic acid tr ^■ (iso-propyl) ester

.3 is 1, 2,4-benzenetricarboxylic acid tr ^■ (n-butyl) ester

.4 is 1, 2,4-benzenetricarboxylic acid tr ^■ (iso-butyl) ester

.5 1, 2,4-benzenetricarboxylic acid tr ^■ (n-pentyl) ester

.6 is 1, 2,4-benzenetricarboxylic acid tr ^■ (2-methylbutyl) ester

.7 is 1, 2,4-benzenetricarboxylic acid tr ^■ (3-methylbutyl) ester A compound of general formula (II) may be:

11.1 is di (2-ethylhexyl) terephthalate

11.2 is di (n-octyl) terephthalate A polymer may be an elastomer or a thermoplastic. A thermoplastic can usually be processed thermoplastically.

A thermoplastic may be, for example: TP.1 is a homopolymer or copolymer which contains in copolymerized form at least one monomer which is selected from C 2 to C 10 monoolefins, for example ethene, propylene, 1,3-butadiene, 2-chloro-1, 3-butadiene, vinyl alcohols or their C 2 - to C 10 -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 C 1 to C 10 alcohols, vinyl aromatics, for example styrene , (Meth) acrylonitrile, α, β-ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride.

TP.2 is a polyvinyl ester

TP.3 is a polycarbonate

TP.4 is a polyether

TP.5 is a polyether ketone

TP.6 is a thermoplastic polyurethane

TP.7 is a polysulfide

TP.8 is a polysulfone

TP.9 is a polyester

TP.10 is a polyalkylene terephthalate

TP.1 1 is a polyhydroxyalkanoate

TP.12 is a polybutylene succinate

TP.13 is a polybutylene succinate adipate

TP.14 is a polyacrylate with identical or different alcohol radicals from the group of

C ₄ - to Cs-alcohols such as butanol, hexanol, octanol, or 2-ethylhexanol

TP.15 is a polymethylmethacrylate TP 16 is a methyl methacrylate-butyl acrylate copolymer

TP 17 is an acrylonitrile-butadiene-styrene copolymer

TP 18 is an ethylene-propylene copolymer

TP 19 is an ethylene-propylene-diene copolymer

TP 20 is a polystyrene

TP 21 is a styrene-acrylonitrile copolymer

TP 22 is an acrylonitrile-styrene-acrylate

TP 23 is a styrene-butadiene-methyl methacrylate copolymer

TP 24 is a styrene-maleic anhydride copolymer

TP 25 is a styrene-methacrylic acid copolymer

TP26 is a polyoxymethylene

TP 27 is a polyvinyl alcohol

TP 28 is a polyvinyl acetate

TP 29 is a polyvinyl butyral

TP 30 is a polyvinyl chloride

TP 31 is a polycaprolactone

TP 32 is polyhydroxybutyric acid

TP 33 is polyhydroxyvaleric acid

TP 34 is polylactic acid

TP 35 is ethylcellulose

TP 36 is cellulose acetate

TP 37 is cellulose propionate

TP 38 is Celite acetate / butyrate

"X" as an entry in a table means that this combination exists.

In general, polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl chloride contained in the disclosed molding composition can be prepared by, for example, suspension polymerization or bulk polymerization. The polyvinyl chloride contained in the disclosed plastisol can be prepared, for example, by microsuspension polymerization or bulk polymerization. The preparation of polyvinyl chloride by polymerization of vinyl chloride and preparation 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.

The K value which characterizes the molar mass of the polyvinyl chloride and is determined in accordance with DIN-EN 1628-2 (Nov 1999) is usually in the range from 57 to 90, preferably in the range from 61 to, for the polyvinyl chloride softened with the disclosed softener composition 85 and more preferably in the range of 64 to 80. Advantageously, the present plasticizer composition is characterized by a high compatibility with the plastic to be softened. In addition, the gelling behavior of the plasticized plastic can be positively influenced by the present plasticizer composition. Furthermore, the present plasticizer composition may be characterized by low volatility, both in processing and during use of the final products. Also, the present plasticizer composition may have a beneficial effect on the mechanical properties of plasticized plastics therewith. Good mechanical properties can be reflected, for example, in a high elasticity of the plasticized plastics. A 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 plastic. A measure of good gelling properties may be a low dissolution temperature and / or a low gelling temperature.

The compatibility (permanence) of plasticizers in plasticized plastics characterizes the extent to which plasticizers tend to exude during use of the plasticized plastics, thereby impairing the performance properties of the plastics.

For example, low volatility in processing may be reflected by low process volatility.

For example, low volatility in use of the final product may be reflected in low film volatility.

Compounds of the general formula (I) have a comparable or lower Lösetem- temperature than bis (2-ethylhexyl) phthalate (125 ° C) according to DIN 53408 (Jun 1967). Because of their dissolution temperature and their plasticizer properties, compounds of the general formula (I) can be used as gelling aids.

Generally, the dissolution temperature / gelling temperature refers to the minimum temperature at which a substantially homogeneous phase forms between polymer and plasticizer.

The present disclosure is a plasticizer composition containing at least one compound of the general formula (I) and at least one compound of the general formula (II).

In a compound of general formula (I), R ^1a , R ^1b and R ^{1c are} independently C3 to C6 alkyl. C3- to Cs-alkyl may be straight-chain or branched. For example, C3 to Cs-alkyl n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl or 3-methylbutyl. It may be further preferred that R ^1a , R ^1b and R ^{1c are} independently C ₄ alkyl. C ₄ alkyl may be straight-chain or branched. For example, C ₄ alkyl may be n-butyl or isobutyl.

Even if R ^1a, R 1 ^b and R ^1c in a compound of general formula (I) are generally independently, R ^1a, R 1 ^b and R ^1c are the same in general.

The disclosed plasticizer composition contains at least one compound of general formula (I). Accordingly, the disclosed plasticizer composition may also contain a mixture of compounds of general formula (I).

The disclosed plasticizer composition may, for example, comprise a mixture of compounds of general formula (I) selected from 1.1, I.2, I.3, I.4, I.5, I.6 and I.7.

In a compound of general formula (II), R ^2a and R ^{2b are} independently Cs-alkyl. Ce-alkyl may be straight-chain or branched. For example, Cs-alkyl may be n-octyl, isooctyl, or 2-ethylhexyl. Although R ^2a and R ^2b in a compound of general formula (II) are generally independent of each other, R ^2a and R ^2b are generally the same.

The disclosed plasticizer composition contains at least one compound of the general formula (II). Accordingly, the disclosed plasticizer composition may also contain a mixture of compounds of general formula (II).

For example, the disclosed plasticizer composition may contain a mixture of compounds of the general formula (II) selected from 11.1 and II.2

A plasticizer composition may include, for example:

Trimellitic acid trialkyl ester Terephthalic acid dialkyl ester

11.1 II.2

1.1 X

1.1 X X

I.2X

I.2 X X

I.3 X

I.3 XX Trimellitic acid trialkyl ester Terephthalic acid dialkyl ester

11.1 II.2

1.4X

1.4 X X

1.5X

1.5 X X

1.6 X

1.6 X X

1.7X

1.7 XX a mixture of compounds 1.1 to I.7 and compound 11.1 or, a mixture of compounds 1.1 to I.7 and compound II.2 or, a mixture selected from compound 1.1, I.2, 13, I.4, I .5, I.6, and I.7 and a mixture selected from Compound 11.1 and II.2.

The content of at least one compound of the general formula (I) in the disclosed plasticizer composition is usually 5 to 70% by weight. It may be preferable that the content is 8 to 70% by weight, and more preferably 10 to 70% by weight. The content of at least one compound of the general formula (I) in the disclosed softening composition may be, for example, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight. The content of at least one compound of general formula (II) in the disclosed

Plasticizer composition is usually 30 to 95 weight percent. It may be preferable that the content is 30 to 92% by weight, and more preferably 30 to 90% by weight. The content of at least one compound of the general formula (II) in the disclosed softening composition may be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight.

The subject matter of the disclosure may thus be a plasticizer composition containing from 5 to 70% by weight of at least one compound of the general formula (I), and to 95 weight percent of at least one compound of general formula (II). It may be preferred that a plasticizer composition contains from 8 to 70 weight percent of at least one compound of general formula (I) and from 30 to 92 weight percent of at least one compound of general formula (II). It may further be preferred that a plasticizer composition contains from 10 to 70% by weight of at least one compound of the general formula (I) and from 30 to 90% by weight of at least one compound of the general formula (II).

A plasticizer composition within the scope of the disclosure may include

5 to 70 percent by weight of a mixture of compounds 1.1 to I.7 and 30 to 95 percent by weight of compound 11.1 or

5 to 70 percent by weight of a mixture of compounds 1.1 to I.7 and 30 to 95 percent by weight of compound II.2 or,

5 to 70% by weight of a mixture selected from Compound 1.1, I.2, 13, I.4, I.5, I.6, and I.7 and 30 to 95% by weight of a mixture selected from Compound 11.1 and II.2.

In the disclosed softener composition, the weight ratio of the at least one compound of the general formula (I) and the at least one compound of the general formula (II) may be in the range of 1:19 to 7: 3. It may be preferred that the weight ratio is in the range of 1: 1.5 to 7: 3. Further, it may be preferable that the weight ratio is in the range of 1: 9 to 7: 3. Thus, the weight ratio of at least one compound of general formula (I) and at least one compound of general formula (II) may be in the range of 1: 15, 1: 5, 1: 1, or 2: 1. A plasticizer composition may contain, in addition to at least one compound of the general formula (I) and (II), at least one plasticizer different from the compounds of the general formulas (I) and (II).

A plasticizer other than the compounds of the general formula (I) or (II) may, for example, be a terephthalic acid dialkyl ester having 4 to 7 carbon atoms in the alkyl chains, a terephthalic acid dialkyl ester having 9 to 13 carbon atoms in the alkyl chains Dialkyl phthalate, a cyclohexane-1,2-dicarboxylic acid dialkyl ester having 4 to 13 carbon atoms in the alkyl chains, a dialkyl cyclohexane-1, 3-dicarboxylate, a dialkyl cyclohexane-1, 4-dicarboxylate, a dialkyl malate, a dialkyl acetyl maleate , a benzoic acid alkyl ester, a dibenzoic acid ester, a saturated monocarboxylic acid alkyl ester, an unsaturated monocarboxylic acid ester, a saturated dicarboxylic acid diester, an unsaturated dicarboxylic acid diester, an aromatic sulfonic acid ester, an alkylsulfonic acid ester, a glycerol ester, an isosorbide ester, a phosphoric acid ester, a citric acid triester, an acylated citric acid triester, an alkylpyrolidone ivat, a 2,5-furandicarboxylic acid dialkyl ester, a 2,5-tetrahydrofurandicarboxylic acid dialkyl ester, a polyester of aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols, an epoxidized vegetable oil or an epoxidized fatty acid monoalkyl ester.

A terephthalic acid dialkyl ester, which is different from the compound of the general formula (II), usually has 4 to 7 C atoms in the alkyl chains. The alkyl chains of the dialkyl terephthalate different from the compound of general formula (II) may independently have a different number of C atoms.

A terephthalic acid dialkyl ester, which is different from the compound of the general formula (II), usually has 9 to 13 C atoms in the alkyl chains. The alkyl chains of the dialkyl terephthalate different from the compound of the general formula (II) independently of one another have a different number of C atoms. A terephthalic acid dialkyl ester other than the compound of the general formula (II) may, for example, be diisononyl terephthalate. A dialkyl phthalate may have 9 to 13 carbon atoms in the alkyl chains. The alkyl chains can independently of one another have a different number of carbon atoms. A dialkyl phthalate may be, for example, di-isononyl phthalate.

A cyclohexane-1,2-dicarboxylic acid dialkyl ester generally has 4 to 13 C atoms in the alkyl chains. The alkyl chains of the cyclohexane-1,2-dicarboxylic acid dialkyl ester can independently of one another have a different number of C atoms. A cyclohexane-1,2-di-carboxylic acid dialkyl ester may be, for example, di- (2-isononyl) -1,2-cyclohexanedicarboxylate, such as Hexamoll®DINCH®. A cyclohexane-1, 3-dicarboxylic acid dialkyl ester may have 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the cyclohexane-1, 3-dicarboxylic acid dialkyl ester may independently have a different number of carbon atoms.

A cyclohexane-1,4-dicarboxylic acid dialkyl ester may have 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the cyclohexane-1, 4-dicarbonsäuredialkylesters may independently have a different number of carbon atoms. A cyclohexane-1,4-dicarboxylic acid dialkyl ester may, for example, be di- (2-ethylhexyl) -cyclohexane-1,4-dicarboxylate.

An dialkyl malate or a dialkyl acetyl maleate may have from 4 to 13 carbon atoms in the alkyl chains. The alkyl chains of the malic dialkyl ester or of the dialkyl acetyl malic ester may independently of one another have a different number of C atoms.

An alkyl benzoate may have 7 to 13 C atoms in the alkyl chain. A benzoic acid alkyl ester may be, for example, isononyl benzoate, isodecyl benzoate, or 2-propylheptyl benzoate.

A dibenzoic acid ester may be, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, or dibutylene glycol dibenzoate

A saturated monocarboxylic acid ester may be, for example, an ester of acetic acid, an ester of butyric acid, an ester of valeric acid, or an ester of lactic acid. A saturated monocarboxylic acid ester may also be an ester of a monocarboxylic acid with a polyhydric alcohol. For example, pentaerythritol may be completely esterified with valeric acid.

An unsaturated monocarboxylic acid ester may be, for example, an ester of acrylic acid. For example, an unsaturated dicarboxylic acid diester may be an ester of fumaric acid.

An alkyl sulfonic acid ester may have 8 to 22 C atoms in the alkyl chain. An alkylsulfonic acid ester may be, for example, a phenyl or cresyl ester of pentadecylsulfonic acid.

An isosorbide ester is usually an isosorbide diester which is esterified with Cs to Ci3 carboxylic acids. An isosorbide diester may have different or identical Cs to C 13 alkyl chains. A phosphoric acid ester may be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, or bis-2 (2-ethylhexyl) phenyl phosphate, 2-ethylhexyldiphenyl phosphate.

In a citric acid triester, the OH group may be present in free or carboxylated form, for example acetylated form. The alkyl chains of the citric acid triester or of the acetylated citric acid triester independently of one another comprise 4 to 8 C atoms.

An alkylpyrrolidone derivative may have 4 to 18 carbon atoms in the alkyl chain. A 2.5-furandicarboxylic acid dialkyl ester may have 5 to 13 carbon atoms in the alkyl chains. The alkyl chains of 2,5-Furandicarbonsäuredialkylesters may independently have a different number of carbon atoms.

A 2,5-tetrahydrofurandicarboxylic acid dialkyl ester may have 5 to 13 carbon atoms in the alkyl chains. The alkyl chains of 2,5-Tetrahydrofurandicarbonsäuredialkylesters can independently have a different number of carbon atoms.

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

When the plasticizer composition disclosed contains at least one plasticizer different from those of the compound of the general formulas (I) and (II), its content in the disclosed plasticizer composition is up to 50% by weight based on the total of all of Softener composition contained plasticizers. It may be preferable that the content in the disclosed plasticizer composition is up to 40% by weight. It may be further preferred that the content in the disclosed softening composition is up to 25% by weight. In general, however, it may be preferable that no plasticizer other than the compounds of the general formulas (I) and (II) is contained in the disclosed plasticizer composition.

Also subject matter of the disclosure is a molding composition containing the disclosed plasticizer composition and at least one polymer. The disclosed molding composition may accordingly also contain a mixture of polymers.

Most often, at least one thermoplastic is included in the molding composition containing the disclosed plasticizer composition. Accordingly, the disclosed molding composition may also contain a mixture of thermoplastics.

A molding compound may contain, for example

Trimellitic acid trialkyl and

Thermoplastic terephthalic acid dialkyl ester

I.3 and 11.1 I.3 and II.2

TP 30 X

TP 30 X X

TP 29 X

TP 29 X X

Homopolymers and / or copolymers of vinyl acetate X

Homo- and / or copolymers of vinyl acetate X X

Homo- and / or copolymers of styrene X.

Homo- and / or copolymers of styrene X X

TP14 X

TP14XX

TP 6X

TP 6 X X

TP 7X

TP 7 XX Trimellitic acid trialkyl and

Thermoplastic terephthalic acid dialkyl ester

I.4 and 11.1 I.4 and II.2

TP 30 X

TP 30 X X

TP 29 X

TP 29 X X

Homopolymers and / or copolymers of vinyl acetate X

Homo- and / or copolymers of vinyl acetate X X

Homo- and / or copolymers of styrene X.

Homo- and / or copolymers of styrene X X

TP14 X

TP14XX

TP 6X

TP 6 X X

TP 7X

TP 7 X X

Depending on the polymer contained in the disclosed molding composition, it may be necessary to include varying amounts of the disclosed plasticizer composition in the disclosed molding composition to achieve the desired thermoplastic properties. The adjustment of the desired thermoplastic properties of the disclosed molding composition is generally the routine activity of those skilled in the art.

When polyvinyl chloride is not contained in the disclosed molding composition, the amount of the disclosed plasticizer composition in the disclosed molding composition is typically 0.5 to 300 phr. It may be preferred that the amount of the disclosed plasticizer composition in the disclosed molding composition is from 0.1 to 130 phr. It may be further preferred that the amount of the disclosed plasticizer composition in the molding composition is from 2.0 to 100 phr. The amount of the disclosed plasticizer composition contained in the disclosed molding composition may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 phr. When polyvinyl chloride is contained in the molding compound, the amount of the disclosed plasticizer composition in the disclosed molding composition is usually 5 to 300 phr. It may be preferred that the amount of the disclosed plasticizer composition in the disclosed molding composition is from 15 to 200 phr. It may be further preferred that the amount of the disclosed plasticizer composition in the disclosed molding composition is from 30 to 150 phr. The amount of the disclosed plasticizer composition contained in the disclosed molding composition may be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 1 15, 120, 125, 130, 135, 140, or 145 phr. In general, the disclosed molding composition contains 20 to 90 weight percent polyvinyl chloride. It may be preferred that the molding composition contains 40 to 90 weight percent polyvinyl chloride, and more preferably 45 to 85 weight percent. For example, the disclosed molding composition may contain 50, 55, 60, 65, 70, 75 or 80 weight percent polyvinyl chloride.

The disclosed molding composition containing at least one thermoplastic and the disclosed plasticizer composition may also contain other additives. Likewise, the disclosed plastisol containing at least one thermoplastic and the disclosed plasticizer composition may also contain other additives. Additives may for example be stabilizers, lubricants, fillers, colorants, flame retardants, light stabilizers, blowing agents, polymeric processing agents, impact modifiers, optical brighteners, antistatic agents, biostabilizers or a mixture thereof. The additives described below do not limit the disclosed molding composition or the disclosed plastisol, but are merely illustrative of the disclosed molding composition or the disclosed plastisol.

Stabilizers may be the usual polyvinyl chloride stabilizers in solid and liquid form, such as Ca / Zn, Ba / Zn, Pb, Sn stabilizers, acid-binding phyllosilicates, carbonates such as hydrotalcite, or mixtures thereof.

The disclosed molding composition or plastisol may contain stabilizer content of from 0.05 to 7 percent by weight based on the total weight of the molding material or the plastisol. It may be preferred that the content of stabilizers is from 0.1 to 5% by weight and more preferably from 0.5 to 3% by weight.

Lubricants are generally used to reduce the adhesion between the disclosed molding material or the disclosed plastisol and surfaces and, for example, are said to reduce friction when mixing, plasticizing or deforming. As lubricants in the disclosed molding composition or in the disclosed plastisol, all common lubricants used in plastics processing can be used. Lubricants commonly used in plastics processing are, for example, hydrocarbons, such as oils, paraffins, PE waxes or mixtures thereof, fatty alcohols having 6 to 20 C atoms, ketones, carboxylic acids, such as fatty acids, montanic acids or mixtures thereof, oxidized PE waxes, metal salts of carboxylic acids, carboxylic acid amides, carboxylic acid esters resulting from the esterification of alcohols such as ethanol, fatty alcohols, glycerol, ethanediol or pentaerythritol with long-chain carboxylic acids. The disclosed molding composition or plastisol may contain lubricity of 0.01 to 10 weight percent based on the total weight of the molding compound or plastic isolate. It may be preferable that the content of the lubricant is from 0.05 to 5% by weight, and more preferably from 0.2 to 2% by weight. Fillers are generally used to positively influence the compressive, tensile and / or flexural strength, hardness and / or heat distortion resistance of the disclosed molding composition or plastisol.

As fillers, for example, carbon black and / or inorganic fillers may be present in the disclosed molding composition or in the disclosed plastisol. Inorganic fillers may be natural calcium carbonates such as chalk, limestone, marbles, synthetic calcium carbonates, dolomite, silicates, silicic acid, sand, diatomaceous earth, aluminum silicates such as kaolin, mica, feldspar, or any mixture of two or more of the aforementioned fillers. The disclosed molding composition or plastisol may contain from 0.01 to 80 percent by weight filler based on the total weight of the molding material or the plastisol. It may be preferable that the content of the filler is 0.01 to 60% by weight, and more preferably 1 to 40% by weight. Thus, the disclosed molding composition or plastisol may contain 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36, or 39 percent by weight fillers.

Colorants may serve to tailor the disclosed molding composition or plastisol to different uses. Colorants may be, for example, pigments and / or dyes.

As pigments, for example, inorganic and / or organic pigments may be included in the disclosed molding composition or in the disclosed plastisol. Inorganic pigments may be cobalt pigments such as COO / Al 2 O 3 and / or chromium pigments such as Cr 2 O 3. Organic pigments may be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and / or dioxazine pigments. The disclosed molding composition or plastisol may contain from 0.01 to 10 percent by weight coloring matter based on the total weight of the molding material or the plastisol. It may be preferable that the content of colorants is 0.05 to 5% by weight, and more preferably 0.1 to 3% by weight.

Flame inhibitors may serve to reduce the flammability of the disclosed molding material or plastisol and to reduce smoke on burning. Flame inhibitors which may be included in the disclosed molding composition or in the disclosed plastisol may, for example, be antimony trioxide, chloroparaffin, phosphate esters, aluminum hydroxide and / or boron compounds.

The disclosed molding composition or plastisol may contain about 0.01 to 10 weight percent of flame retardants based on the total weight of the molding material or the plastisol. It may be preferable that the content of flame retardants is 0.2 to 5% by weight, and more preferably 0.5 to 2% by weight.

Light stabilizers, such as UV absorbers, can serve to protect the disclosed molding material or plastisol by damage from the action of light.

Light stabilizers may, for example, be hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates, hindered amine light stabilizers, such as derivatives of 2,2,6,6-tetramethylpiperidine or mixtures of the abovementioned compounds.

The disclosed molding material or plastisol may contain from 0.01 to 7 weight percent of light stabilizers based on the total weight of the molding material or the plastisol. It may be preferable that the content of the light stabilizer is 0.02 to 4% by weight, and more preferably 0.5 to 3% by weight.

Also, in the disclosed molding composition, the disclosed plasticizer composition and at least one elastomer may be included.

Accordingly, the disclosed plasticizer composition and a mixture of elastomers may also be included in the disclosed molding composition.

An elastomer may be, for example, a rubber. A rubber may be a natural rubber or a synthetic rubber. Synthetically produced rubber may be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber. As a rule, the disclosed molding composition comprises at least natural rubber and / or at least one synthetic rubber, wherein the rubber or rubber mixture contained can be vulcanized with sulfur.

In most cases, the disclosed molding composition contains at least one elastomer in a proportion of 20 to 95 percent by weight based on the total weight of the molding composition. It may be preferred that the disclosed molding composition contains at least one elastomer at a level of from 45 to 90 percent by weight. Further, it may be preferable that the disclosed molding composition contains at least one elastomer in a proportion of 50 to 85% by weight. The disclosed molding composition may contain, for example, 55, 60, 65, 70, 75 or 80 percent by weight of at least one elastomer.

When at least one elastomer is contained in the disclosed molding composition, especially at least one of natural rubber and at least one synthetic rubber, the amount of the disclosed plasticizer composition in the molding composition is usually 1 to 60 phr. It may be preferable that the amount of the disclosed plasticizer composition in the molding composition is 2 to 40 phr and further 3 to 30 phr. The amount of the disclosed plasticizer composition contained in the molding composition may be, for example, 5, 10, 15, 20 or 25 phr. Also, in the disclosed molding composition, a mixture of at least one thermoplastic and at least one elastomer may be included. Thus, in the disclosed molding composition, a mixture of polyvinyl chloride and at least one elastomer may be included.

If polyvinyl chloride and at least one elastomer are present in the molding composition, the content of elastomer is generally 1 to 50 percent by weight, based on the total weight of the molding composition. It may be preferable that the content of the elastomer is 3 to 40% by weight based on the total weight of the molding compound. It may further be preferred that the content of elastomer is 5 to 30 percent by weight based on the total weight of the molding composition. The disclosed molding composition may contain, for example, 10, 15, 20 or 25 percent by weight of elastomer.

Depending on the composition of the blend of polyvinyl chloride and at least one elastomer in the molding composition, the amount of plasticizer composition disclosed in the molding composition can vary widely to achieve the desired properties. It corresponds to the routine activity of those skilled in corresponding amounts of the disclosed

Softener composition to use to achieve the desired properties. In general, the amount of the disclosed plasticizer composition in the molding composition containing polyvinyl chloride and at least elastomer is 0.5 to 300 phr. It may be preferred that the amount of the disclosed plasticizer composition in the molding composition containing polyvinyl chloride and at least one elastomer is from 1 to 150 phr and further from 2 to 120 phr. The amount of the disclosed plasticizer composition contained in the molding composition 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, 1 10 or 1 15 phr. A molding composition containing the disclosed plasticizer composition and at least one elastomer may also contain other additives. Additives may be, for example, carbon black, silica, phenolic resins, vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, activators, various oils, anti-aging agents or mixtures of said additives.

Further additives may be substances which, on the basis of his specialist knowledge, the skilled person would mix into tires or other rubber compounds in order to achieve a specific effect.

Also within the scope of the disclosure is a plastisol containing the disclosed plasticizer composition and at least one polymer. The disclosed plastisol may accordingly also contain a mixture of polymers.

In general, a plastisol is a suspension of finely powdered polymer in liquid plasticizer, the rate of dissolution of the polymer in the liquid plasticizer being very low at room temperature. Upon heating the suspension of fine powdered polymer in liquid plasticizer, a substantially homogeneous phase forms between polymer and plasticizer. The individual isolated plastic aggregates swell and combine to form a three-dimensional highly viscous gel. This process is usually referred to as gelling and takes place from a certain minimum temperature. This minimum temperature is generally referred to as gelling or dissolving temperature. The introduction of the necessary heat can be done via the parameters temperature and / or residence time. The faster the gelation takes place (indication here is the dissolving temperature, ie the lower it is, the faster the plastisol gels), the lower the temperature (with the same residence time) or the residence time (at the same temperature) can be selected. As a rule, at least one thermoplastic is contained in a plastisol.

A plastisol may contain, for example Trimellitic acid trialkyl and

Thermoplastic terephthalic acid dialkyl ester

I .3 and 11.1 I .3 and W .2

TP 30 X

TP 30 X X

TP 29 X

TP 29 X X

Homopolymers and / or copolymers of vinyl acetate X

Homo- and / or copolymers of vinyl acetate X X

Homo- and / or copolymers of styrene X.

Homo- and / or copolymers of styrene X X

TP14 X

TP14XX

TP 6X

TP 6 X X

TP 7X

TP 7 X X

Trimellitic acid trialkyl and

Thermoplastic terephthalic acid dialkyl ester

I.4 and II.1.1.4 and W.2

TP 30 X

TP 30 X X

TP 29 X

TP 29 X X

Homopolymers and / or copolymers of vinyl acetate X

Homo- and / or copolymers of vinyl acetate X X

Homo- and / or copolymers of styrene X.

Homo- and / or copolymers of styrene XX Trimellitic acid trialkyl and

Thermoplastic terephthalic acid dialkyl ester

I.4 and 11.1 I.4 and II.2

TP14 X

TP14XX

TP 6X

TP 6 X X

TP 7X

TP 7 X X

Depending on the polymer contained in the plastisol, it may be necessary to include different amounts of the disclosed plasticizer composition in the plastisol to achieve the desired plastisol properties. The setting of the desired plastisol properties is generally subject to the routine activity of the skilled person.

If the plastisol contains polyvinyl chloride, the proportion of the disclosed plasticizer composition in the plastisol is usually from 30 to 400 phr, preferably from 50 to 200 phr.

The content of plasticizers of the general formula (I) in a plastisol containing polyvinyl chloride is usually at least 10 phr, may preferably be at least 15 phr and may in particular be at least 20 phr.

The disclosed plasticizer composition can be used as a plasticizer for a polymer or a mixture of polymers.

The disclosed plasticizer composition can be used as a plasticizer for a thermoplastic or a mixture of thermoplastics.

The disclosed plasticizer composition can also be used as a plasticizer for an elastomer or blend of elastomers. An elastomer may be a natural rubber or a synthetic one

Be rubber. Synthetically prepared rubber may be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, or any mixture thereof. The disclosed plasticizer composition may also be used as a plasticizer for a blend containing at least one elastomer and at least one thermoplastic. Most commonly, the disclosed softener composition is used as a plasticizer for polyvinyl chloride or a blend of polymers containing polyvinyl chloride.

The disclosed plasticizer composition can be used as a plasticizer in a plastisol.

Most of the disclosed softening composition is used as a plasticizer in a plastisol containing polyvinyl chloride.

The disclosed molding composition is used in the production of moldings or films. Shaped bodies may be, for example, containers, apparatus or foamed devices.

Containers may include, for example, housings of electrical appliances such as kitchen appliances or computer housings, pipes, hoses such as water or irrigation hoses, industrial rubber hoses, chemical hoses, wire or cable sheathing, tool sheathing, bicycle, scooter, wheelbarrow handles, metal coatings or packaging containers ,

Apparatus may 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, vibration dampers, or erasers.

Foamed devices may be, for example, upholstery, mattresses, foams or insulating materials.

Films may include, for example, tarpaulins such as truck tarpaulins, roof tarpaulins, geomembranes, stadium roofs or tarpaulins, gaskets, composite films such as laminated safety glass films, self-adhesive films, laminating films, shrink films, outdoor flooring, tape foils, coatings, swimming pool sheeting, decorative sheeting, tablecloths or artificial leather , The disclosed molding composition can be used to make moldings or films which come into direct contact with humans or foods.

Shaped bodies or films which come into direct contact with humans or foods may be, for example, medical devices, hygiene products, food packaging, interior products, baby and children's products, childcare articles, sports or leisure products, clothing, fibers or fabrics.

Medical devices that can be made using the disclosed molding material may include, for example, enteral or hemodialysis tubes, breathing tubes, drainage tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves, or respiratory masks.

Food packages that can be made using the disclosed molding composition may include, for example, cling film, food hoses, drinking water hoses, food storage or freezing containers, lid seals, caps, bottle caps or artificial wine corks.

Indoor products which can be produced using the disclosed molding composition can be, for example, floor coverings which are homogeneous or consist of several

Layers consisting of at least one foamed layer, such as floor coverings, mudflap mats, sports floors, Luxury Vinyl Tiles (LVT), imitation leather, wall coverings, foamed or unfoamed wallpapers in buildings, carcasses or console covers in vehicles

For example, baby and child products that can be made using the disclosed molding composition may be toys such as dolls, toy figures or kneading, inflatable toys such as balls or rings, stopper socks, buoyancy aids, stroller covers, changing pads, hot water bottles, teething rings or vials.

Sports or leisure products that can be made using the disclosed molding composition may be, for example, exercise balls, exercise mats, seat cushions, massage balls or rollers, shoes, shoe soles, balls, air mattresses, or water bottles. Apparel that can be made using the disclosed molding composition can be, for example, latex clothing, protective clothing, rain jackets or rubber boots.

Piastisols are typically processed at ambient temperature by various methods, such as brushing, casting, such as the shell casting or rotary casting, dipping drive, printing process, such as screen printing, spraying and the like into the shape of the finished product. Subsequently, the gelation is carried out by heating, after cooling a homogeneous, more or less flexible product is obtained. The disclosed plastisol can be used for the production of films, wallpapers, seamless hollow bodies,

Gloves or for use in the textile sector, such. B. be used for textile coatings.

Films may include, for example, truck tarpaulins, roof tarpaulins, covers in general, such as boat covers, stroller covers or stadium roofs, tarpaulins, geomembranes, tablecloths, coatings, swimming pool foils, artificial leather or decorative sheeting.

For example, gloves can be gardening gloves, medical gloves, chemical gloves, protective gloves or disposable gloves.

Further, the disclosed plastisol may be used, for example, to make gaskets such as gaskets, cowls or console covers in vehicles, dolls, toy figures or kneading, inflatable toys such as balls or rings, stopper socks, buoyancy aids, changing pads, exercise balls, exercise mats, seat cushions, vibrators, mas - Sawing balls or rolls, latex clothing, protective clothing, rain jackets or rubber boots are used.

The disclosed plastisol usually contains polyvinyl chloride.

The subject of the present disclosure is also the use of the disclosed plasticizer composition as a calendering aid or rheology aid. The subject of the present disclosure is also the use of the disclosed plasticizer composition in surface-active compositions, such as flow or film binders, defoamers, antifoaming agents, wetting agents, coalescing agents or emulsifiers. The disclosed plasticizer composition can also be used in lubricants such as lubricating oils, greases or lubricating pastes. Further, the disclosed softening composition can be used as a quenching agent for chemical reactions, phlegmatizers, in pharmaceutical products, in adhesives, in sealants, in printing inks, in impact modifiers or leveling agents.

The subject matter of the disclosure are molded articles or films containing the disclosed plasticizer composition. It is based on the use of molding materials for the manufacture of ment made of molded articles or films reference to moldings or films reference. The examples of moldings or films cited here are to be used to design the terms moldings or film in these sections.

Preparation of the compound of the general formula (I)

Compounds of the general formula (I) can be prepared, for example, by esterification of corresponding tricarboxylic acids, for example 1, 2,4-benzenetricarboxylic acid, with the corresponding aliphatic alcohols. Methods and specific procedures are either known to those skilled in the art or are apparent to him by his general knowledge.

These include the reaction of at least one alcohol component selected from the alcohols R ^1a -OH, R ^1b -OH and R ^1c -OH with a corresponding tricarboxylic acid, for example

1, 2,4-benzenetricarboxylic acid, or a suitable derivative thereof. Suitable derivatives are, for. As the acid halides and acid anhydrides. An acid halide may be, for example, an acid chloride. The reaction can be carried out in the presence of an esterification catalyst. As the esterification catalyst customary catalysts can be used, for. For example, mineral acids such as sulfuric acid or phosphoric acid; organic sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid; amphoteric catalysts, in particular titanium, tin (IV) - or zirconium compounds, such as Tetraa Ikoxytitane, z. As tetra butoxytitanium, or tin (IV) oxide. The resulting in the reaction water can be removed by conventional means, for. B. by distillation, are removed. For example, WO 02/038531 describes a process for preparing esters in which a) in a reaction zone, a mixture consisting essentially of the acid component or an anhydride thereof and the alcohol component is boiled in the presence of an esterification catalyst, b) the alcohol and water-containing vapors are separated into a fraction rich in alcohol and a fraction rich in water by rectification, c) the alcohol-rich fraction is returned to the reaction zone and the water-rich fraction

Fraction from the proceedings derives. As esterification catalysts, the aforementioned catalysts are used. 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 acid component (or anhydride) and alcohol component. Further detailed illustrations for carrying out 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 referred to in their entirety. In general, the esterification of the corresponding tricarboxylic acids, for example

1, 2,4-benzenetricarboxylic acid, in the presence of the above-described alcohol components R ^1a - OH, R ^1b -OH and / or R ^1c -OH by means of an organic acid or mineral acid, in particular concentrated sulfuric acid. It may be advantageous that the alcohol component is used at least in twice the stoichiometric amount, based on the 1, 2,4-benzenetricarboxylic acid or a derivative thereof. The esterification can be carried out at ambient pressure or reduced or elevated pressure. It may be preferred that the esterification is carried out at ambient or reduced pressure.

The esterification may be carried out in the absence of an added solvent or in the presence of a solvent.

If the esterification is carried out in the presence of a solvent, it is preferably a solvent which is inert under the reaction conditions. An inert solvent is generally understood as meaning a solvent which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. Preferably, the inert solvent can 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 is selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, di-butyl ether, THF, dioxane and mixtures thereof becomes.

The esterification is usually carried out in a temperature range of 50 to 250 ° C.

If the esterification catalyst is selected from organic acids or mineral acids, the esterification is usually carried out in a temperature range of 50 to 160 ° C. If the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250 ° C.

The esterification can take place in the absence or in the presence of an inert gas. An inert gas is generally understood as meaning a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. It may be preferred that the esterification takes place without the addition of an inert gas.

For example, the alcohol and the acid are combined in a 2: 1 functional group molar ratio in a stirred flask together with the esterification catalyst aluminum tri-methyl sulfonate 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 in the reaction is distilled off azeotropically together with the alcohol and then separated off. The alcohol is returned to the reaction mixture. The 1, 2,4-benzenetricarboxylic acid and aliphatic alcohols used for the preparation of the compounds of the general formula (I) can either be obtained commercially or prepared by synthesis routes known from the literature.

transesterification

The compounds of the general formula (I) can also be prepared by transesterification. Transesterification procedures and specific procedures are either known to those skilled in the art or are apparent to him by his general knowledge. In general, starting materials are compounds of the general formula (I) in which R ^1a R ^1b and R ^1c independently of one another represent d- to C 2 -alkyl. These include, for example, the reaction of corresponding trialkyl tricarboxylates, for example trimethyl trimellitate, triethyl trimellitate, dimethyl trimethyl end-trimethyl ester or methyl trimellitate or mixtures thereof, with at least one alcohol component selected from the alcohols R ^1a -OH R ^1b -OH and R ^1c- OH, where R ^1a , R ^1b and R ^{1c is} C ₃ - to C ₅ -alkyl, in the presence of a suitable transesterification catalyst.

As transesterification catalysts, for example, the usual, usually for

Transesterification reactions used catalysts into consideration, which are usually used in esterification reactions. These include z. For example, mineral acids such as sulfuric acid or phosphoric acid; organic sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid; or the 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.

The amount of transesterification catalyst used may generally be from 0.001 to 10% by weight. It may be preferable that the amount is 0.05 to 5% by weight. The reaction mixture is usually heated to the boiling point of the reaction mixture, so that the reaction temperature, depending on the reactants in a temperature range of 20 to 200 ° C. The transesterification can be carried out at ambient pressure or reduced or elevated pressure. It may be preferred that the transesterification is carried out at a pressure of 0.001 to 200 bar, and more preferably at a pressure of 0.01 to 5 bar. The lower-boiling alcohol eliminated during the transesterification can be distilled off continuously in order to shift the equilibrium of the transesterification reaction. The distillation column required for this purpose is usually in direct contact with the transesterification reactor. For example, the distillation column can be installed directly on the transesterification reactor. In the case of using multiple series-connected transesterification reactors, each of these reactors may be equipped with a distillation column or, preferably from the last boilers of the transesterification reactor cascade, the vaporized alcohol mixture may be fed via one or more manifolds to a distillation column. The recovered in this distillation higher boiling alcohol is preferably recycled back to the transesterification.

In the case of using an amphoteric catalyst whose separation generally succeeds by hydrolysis and subsequent separation of the metal oxide formed, for. B. by filtration. It may be preferred that after the reaction, the catalyst is hydrolyzed by washing with water and the precipitated metal oxide is filtered off. The filtrate may be subjected to further workup to isolate and / or purify the product. It may be preferred that the product is separated by distillation.

The transesterification of the tri (C 1 -C 2) -alkyl esters of corresponding tricarboxylic acids, for example 1, 2,4-benzenetricarboxylic acid, with at least one alcohol component selected from the alcohols R ^1a -OH R ^1b -OH and R ^1c -OH, where R ^1a , R ^1b and R ^{1c are} C ₃ - to C ₅ -alkyl, may preferably be carried out in the presence of at least one titanium (IV) -alcoholate. Preferred titanium (IV) alcoholates are tetrapropoxy titanium, tetrabutoxy titanium or mixtures thereof. It may be preferred that the alcohol component is used at least in twice the stoichiometric amount, based on the tri- (C 1 -C 2 -alkyl) esters used.

The transesterification can be carried out in the absence or in the presence of an added solvent. It may be preferred that the transesterification is carried out in the presence of an inert solvent. Suitable solvents are those mentioned above for the esterification. These include especially toluene and THF.

The temperature in the transesterification is usually in a range of 20 to 200 ° C.

The transesterification can be carried out in the absence or in the presence of an inert gas. An inert gas is generally understood as meaning a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. It may be preferable that the transesterification is carried out without adding an inert gas. Preparation of compounds of the general formula (II) The compounds of the general formula (II) can either be obtained commercially or prepared by methods which are either known to the person skilled in the art or can be deduced from his general knowledge.

In general, the terephthalic acid dialkyl esters are obtained by esterification of terephthalic acid or suitable derivatives thereof with the corresponding alcohols. Methods and specific procedures are either known to those skilled in the art or are apparent to him by his general knowledge.

The process for the preparation of the compounds of general formula (II) has in common that starting from terephthalic acid or suitable derivatives thereof, an esterification or a transesterification is carried out, wherein the corresponding Cs-alkanols are used as starting materials. These alcohols are usually not pure substances, but mixtures of isomers whose composition and degree of purity depends on the particular method with which they are presented.

Preferred Cs-alkanols which are used for the preparation of the compounds (II) contained in the plasticizer composition according to the invention may be straight-chain or branched or consist of mixtures of straight-chain and branched Cs-alkanols. These include n-octanol, isooctanol or 2-ethylhexanol. It may be preferred that 2-ethylhexanol is used.

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

Substantially straight-chain octanols can be obtained, for example, by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptene and subsequent hydrogenation of the resulting n-octanal to n-octanol. The 1-epoxide required for this purpose can be obtained, for example, from the Fischer-Tropsch synthesis of hydrocarbons. In contrast to 2-ethylhexanol or n-octanol, due to its method of preparation, the isooctanol alcohol is generally not a uniform chemical compound but an isomeric mixture of differently branched Cs-alcohols, for example Dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5-methyl-1-heptanol which, depending on the conditions of preparation used and can be present in different ratios in isooctanol method. Isooctanol is usually prepared by the codimerization of propene with butenes, such as n-butenes, and subsequent hydroformylation of the resulting mixture of heptene isomers. The octanal isomer mixture obtained in the hydroformylation can then be hydrogenated in a conventional manner to the isooctanol.

The codimerization of propene with butenes to isomeric heptenes can be carried out, for example, with the aid of the homogeneously catalyzed Dimersol® process (for example Chauvin et al., Chem. Ind., May 1974, pp. 375-378), in which the catalyst used is a soluble nickel Phosphine complex in the presence of an ethylaluminum chlorine compound, for example Ethylaluminiumdichlo- rid serves. As phosphine ligands for the nickel complex catalyst may, for. For example, tributylphosphine, tri-isopropylphosphine, tricyclohexylphosphine and / or Tribenzylphosphin be used. The reaction generally takes place at temperatures of 0 to 80 ° C., it being advantageous to set a pressure at which the olefins are dissolved in the liquid reaction mixture (for example Cornils, Hermann: Applied Homogeneous Catalysis with Organo metallic Compounds; 2nd edition, Vol 1, pages 254-259, Wiley-VCH, Weinheim 2002).

As an alternative to the Dermersol® process, which is operated with nickel catalysts homogeneously dissolved in the reaction medium, the codimerization of propene with butenes can also be carried out with heterogeneous NiO catalysts deposited on a support, with similar properties

Hepten isomer distributions are obtained 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 well-suited specific nickel heterogeneous catalyst for Olefindimerisierung or codimerization is z. As disclosed in WO 9514647.

Instead of catalysts based on nickel, it is also possible to use brominated-acid heterogeneous catalysts for the codimerization of propene with butenes, as a rule higher-branched heptenes than in the nickel-catalyzed process are obtained. Examples of catalysts suitable for this purpose are solid phosphoric acid catalysts z. For example, diatomaceous earth impregnated with phosphoric acid or diatomaceous earth, as used for example by the PolyGas® process for Olefindi- or oligomerization (for example, Chitnis et al; Hydrocarbon Engineering ^ 0, No. 6 - June 2005). For the codimerization of propene and butenes to heptenes very well suitable Brønsted-acidic catalysts are usually zeolites, which, for example, uses the further developed based on the PolyGas® process EMOGAS® process. The 1-heptene and the heptene isomer mixtures are prepared by the known processes described above in connection with the preparation of n-heptanal and heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, in n-octanal or octanal isomer mixtures. These are then z. B. hydrogenated by means of one of the above-mentioned in connection with the n-heptanol and isoheptanol preparation catalysts to the corresponding octanols nolen.

Examples

The invention will be explained in more detail with reference to the figures described below and the examples. The figures and examples are not to be understood as limiting the invention. In the examples the following starting materials are used:

In all examples, homopolymeric emulsion PVC was used as Solvin® 367 NC and / or Vinnolit® P 70, isononylbenzot as Vestinol® INB, isodecylbenzoate as Jayflex® MB 10, di- (2-ethylhexyl) terephthalate as EASTMAN 168 ™, Diisononyl phthalate as Palatinol® N, trimellitic tri- (2-ethylhexyl) ester as Palatinol® TOTM and the Ba-Zn stabilizer as reagent SLX / 781 used. The product properties are, as far as available from the data sheets of the manufacturers, indicated in the following table. ProductsVestinol® Jayflex® EASTMAN Palatinol® Palatinol® properties INB MB 10 168 ™ N TOTM

0.955 - 0.950 - 0.98 g / ml 0.970 - 0.98 - 0.99

0.963 g / ml 0.955 g / ml at 20 ° C 0.977 at g / ml

Density at 20 ° C, at 20 ° C, 20 ° C, DIN 20 ° C, DIN

DIN 51757 ASTM D-51757 51757

(01/1 1) 4052-15 (01/1 1) (01/1 1)

8.4 mPa ^* s 5 - 15 49 - 63 cP 68 - 82 293.6 at 20 ° C, mPa ^* s at 25 ° C, mPa ^* s at mPa ^* s at

Viscosity DIN 53015, 20 ° C, ASTM D 20 ° C, 20 ° C, DIN

(02/01) ASTM D-445-15 ASTM D 53015,

445-15 7042-14 (02/01)

Max. 0.07 max. 0.07 max. 0.06 0.079 mg

mg KOH / g, mg KOH / g, mg KOH / g, KOH / g, DIN

Acid number DIN EN ISO ASTM D- DIN EN ISO EN ISO

21 14 1045-14 21 14 21 14

(06/02) (06/02) (06/02)

1 .488 - 1 .489 - 1 .486 - 1 .484 - 1 .485 -

1 .494 at 1 .491 at 1 .488 at 1 .488 at 1 .487

Refraction20 85 ° C, 20 ° C, 25 ° C 20 ° C, DIN 20 ° C, DIN

index DIN ASTM D-51423/2 51423/2

51423/2 1218 (02/10) (02/10)

(02/10)

EXAMPLES

I) Preparation of two compounds of the general formula (I) according to the invention: Example 1

Synthesis of 1, 2,4-benzenetricarboxylic acid tris (iso-butyl) ester (compound I.4)

1000 g of 1, 2,4-benzenetricarboxylic anhydride and 1400 g of isobutanol were initially introduced under protective gas, for example nitrogen. The complete apparatus was still flowed through with a slight protective gas flow. After 15 minutes, 1 ml of the titanium catalyst (Tyzor® TPT-20B, Ketal BV Village, 4700 BN Roosendaal / NL, butoxyisopropoxytitanium, CAS No. 68955-22-6, density at 20 ° C ca. 0.97 g / ml) was added. While stirring, the mixture was heated to reflux. With the aid of a water separator, the course of the reaction was controlled. After about 150 ml of water had collected in the water separator, the acid number was determined (according to DIN EN ISO 21 14 06/2002). At a value of 55 mg KOH or below, part of the wet isobutanol was replaced with fresh, dry isobutanol and the reaction continued under reflux until the acid number had fallen below a value of 1 mg KOH. The reaction mixture was cooled to about 100 ° C and then a 20% aqueous sodium hydroxide solution was added and stirred for 30 minutes. The amount of aqueous sodium hydroxide solution required is calculated according to the acid number SZ:

Quantity 20% NaOH (aq) in ml = 5 ^* (SZ ^* product weight / 1000) ^* 1, 4

Excess alcohol was distilled off in vacuo. In the still warm mixture about 50 g of bleaching earth was added and stirred. This was filtered off together with the precipitated catalyst residues.

A total of 1850 g (95% yield) of a slightly yellowish oily liquid with a GC purity of 94% was obtained.

Example 2

Synthesis of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3)

The synthesis of 1, 2,4-benzenetricarboxylic tri- (n-butyl) ester was carried out analogously to the synthesis in Example 1. Instead of isobutanol, an equal amount of n-butanol is used.

The product was obtained as a light yellowish oil in a yield of 1920 g (98%) and a purity of 96%. The following table gives the properties of the compounds as described above.

1, 2,4-Benzoltricar- 1, 2,4-Benzoltricar- bonsäure tri- (n-butyl) - bonsäure tri- (iso- ester butyl) ester

Product Property Unit Method (Compound I.3) (Compound I.4)

DIN 51757

Density, 20 ° C g / cm ³ Ed.4 1 .0632

01/1 1 1 .0499

DIN 51562-1

Viscosity, 20 ° C mPa ^* s 195

01/99 397

DIN ISO 6271

Pt / Co color number 76

03/05 75

DIN 51423-2

Refractive index, n _D ²⁰ 1 ^.4930

02/10 1 .4878

DIN EN ISO

mg

Acid number 21 14 0.081

KOH / g

06/02 0.089

DIN 51777, Tl.

Water content wt.% 1 0.025

03/83 0.021

GC purity% 96.1 94.3

Dissolution temperature DIN 53408

° C 108

Microscope method 06/67 106 II) Application tests: ll.a) Determination of the dissolving temperature according to DIN 53408 (06/67) and the dynamic viscosity according to DIN 51562-1 01/99:

To characterize the gelling behavior of the compounds according to the invention of the general formula (I) in PVC, the dissolution temperature was determined in accordance with DIN 53408 (06/67). The lower the dissolution temperature, the better the gelling behavior of the substance in question for PVC.

In the table below, the dissolution temperatures and dynamic viscosities of 1, 2, 4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) and 1, 2,4-benzenetricarboxylic tri- (iso-butyl) ester (compound I.4), and as a comparison the values of the gelling aids isononylbenzoate (as Vestinol® INB) and isodecylbenzoate (as Jayflex® MB 10), and the plasticizer di (2-ethylhexyl) terephthalate ( as EASTMAN 168 ™), diisononyl phthalate (as Palatinol® N) and trimellitic acid tri- (2-ethylhexyl) ester (as Palatinol® TOTM).

As can be seen from the table, compound I.3 and compound I.4 show a lower dissolving temperature for PVC than the gelling aids Vestinol® INB and Jayflex® MB10. The dynamic viscosity is slightly higher. As can also be seen from the table, 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester and 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester are compared with the plasticizers EASTMAN 168 ™, Palatinol® N and Palatinol® TOTM significantly lower solution temperature for PVC.

II.b) Determination of the gelling behavior of plastisols with the softener compositions according to the invention:

To investigate the gelling behavior of plastisols based on the plasticizer compositions according to the invention, plastisols were the PVC and a mixture of the

Plasticizer di (2-ethylhexyl) terephthalate (as EASTMAN 168 ™) with 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) or 1, 2,4- Benzene tricarboxylic acid tris (iso-butyl) ester (compound I.4) in different proportions (EASTMAN 168 ™ to 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) 88/12, 75/25 and 78/22, or EASTMAN 168 ™ to 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) 85/15), according to the following recipe produced:

In addition, plastisols were prepared as a comparison which, apart from PVC, exclusively contain the soft materials di (2-ethylhexyl) terephthalate (as EASTMAN 168 ™), diisononyl phthalate (as Palatinol® N) or trimellitic acid tri- (2-ethylhexyl) ester ( as Palatinol® TOTM) or plastisols containing 73% of the plasticizer EASTMAN 168 ™ with 27% of the gelling assistant Vestinol® INB and a plastisol with 64% of the plasticizer EASTMAN 168 ™ with 36% of the gelling agent Jayflex® MB 10. phr

PVC (mixture of 70 parts by weight homopolymer 100

Emulsion PVC type Solvin® 367 NC and 30 parts by weight

Homopolymeric emulsion PVC type Vinnolit® P 70)

Plasticizer Composition Comparison 100

Ba-Zn stabilizer, type Reagens® SLX / 781 2 Composition dissolution temperature

according to rheometer method

100% 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester 1 16

(Compound I.3)

100% 1, 2,4-benzenetricarboxylic acid tris (iso-butyl) ester 125

(Compound I.4)

100% di (2-ethylhexyl) terephthalate 155

(as EASTMAN 168TM)

100% diisononyl phthalate 150

(as Palatinol® N)

12% 1, 2, 4-benzenetricarboxylic acid tri- (n-butyl) ester (Verbin150

I.3) + 88% di (2-ethylhexyl) terephthalate

(as EASTMAN 168 ™)

15% 1, 2, 4-benzenetricarboxylic acid tri- (iso-butyl) ester (Verbin 150

I.4) + 85% di- (2-ethylhexyl) terephthalate

(as EASTMAN 168 ™)

27% isononyl benzoate (as Vestinol® INB) + 73% di- (2-ethyl-150

hexyl) terephthalate (as EASTMAN 168 ™)

36% isodecyl benzoate (as Jayflex® MB10) + 64% di (2-150

ethylhexyl) terephthalate (as EASTMAN 168 ™)

The plastisols were prepared by weighing the two types of PVC together in a PVC-free device. In a second PVC-free device, the liquid components were weighed. Using a dissolver (Jahnke & Kunkel, IKA-Werk, type RE-166 A, 60-6000 1 / min, diameter of the dissolver disk = 40 mm), the PVC was stirred into the liquid components at 400 rpm. After a plastisol had been formed, the speed was increased to 2500 1 / min 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, with the aim of removing the air contained in the plastisol. Thereafter, the plastisol was returned to ambient pressure. Measurement of the rheological measurements for all plastisols was 30 min after homogenization.

The viscosity measurements were carried out with an oscillatory and rotary rheometer MCR 302 from Anton Paar in an oscillation test.

• Measuring system plate / plate d = 50 mm

Amplitude γ: 1%

• Frequency: 1 Hz

• Slit width: 1 mm Starting temperature: 20 ° C

Temperature profile: 20 - 200 ° C

Temperature increase 10 ° C / min

Measuring points: 201

Measuring point duration: 0.09 min

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 minutes with γ = 1%. With the second ramp the temperature program started. The memory module and the loss modulus were recorded during the measurement. From the quotient of these two quantities, the complex viscosity η ^{* is} calculated. The temperature at which the viscosity maximum was reached is considered to be the gelation temperature of the plastisol.

As can be seen very clearly in FIG. 1, the plastisols with the softening composition according to the invention gel at much lower temperatures than the plastisol containing exclusively Eastman 168 ™. Already at a composition of 88 wt.% Eastman 168 ™ and 12 wt.% Of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (compound I.3), a gelling temperature of 150 ° C is achieved the gelation of the plasticizer Palatinol® ^® N is and is sufficient for many plastisol applications. By further increasing the proportion of 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) in the plasticizer compositions according to the disclosure, the gelling temperature of the plastisols can be further significantly lowered.

As can be seen from FIG. 2, even at a composition of 85% Eastman 168 ™ and 15% by weight of 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4), a gelling temperature is obtained of 150 ° C, which corresponds to the gelling temperature of the plasticizer Palatinol ^® N and which is sufficient for many plastisol applications. By further increasing the proportion of 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) in the plasticizer compositions according to the disclosure, the gelling temperature of the plastisols can be further significantly reduced.

Both figures contain two comparative examples with gelling aids. A plastisol from 73 wt.% Of the plasticizer weight Eastman 168 ™ 27.% Of Gelierhilfsmittels Vestinol ^® INB and a plastisol with 64 wt.% Of the plasticizer Eastman 168 ™ with 36 wt.% Of Gelierhilfsmittels Jayflex ^® MB 10. In both cases the gelling temperature of 150 ° C is also reached, which corresponds to the gelling temperature of Palatinol ^® N.

By contrast, in the case of the plasticizer compositions of the gelling aids Vestinol® INB and Jayflex® MB 10, significantly higher proportions of Vestinol® INB (27% by weight) or Jayflex® MB 10 (36% by weight) are required to produce a gelling temperature the plastisole of 150 ° C too achieve. 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound l.3) or 1, 2,4-Benzoltricar- bonsäure tri- (iso-butyl) ester (compound I.4) therefore have a significantly better gelling than the commercially available gelling aids Vestinol® INB and Jayflex® MB 10.

ll.c) Determination of the process volatility of the softener compositions according to the invention in comparison with softener compositions of commercially available gelation auxiliaries. As described under ll.b), plastisols were prepared with a plasticizer composition comprising 12% by weight of 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) and 88% by weight Eastman 168 ™ or from 15% 1, 2, 4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4 ) and 85% by weight Eastman 168 ™ and with the softener compositions comprising 27% by weight Vestinol® INB and 73% by weight Eastman 168 ™ and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 ™. The following recipe was used.

Plastisols containing exclusively Eastman 168 ™, Palatinol® N or 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) were prepared as a comparison. The following recipe was used.

Production of a prefilm

In order to be able to determine performance properties of the plastisols, the liquid plastisol must be converted into a processable, solid film. For this, the plastisol was pregelled at low temperature. The pre-gelation of the plastisols took place in a Mathis oven.

Settings at Mathisofen: • Exhaust air: flap completely open

• Fresh air: open

• Recirculation: maximum position

• Upper / lower air: upper air position 1

Production of the pre-foil:

A new relay paper was clamped in the fixture at the Mathisofen. The oven was preheated to 140 ° C; the gel time is set to 25 s. For the gap adjustment, the gap between the paper and the doctor blade was adjusted to 0.1 mm with the thickness template. The thickness gauge was set to 0.1 mm. Then, the gap was set to a value of 0.7 mm on the dial gauge. The plastisol was applied to the paper and smoothed with a squeegee. Then the jig was driven into the oven via the start button. After 25 s, the clamping device drove out of the oven again. The plastisol was gelled and the resulting film was peeled off the paper in one piece. The thickness of this film was about 0.5 mm.

Determination of process volatility

To determine the process volatility, 3 square specimens (49 × 49 mm) were punched out with a Shore hardness punching iron from the prefilm, weighed and then gelled for 2 minutes at 190 ° C. in a Mathis oven. After cooling, these specimens were reweighed and the% weight loss calculated. The specimens were always positioned exactly in the same position of the relay paper. For this purpose, a line was drawn across the paper at the height of the hole in the frame to which the template for the Petri dishes was attached. The position for the 3 specimens was aligned at this line. They lay evenly across the width on the paper centered on the line.

As can be clearly seen in Figure 3, the process volatility of the plasticizer composition of the present invention is 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight of Eastman 168 ™ or 15% 1, 2,4-benzenetricarboxylic acid tri (isobutyl) ester (Compound I.4) and 85% by weight Eastman 168 ™ significantly lower than the process volatility of the 527% Vestinol softener compositions ® INB and 73% by weight Eastman 168 ™ or 36% by weight Jayflex® MB 10 and 64% Eastman 168 ™. In the case of the plasticizer compositions according to the disclosure, significantly less plasticizer is lost during the processing of the plastisols.

The process volatility of the plasticizer composition according to the present invention comprises 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (compound I.3) and 88% by weight of Eastman 168 ™ or 15% 1, 2, 4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight Eastman 168 ™ is slightly higher than that of the pure plasticizers Eastman 168 ™ or Palatinol® N, and significantly lower than the process volatility of the pure gelling agent

I, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4)

II. D) Determination of the Shore A hardness of films of plastisols with the plasticizer compositions according to the invention in comparison to films of plastisols with the plasticizer compositions of commercially available gelling aids

For the determination of the Shore A hardness, 49 × 49 mm pieces of film were punched out of the prefilms and, as described in ll.c), punched in the triple pack for 2 minutes at 190 ° C., analogously to the volatility test. In total, 27 pieces of film were gelled. These 27 pieces were superimposed in the press frame and pressed at 195 ° C to a 10 mm thick Shore logs.

Description of Shore hardness measurement:

• Method: DIN EN ISO 868, Oct. 2003

· Title: Determination of indentation hardness with a durometer (Shore hardness)

• Device: Fa. Hildebrand- Digital Durometer Model DD-3

• test specimen:

• Dimensions: 49mm x 49mm x 10mm (length x width x thickness)

• Production: pressed from approx. 27, 0.5mm thick gelling foils,

· Pressing temperature: 195 ° C = 5 ° C above the production of the gelling foils

• Storage time before measurement: 7d in the climatic room at 23 ° C and 50% rel. humidity

• Measuring time (duration of the needle on the specimen until reading the value) 15 s

• Ten individual values were measured and from this the mean value was calculated.

As can be clearly seen in Figure 4, the Shore A hardness of the plastisol sheet having the disclosed plasticizer composition is 12 weight percent of 1,2-tri (n-butyl) 2,4-benzenetricarboxylic acid (Compound I) 3) and 88% by weight Eastman 168 ™ or 15% by weight 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) and 85% by weight Eastman 168 ™ lower than the Shore A hardness of the films of the plastisols with the softener compositions of 27 wt.% Vestinol® INB and 73 wt.% Eastman 168 ™ and 36 wt.% Jayflex® MB 10 and 64 wt.% Eastman 168 ™ , The use of the disclosed plasticizer compositions thus leads to a higher elasticity of the PVC articles. The Shore A hardness of the PVC plastisol film with the disclosed plasticizer composition of 12 wt.% 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (compound I.3) and In addition, 88% by weight of Eastman 168 ™ or 15% by weight of 1,2,4-benzenetricarboxylic acid tris (isobutyl) ester (compound I.4) and 85% by weight of Eastman 168 ™ are also significantly lower as the Shore A hardness of the PVC plastisol film with the pure plasticizer Eastman 168 ™ but comparable to the Shore A hardness of the film made of the PVC plastisol with the pure plasticizer Palatinol® N.

The Shore A hardness of the disclosed plasticizer composition is 15% by weight of 1, 2,4-tricarboxylic acid tri- (isobutyl) ester (Compound I.4) and 85% by weight Eastman 168 ™ significantly lower than the Shore A hardness of the films containing only the plasticizer Eastman 168 ™ or the gelling aid 1, 2, 4-benzenetricarboxylic tri- (iso-butyl) ester.

Il.e) Determination of the film volatility of films of plastisols with the plasticizer compositions according to the invention in comparison with films of plastisols with the plasticizer compositions of commercially available gelling aids

For the film volatility test, plastisols having the disclosed plasticizer composition were prepared from 12% by weight of 1,2,3-tri (n-butyl) 1,4-benzenetricarboxylic acid ester (Compound I.3) and 88% by weight Eastman 168 ™ resp 15% by weight of 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) and 85% by weight of Eastman 168 ™ and plastisols with the softener compositions of 27% by weight of Vestinol® INB and 73% by weight Eastman 168 ™ and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 ™ prepared as described under II.c). For comparison, PVC plastisols were also prepared containing exclusively Eastman 168 ™ Palatinol® N or 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4). For the tests, however, not only was a preliminary film produced, but the plastisol was gelled directly at 190 ° C. for 2 minutes in the Mathis oven. On the approximately 0.5 mm thick films thus obtained, the film volatility test was carried out.

Testing the film volatility for 24 h at 130 ° C:

To determine the film volatility, four individual sheets (150 × 100 mm) were cut out, punched and weighed from the plastisols gelled at 190 ° C. for 2 minutes. The films were hung on a rotating star in a Type 5042 E Heraeus drying oven set at 130 ° C. In the cabinet, the air was changed 18 times per hour. This corresponds to 800l / h fresh air. After 24 hours in the cabinet, the slides were removed and weighed back. The percent weight loss indicates the film volatility of the softener compositions.

As can be seen clearly from FIG. 5, the film volatility of the disclosed plasticizer composition is 12% by weight of tri (n-butyl) 2,4-benzenetricarboxylate (compound I.3) and 88% by weight. % Eastman 168 ™ or 15% by weight of 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight of Eastman 168 ™ significantly lower than the film volatility of Plasticizer compositions comprising 27% by weight Vestinol® INB and 73% by weight Eastman 168 ™ and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 ™. In the disclosed plasticizer compositions, therefore, less plasticizer escapes in the finished, plasticized PVC article.

The film volatility of the disclosed plasticizer composition was 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight of Eastman 168 ™ and 15% by weight, respectively , 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight Eastman 168 ™ is comparable to that of the pure plasticizers Eastman 168 ™ resp. Palatinol® N and significantly lower than that of the pure 1, 2,4-benzenetricarboxylic tri- (iso-butyl) ester (Compound

I.4).

II. F) Determination of the compatibility (permanence) of films of plastisols with the plasticizer compositions according to the invention in comparison to films of plastisols with the plasticizer compositions of commercially available gelling auxiliaries

For compatibility testing, plastisols having the disclosed softening composition were prepared from 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% Eastman 168 ™ and 15 respectively % By weight of 1,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) and 85% by weight of Eastman 168 ™ and plastisols with the plasticizer compositions of 100% by weight 1, 2, 4-benzenetricarboxylic acid tris (iso-butyl) ester (Compound I.4), 27% Vestinol® INB and 73% by weight Eastman 168 ™ and 36% by weight Jayflex® MB 10 and 64% Eastman 168 ™ as prepared under ll.c). As a comparison, plastisols were also produced exclusively containing the plasticizers Eastman 168 ™ or Palatinol® N. For the tests, however, not only was a preliminary film produced, but the plastisol was gelled directly at 190 ° C. for 2 minutes in the Mathis oven. On the approximately 0.5 mm thick films thus obtained, the compatibility test was carried out. Test method:

Purpose of the test procedure

The test serves to qualitatively and quantitatively measure the compatibility of plasticized PVC formulations. It is carried out at elevated temperature (70 ° C) and humidity (100% rel. H). The data obtained are evaluated against the storage time.

Specimens For the standard test, 10 test specimens (foils) with a size of 75 × 1 × 10 × 0.5 mm were used per formulation. The films were punched on the broadside, labeled and weighed. The label must be smudge-proof and can z. B. done with the soldering iron. Testers

Warming cabinet, analytical balance, temperature measuring device with sensor for measuring the interior temperature of the heating cabinet, basin made of glass, metal frames made of stainless material;

Test temperature: 70 ° C

Test medium: water vapor formed at 70 ° C from demineralized water

Execution:

The temperature in the interior of the heating cabinet was set to the required 70 ° C. The test films were hung on a wire rack and placed in a glass pan about 5 cm high with water (deionized water). Only films of the same composition may be stored in a designated and numbered basin in order to avoid mutual interference and to facilitate removal after the respective storage periods. The glass pan was sealed with a PE film so that it could not escape the water vapor that later formed in the glass pan.

Storage time In the 1, 3, 7, 14 and 28-day intervals, 2 films (duplicate determination) were taken from the glass trough and air-conditioned for 1 hour, hanging freely. Thereafter, the films in the fume hood were cleaned with methanol (towel moistened with methanol). Subsequently, the films were dried for 16 h at 70 ° C in a drying oven (natural convection) hanging freely. After removal from the drying oven, the films were conditioned to hang freely in the laboratory for 1 h and then weighed again. As test result was specified respectively

the arithmetic mean of the weight changes to the samples before placing in the oven. As can be clearly seen in Figure 6, the sweat performance of the disclosed softener composition is 12% by weight of 1,2,3,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight Eastman 168 ™ or 15% by weight of 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight of Eastman 168 ™ significantly better than the exudation behavior of the softener compositions of FIG. 27 % By weight Vestinol® INB and 73% by weight Eastman 168 ™ and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 ™. The tolerable Thus, the softener composition disclosed is better than the compatibility of the plasticizer compositions comprising 27% by weight of Vestinol® INB and 73% by weight of Eastman 168 ™ and 36% by weight of Jayflex® MB 10 and 64% by weight of Eastman 168 ™. III. Comparative experiments on the volatility of Trialkyltrimellitaten

Trialkyl trimellitates differing in carbon number in their alkyl chains were examined for their process volatility and film volatility. The determination of the process volatility was carried out analogously to II. C), the determination of the film volatility was carried out analogously to II. E). For the study, plastisols with the following formulation were used:

The comparison shows that TMTM has higher volatilities than TBTM.

Claims

claims

1 . Plasticizer composition comprising a) at least one compound of the general formula (I),

wherein

R ^1a , R ^1b and R ^1c independently of one another are C3- to Cs-alkyl are at least one compound of the general formula (II),

wherein

R ^2a and R ^{2b are} independently Cs-alkyl.

2. Plasticizer composition according to claim 1, wherein in the at least one compound of the general formula (I) R ^1a , R ^1b and R ^1c independently of one another are n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2- methylbutyl

or 3-methylbutyl.

A plasticizer composition according to any one of the preceding claims wherein in the at least one compound of general formula (II) R ^2a and R ^{2b are} 2-ethylhexyl.

A plasticizer composition according to any one of the preceding claims, wherein the plasticizer composition contains at least one plasticizer which is different from the compounds of general formulas (I) and (II).

5. A molding composition comprising at least one polymer and a plasticizer composition according to claim 1 to 4.

6. A molding composition according to claim 5, wherein the at least one polymer contained is a thermoplastic.

7. Molding composition according to claim 6, wherein the at least one thermoplastic contained is selected from polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and / or copolymers of vinyl acetate, homopolymers and / or copolymers of styrene, polyacrylate, thermoplastic polyurethane (TPU) and polysulfide.

8. A molding composition according to claim 5, wherein the at least one polymer contained is an elastomer, and the elastomer is selected from natural rubber or synthetic rubber

9. Plastisol containing at least one polymer and a plasticizer composition according to claim 1 to 4.

10. A plastisol according to claim 9, wherein the at least one polymer contained is a thermoplastic.

1 1. The plastisol of claim 9, wherein the at least one polymer contained is polyvinyl chloride.

Use of the plasticizer composition according to claims 1 to 4, as a plasticizer in a molding composition.

Use of the plasticizer composition according to claims 1 to 4, as a plasticizer in a plastisol.

14. Use of a molding composition according to claim 5 to 8, for the production of moldings or films.

15. Use of a molding composition according to claim 5 to 8, for the production of moldings and films that come into direct contact with humans or food.

16. The use of a plastisol, according to claim 9 to 1 1, for the production of films, Teta peten, seamless hollow bodies, gloves, gaskets, cover gaskets, panels or console covers in vehicles, dolls, playing figures or kneading, inflatable toys, such as balls or rings , Stopper socks, swimming aids, changing pads, exercise balls, exercise mats, seat cushions, vibrators, massage balls or rollers, latex clothing, protective clothing, rain jackets or rubber boots or coatings.

17. Shaped bodies or films containing the plasticizer composition according to claim 1 to 4.