TW201609903A - Plasticizer composition comprising polymeric dicarboxylic esters and 1,2-cyclohexane-dicarboxylic esters - Google Patents

Abstract

The present invention relates to a plasticizer composition which comprises at least one polymeric dicarboxylic ester and at least one 1,2-cyclohexanedicarboxylic ester, to molding compositions which comprise a thermoplastic polymer or an elastomer and such a plasticizer composition, and the use of these plasticizer compositions and molding compositions.

Description

Plasticizer composition comprising a polymeric dicarboxylate and 1,2-cyclohexanedicarboxylate BACKGROUND OF THE INVENTION

The present invention relates to a plasticizer composition comprising at least one polymeric dicarboxylate and at least one 1,2-cyclohexanedicarboxylate; comprising a thermoplastic polymer or elastomer and molding of the plasticizer composition Compositions; and the use of such plasticizer compositions and molding compositions.

The desired processing characteristics or desired performance characteristics are obtained in a variety of plastics by adding a substance known as a plasticizer to make the plastic softer, more flexible, and/or more extensible. In general, plasticizers are used to move the thermoplastic range of the plastic toward lower temperatures to achieve the desired elastic properties in the low processing temperatures and operating temperature regions.

The production of polyvinyl chloride (PVC) is the highest of any plastic. Because of the versatility of this material, it is now found in many of the products used in everyday life. Therefore PVC is of great economic importance. Essentially, PVC is a hard and brittle plastic at up to about 80 ° C and is used in the form of rigid PVC (PVC-U) by the addition of heat stabilizers and other adjuvants. Flexible PVC (PVC-P) is obtained only by the addition of a suitable plasticizer and can be used in many applications where rigid PVC is not suitable.

An example of another important thermoplastic polymer that typically uses a plasticizer is polyethyl b. Allyl butyral (PVB), homopolymers and copolymers of styrene, polyacrylates, polysulfides, and thermoplastic polyurethanes (PU).

The suitability of the substance for the plasticizer of a particular polymer depends primarily on the characteristics of the polymer to be plasticized. Plasticizers which have high compatibility with the polymer to be plasticized, impart good thermoplastic properties and have only low tendency to evaporate and/or bleed out (high durability) are generally required.

For the plasticization of PVC and other plastics, a large number of different compounds are available on the market. In the past, phthalic acid diesters formed with alcohols of different chemical structures were generally used as plasticizers because of their high compatibility with PVC and advantageous performance characteristics, an example of which is diethylhexyl phthalate (DEHP). ), diisodecyl phthalate (DINP) and diisodecyl phthalate (DIDP).

It is necessary to replace at least some of the aforementioned phthalate plasticizers in view of the suspicion that they are detrimental to health. This is especially true for sensitive areas of application, such as children's toys, food and beverage packaging or medical products.

Various alternative plasticizers of different properties for different plastics and especially for PVC are known in the prior art.

A class of plasticizers is known from the prior art which can be used as a substitute for phthalates based on cyclohexane polycarboxylic acids as described in WO 99/32427. These compounds are toxicologically acceptable and even useful for sensitive applications compared to their unhydrogenated aromatic analogs.

WO 00/78704 describes selected dialkylcyclohexane-1,3-dicarboxylates and dialkylcyclohexane-1,4-dicarboxylates which are useful as plasticizers in synthetic materials.

Another known from the prior art and capable of being used as a substitute for phthalates A class of plasticizers is a substitute for terephthalate as described, for example, in WO 2009/095126.

In addition, monomer plasticizers and various polyesters are also used as plasticizers. Usually by polyol (for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol Esterification of 1,6-hexanediol with polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid to prepare polyester plastic Chemical agent. Depending on the case, it is possible to terminate with a terminal alcohol group (in the case of an alcohol excess synthesis) with a monocarboxylic acid such as acetic acid, or with a terminal acid group (in the case of an acid excess synthesis) such as 2-ethyl. One of the hexanol, isodecyl alcohol, 2-propylheptanol or isodecyl alcohol is capped. Polyester plasticizer is mainly used to produce flexible PVC based foils, coatings, profiles, coverings and cables, especially when it is resistant to the extraction of mineralizers, oils and fats. When the demand for sex and UV resistance and volatility is strengthened.

No. 5,281,647 describes a process for the production of polyester plasticizers, such as azelaic acid, glutaric acid, azelaic acid and/or adipic acid dicarboxylic acid with a strong hindered diol and a small amount of linear The diol reacts to form a polyester, after which the acidic end groups of the polyester are esterified with another alcohol and their use for plasticizing rubber and PVC is also described. In particular, polyester plasticizers are prepared based on adipic acid, trimethylpentanediol and propylene glycol, and the terminal acid groups are esterified with 2-ethylhexanol. These polyesters are said to be suitable as plasticizers for PVC and rubber and are distinguished by their high extraction resistance with respect to oils and soapy water.

RO 104 737 describes polyester plasticizers based on adipic acid and propylene glycol, the terminal acid groups of which are esterified with 2-ethylhexanol. Polyester is said to be suitable as a plasticizer for PVC and is particularly remarkable for its high stability during storage.

EP 1 113 034 describes polyester plasticizers obtainable by reaction of aliphatic dicarboxylic acids, neopentyl alcohols, at least one other diol and isomeric sterols, processes for their preparation and their use as plasticizers Use. Polyesters are said to be distinguished, inter alia, by their low migration tendency relative to acrylonitrile-butadiene-styrene copolymers, polystyrene and polymethyl methacrylate.

Another known measure of setting the desired plasticizer properties is the use of a plasticizer (for example at least one plasticizer which imparts good thermoplastic properties but does not gel well) and at least one plasticization imparting good gelling properties. a mixture of agents.

WO 03/029339 discloses PVC compositions comprising a cyclohexane polycarboxylate and a mixture of a cyclohexane polycarboxylate and other plasticizers. Other plasticizers which are stated to be suitable are non-polymeric ester plasticizers such as terephthalate, phthalate, isophthalate and adipate. Further disclosed are PVC compositions comprising a mixture of a cyclohexane polycarboxylate and various fast gelling plasticizers. Suitable fast gelling plasticizers especially mention various benzoates, aromatic sulfonates, citrates and phosphates. Polyester plasticizers are only mentioned as part of an extremely comprehensive list and are not specifically specified in any way in the patent specification.

However, from a toxicological point of view, a substantial disadvantage of most of the plasticizers and plasticizer compositions described above for suitable alternatives to phthalates is their lack of plasticity, especially The effective compatibility of PVC; in other words, it flows out to a large extent during use and thus results in partial loss of the elastic properties of the plasticized plastic produced using such plasticizers. This is especially true for polyester plasticizers, which are important for a variety of applications, especially for the enhanced resistance of the plasticizer to mineral spirits, oils and fats, and the need for UV resistance and volatility. of.

It is an object of the present invention to provide a toxicologically acceptable plasticizer composition comprising at least one polyester plasticizer of a thermoplastic polymer and an elastomer which has high compatibility with the polymer to be plasticized and which Show little or no tendency to ooze during work, and even longer The elastic properties of the plasticized plastic produced by the use of such plasticizers are maintained during the time period.

Surprisingly, this object is achieved by a plasticizer composition comprising: a) one or more compounds of formula (I),

Wherein X is independently of each other an unbranched chain or a branched chain C ₂ -C ₈ alkyl group or an unbranched chain or a branched chain C ₂ -C ₈ extending alkenyl group containing at least one double bond, and Y is an unbranched chain or branch chain C ₂ -C ₁₂ alkylene containing at least one double bond or unbranched or branched C ₂ -C ₁₂ alkenylene group, a is an integer of from 1 to 100, and, R ¹ each independently selected from unbranched a chain or branched C ₄ -C ₁₂ alkyl radical in which the groups X present in the compound (I) may be the same or different, and wherein in the case where the compound (I) contains more than one group Y, such The groups may be the same or different; b) one or more compounds of formula (II),

Wherein R ² and R ³ are independently of each other selected from the group consisting of a branched chain and an unbranched chain C ₇ -C ₁₂ alkyl radical.

Another subject of the invention is a molding composition comprising at least one thermoplastic polymer or elastomer and a plasticizer composition as defined above and below.

A further subject of the invention is the use of a plasticizer composition as defined above and below as a plasticizer for thermoplastic polymers, more particularly polyvinyl chloride (PVC) and elastomers.

Another subject of the invention is the use of such a molded composition for the production of molded articles and foils.

[Description of the Invention]

The plasticizer composition of the present invention has the following advantages:

- The plasticizer composition of the invention is distinguished by the high compatibility with the polymer to be plasticized, more particularly PVC.

- The plasticizer composition of the present invention does not exhibit at all or only shows a slight tendency to flow out during the working of the final product. Therefore, the elastic properties of the plasticized plastic produced using these plasticizer compositions are obtained even during a longer period of time.

- The plasticizer composition of the invention is suitable for achieving extremely different and complex additions of plastics The multiplicity of work characteristics and performance characteristics.

- The plasticizer composition of the present invention is suitable for the production of molded articles and foils for sensitive fields of application, such as medical products, food and beverage packaging, indoor products such as houses and vehicles, toys, child care articles, etc. .

- The compound (I) present in the plasticizer composition of the present invention can be produced using a readily available starting material.

- The preparation method of the compound (I) used according to the invention is simple and effective. Therefore, the compound (I) can be easily supplied on an industrial scale.

For purposes of this invention, the expression "C ₂ -C ₁₂ alkylene (C ₂ -C ₁₂ alkylene)" means a divalent 2-12 carbon atoms, the hydrocarbon radical. The divalent hydrocarbyl radical may be unbranched or branched. It includes, for example, 1,2-extended ethyl, 1,2-extended propyl, 1,3-propenyl, 1,3-butylene, 1,4-tert-butyl, 2-methyl-1, 3-propyl, 1,1-dimethyl-1,2-extended ethyl, 1,4-exylpentyl, 1,5-amylpentyl, 2-methyl-1,4-butylene , 2,2-dimethyl-1,3-propanyl, 1,6-exexyl, 2-methyl-1,5-exopentyl, 3-methyl-1,5-amyl, 2,3-Dimethyl-1,4-tert-butyl, 1,7-heptyl, 2-methyl-1,6-exexyl, 3-methyl-1,6-extension, 2- Ethyl-1,5-exopentyl, 3-ethyl-1,5-exopentyl, 2,3-dimethyl-1,5-exopentyl, 2,4-dimethyl-1, 5-exetyl, 1,8-exenyl, 2-methyl-1,7-ethanyl, 3-methyl-1,7-ethanyl, 4-methyl-1,7-extension Heptyl, 2-ethyl-1,6-extended hexyl, 3-ethyl-1,6-exexyl, 2,3-dimethyl-1,6-exexyl, 2,4-dimethyl- 1,6-extension, 1,9-extension, 2-methyl-1,8-exenyl, 3-methyl-1,8-exenyl, 4-methyl-1,8- Octyl, 2-ethyl-1,7-heptyl, 3-ethyl-1,7-heptyl, 1,10-extenylene, 2-methyl-1,9-extension , 3-methyl-1,9-extended fluorenyl, 4-methyl-1,9-extended fluorenyl, 5-methyl-1,9-extended fluorenyl, 1,11-exedecyl, 2-methyl- 1,10-extended thiol, 3-methyl-1,10-extended fluorenyl, 5-methyl-1,10-extended fluorenyl, 1,12-extended dodecyl and the like. Preferably, "C ₂ -C ₁₂ alkylene" comprises a branched or unbranched chain C ₂ -C ₈ alkyl, more preferably branched or unbranched C ₂ -C ₅ -alkyl, more particularly 1,2-propenyl, 1,3-propenyl, 1,4-tert-butyl and 2,2-dimethyl-1,3-propanyl.

The expression "C ₂ -C ₁₂ alkylene" also includes the expression "C ₂ -C ₈ alkylene", "C ₂ -C ₆ alkylene" and "C ₂ -C ₅ alkylene" in its definition. .

For purposes of this invention, the expression "C ₂ -C ₁₂ alkenylene group (C ₂ -C ₁₂ alkenylene)" based on divalent hydrocarbon radical having 2 to 12 carbon atoms, which may be unbranched or branched chain, Chain, wherein the backbone has at least one double bond. The "C ₂ -C ₁₂ olefin" preferably comprises a branched chain having one double bond and an unbranched chain C ₂ -C ₈ extended alkenyl group. It includes, for example, a vinyl group, a propylene group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 1-methyl-propenyl group, a 2-methyl-propenyl group, and 1 - pentenyl, 2-pentenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-exenyl, 2-hexenyl , 3-extended hexenyl, 1-methyl-1-endopentenyl, 1-methyl-2-endopentyl, 1-methyl-3-strenyl, 1,4-dimethyl -1-butenyl, 1,4-dimethyl-2-butenyl, 1-enheptenyl, 2-epienyl, 3-epienyl, 1-exene octene Base, 2-extenyl, alkenyl, and the like. Particularly preferably, the "C ₂ -C ₁₂ -extended alkenyl group" comprises a branched chain having one double bond and an unbranched chain C ₂ -C ₆ -extended alkenyl group, more particularly a branched chain having an double bond and an unbranched chain C _2- C _{4 is} an alkenyl group.

The double bonds in the C ₂ -C ₁₂ -extended alkenyl group can be present independently of one another in an E or Z configuration or as a mixture of two configurations.

The expression "C ₂ -C ₁₂ extended alkenyl" also includes the expression "C ₂ -C ₈ extended alkenyl" and "C ₂ -C ₆ extended alkenyl".

For purposes of this invention, the expression "C ₄ -C ₁₂ alkyl (C ₄ -C ₁₂ alkyl)" means having unbranched or branched alkyl group having 4 to 12 carbon atoms. It includes n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethyl Propyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-B Butyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1- Ethyl-2-methylpropyl, n-octyl, isooctyl, 2-ethylhexyl, n-decyl, isodecyl, 2-propylhexyl, n-decyl, isodecyl, 2-propyl Heptyl, n-undecyl, isoundtyl, n-dodecyl, isododecyl and the like. Preferably, "C ₄ -C ₁₂ alkyl" comprises a branched or unbranched chain C ₇ -C ₁₂ alkyl group, more particularly a branched or unbranched chain C ₈ -C ₁₀ alkyl group.

The expression "C ₄ -C ₁₂ alkyl" also includes the expression "C ₇ -C ₁₂ alkyl" and "C ₈ -C ₁₀ alkyl" in its definition.

The X in the formula (I) is independently preferably, at each occurrence, an unbranched chain or a branched C ₂ -C ₈ alkyl group, more preferably an unbranched chain or a branched C ₂ -C ₆ alkyl group. . More specifically, X in the general formula (I) is independently an unbranched chain C ₂ -C ₅ alkyl (=(CH ₂ ) _k , where k = 2, 3, 4 or 5) ), especially 1,3-propyl and 1,4-tert-butyl.

Y in the formula (I) is preferably an unbranched chain or a branched C ₂ -C ₁₂ alkyl group, more preferably an unbranched chain or a branched C ₂ -C ₅ alkyl group. More specifically, Y in the formula (I) is a branched or unbranched chain C ₃ -C ₅ alkyl, especially 1,2-propyl, 1,3-propyl, 1,4 - butyl and 2,2-dimethyl-1,3-propanyl.

The radical group R ¹ in the formula (I) is preferably, independently of each other, a C ₈ -C ₁₀ alkyl group, for example, n-octyl, isooctyl, 2-ethylhexyl, n-decyl, isodecyl, 2-propylhexyl, n-decyl, isodecyl or 2-propylheptyl. The radical group R ¹ in the formula (I) is particularly preferably all n-octyl, isodecyl or 2-propylheptyl.

The group X present in the compound (I) is preferably the same.

If compound (I) contains more than one group Y, it is the same in the first preferred variant.

If the compound (I) contains more than one group Y, it is different in the second variant.

In a first particularly preferred variant, the group X present in the compound (I) is the same, wherein the compound (I) contains more than one different group Y.

In a second particularly preferred variant, the group X present in the compound (I) is the same, wherein the compound (I) contains more than one identical group Y.

In the compound of the formula (I), a is preferably an integer of from 1 to 70, more preferably an integer of from 2 to 50, still more particularly an integer of from 5 to 40.

The compound of the formula (I) used in the plasticizer composition of the present invention is not a mono-compound because of its polymerization property, but is actually a mixture of different compounds. In one aspect, compound (I) has a different chain length and is therefore characterized by an average molar mass. On the other hand, the two radical groups R ¹ and the groups X and Y present in the repeating unit may be different. Furthermore, the radical group R ¹ may comprise a mixture of isomers as defined below.

The weight average molar mass of the polyester plasticizer of the formula (I) present in the plasticizer composition of the invention is usually in the range of from 500 to 15,000, preferably in the range of from 2,000 to 10,000, more preferably in the range of from 3,000 to 10,000. To the 8000 range. The weight average molar mass is generally determined by gel permeation chromatography (GPC) in tetrahydrofuran relative to polystyrene standards.

Polyester plasticizer of the general formula (I) present in the plasticizer composition of the present invention It generally has a range of from 1.000 g/cm3 to 1.200 g/cm3, preferably from 1.010 g/cm3 to 1.170 g/cm3, more preferably from 1.020 g/cm3 to 1.150 g/cm3, according to DIN 51757 at 20 °C. Density inside.

The polyester plasticizer of the formula (I) which is present in the plasticizer composition of the invention generally has a range of from 1000 mPa*s to 20,000 mPa*s, preferably 1200 mPa*, at 20 ° C according to DIN EN ISO 3219. From s to 15000 mPa*s, more preferably in the range of 1500 mPa*s to 14000 mPa*s. In order to determine the dynamic viscosity according to DIN EN ISO 3219, a smaller sample of each plasticizer is placed on the stator of a stator-rotor unit of a suitable rheometer by means of a straw, the rheometer comprising a cone plate of 25 mm diameter Measuring unit. Subsequently, the dynamic viscosity was measured by a rotation test at 20 ° C and 128 rpm.

The polyester plasticizer of the formula (I) which is present in the plasticizer composition of the invention generally has a range of from 1.440 to 1.485, preferably from 1.450 to 1.480, more preferably from 1.460 to 1.475, according to DIN 51423. The refractive index nD20 in the range.

In the compound of the formula (II), the radical groups R ² and R ³ are each independently preferably n-octyl, n-decyl, isodecyl, 2-ethylhexyl, isodecyl, 2-propene. Heptyl, n-undecyl or isoundtyl.

In another preferred embodiment, the radical groups R ² and R ^{3 in} the compound of formula (II) are the same.

Particularly preferably, in the compound of the formula (II), the radical groups R ² and R ³ are both 2-ethylhexyl, all isodecyl or both 2-propylheptyl.

A particularly preferred compound of formula (II) is bis(isodecyl) 1,2-cyclohexanedicarboxylate.

In a preferred embodiment of the present invention, in the compounds of the formulae (I) and (II), X is an unbranched chain or a branched C ₂ -C ₆ alkyl group, and Y is independently an unbranched chain. Or a branched chain C ₂ -C ₅ alkyl, a is an integer from 5 to 40, R ^{1 is} independently C ₈ -C ₁₀ alkyl, and R ² and R ³ are both C ₈ -C ₁₁ alkyl, Wherein the group X present in the compound (I) is the same.

In a particularly preferred embodiment of the present invention, in the compounds of the formulae (I) and (II), X is an unbranched chain C ₂ -C ₅ alkylene group, and Y is independently an unbranched chain or branch a chain C ₃ -C ₅ alkylene, a is an integer from 5 to 40, the R ¹ radical group is an n-octyl group, an isodecyl group or a 2-propylheptyl group, and both R ² and R ³ are 2 Ethylhexyl, all isodecyl or both 2-propylheptyl, wherein the group X present in the compound (I) is the same.

By adjusting the fraction of the compounds (I) and (II) in the plasticizer composition according to the present invention, the plasticizing properties can be applied to individual applications. This can be achieved by routine experimentation. In order to further modify the plasticizer characteristics of the plasticizer composition according to the present invention, for example, when the plasticizer composition is used for a specific application, the addition of a plasticizer other than the compounds (I) and (II) may be helpful. Thus, as defined above, the plasticizer composition may comprise at least one other plasticizer which is different from compounds (I) and (II).

At least one other plasticizer different from the compounds (I) and (II) is selected from the group consisting of alkyl aralkyl phthalate, trialkyl trimellitate, alkyl benzoate, diphenyl diol. Formate, 1,2-cyclohexanedicarboxylate other than compound (II), 1,3-cyclohexanedicarboxylate, 1,4-cyclohexanedicarboxylate, hydroxybyl Acid esters, saturated monocarboxylic acid esters, unsaturated monocarboxylic acid esters, saturated dicarboxylic acid esters, unsaturated dicarboxylic acid esters, decylamines and esters of aromatic sulfonic acids, alkyl sulfonates, glycerol esters, Isosorbide, phosphate, citrate, alkyl pyrrolidone derivative, 2,5-furandicarboxylate, 2,5-tetrahydrofuran dicarboxylate, epoxidized vegetable oil and epoxidized fatty acid A monoalkyl ester and a polyester of an aliphatic and/or aromatic polycarboxylic acid other than the compound (I) and at least a glycol.

Suitable alkyl aralkyl phthalates are, for example, butyl phthalate. The trialkyl trimellitate preferably has, in each case, from 4 to 13 C atoms, more particularly from 7 to 11 C atoms, independently of one another in the alkyl chain. Suitable alkyl benzoates have in each case independently from one another in the alkyl chain from 7 to 13 C atoms, more particularly from 9 to 13 C atoms. Suitable alkyl benzoates are, for example, isodecyl benzoate, isodecyl benzoate or 2-propylheptyl benzoate. Suitable diol dibenzoates are diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate and dibutylene glycol dibenzoate. Suitable 1,2-cyclohexanedicarboxylates other than the compound (II) preferably have from 1 to 6 C atoms, especially from 3 to 6 C atoms, in the alkyl chain.

Suitable dialkyl 1,3-cyclohexanedicarboxylates have from 4 to 13 C atoms, preferably from 8 to 13 C atoms, independently of one another in the alkyl chain. Suitable dialkyl 1,4-cyclohexane-dicarboxylates have from 4 to 13 C atoms, preferably from 8 to 11 C atoms, independently of one another in the alkyl chain. An example of a suitable dialkyl 1,4-cyclohexanedicarboxylate is bis-(2-ethylhexyl)-cyclohexane-1,4-dicarboxylate. The saturated monocarboxylic acid ester is an ester such as acetic acid, butyric acid, valeric acid or lactic acid. Suitable unsaturated monocarboxylic esters are, for example, acrylates. Suitable saturated dicarboxylic acid esters are, for example, esters of succinic acid, glutaric acid, adipic acid, pimelic acid or malic acid. Suitable saturated dicarboxylic acid esters are, for example, esters of maleic acid and fumaric acid. Suitable alkyl sulfonates preferably have an alkyl radical containing from 8 to 22 C atoms. It includes, for example, a phenyl or tolyl ester of pentadecanesulfonic acid. Suitable isosorbide esters are isosorbide diesters which are preferably esterified with C ₈ -C ₁₃ carboxylic acids. Suitable phosphates are tris-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyl phosphate diphenyl ester, bis(2-ethylhexyl)phenyl phosphate and 2-ethyl phosphate. Hexyl ester diphenyl ester. In citric acid triesters, the OH group may be present in free or carboxylated form, preferably in the form of acetamidine. The alkyl radicals of the acetylated citrate are preferably independently of one another from 4 to 8 C atoms, more particularly from 6 to 8 C atoms. Suitable are alkylpyrrolidone derivatives having an alkyl radical having from 4 to 18 C atoms. Suitable dialkyl 2,5-furandicarboxylates in each case have from 7 to 13 C atoms, preferably from 8 to 12 C atoms, independently of one another in the alkyl chain. Suitable dialkyl 2,5-tetrahydrofuran dicarboxylates in each case have from 7 to 13 C atoms, preferably from 8 to 12 C atoms, independently of one another in the alkyl chain. Suitable epoxidized vegetable oils are, for example, epoxidized soybean oil, such as available from Galata-Chemicals, Lampertheim, Germany. For example, under the trade name reFIex ^TM available from PolyOne, USA of epoxidized fatty acid monoalkyl ester is also suitable.

In all the above cases, the alkyl radicals can in each case be linear or branched and in each case the same or different. Refer to the general observations given at the outset for suitable and preferred alkyl radicals.

At least one of the compounds (I) and (II) different from the compound (I) and (II) in the plasticizer composition of the present invention, based on at least one other plasticizer in the plasticizer composition and the total weight of the compounds (I) and (II) The amount of other plasticizer is from 0% by weight to 50% by weight, preferably from 0% by weight to 40% by weight, More preferably from 0% by weight to 30% by weight, and especially from 0% by weight to 25% by weight.

In a preferred embodiment, no other plasticizers as defined above which are different from compounds (I) and (II) are added to the plasticizer composition according to the invention.

The amount of the compound of the formula (I) in the plasticizer composition of the present invention is preferably from 10% by weight to 99% by weight based on the total weight of the compounds (I) and (II) in the plasticizer composition. It is preferably from 30% by weight to 95% by weight, and more particularly from 50% by weight to 90% by weight.

The amount of the compound of the formula (II) in the plasticizer composition of the present invention is preferably from 1% by weight to 90% by weight based on the total weight of the compounds (I) and (II) in the plasticizer composition. It is preferably from 5 wt% to 70 wt%, and more particularly from 10 wt% to 50 wt%.

In the plasticizer composition of the present invention, the weight between the compound of the formula (II) and the compound of the formula (I) is preferably in the range of 1:100 to 10:1, more preferably 1:20. Within the range of 2:1, and especially in the range of 1:10 to 1:1.

Molding composition

Another subject of the invention relates to a molded composition comprising at least one polymer and a plasticizer composition as defined above.

In a preferred embodiment, the polymer present in the molding composition comprises a thermoplastic polymer.

Suitable thermoplastic polymers include all polymers that are thermoplastically treatable. More particularly, the thermoplastic polymers are selected from the group consisting of: - homopolymers or copolymers comprising at least one copolymerized monomer selected from the group consisting of C ₂ -C ₁₀ monoolefins (such as ethylene or propylene), 1 , 3-butadiene, 2-chloro-1,3-butadiene, ester of C ₂ -C ₁₀ -alkanoic acid with vinyl alcohol, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, acrylic acid Glycidyl ester, glycidyl methacrylate, acrylate and methacrylate of alcohol component having branched and unbranched C ₁ -C ₁₀ alcohols, aromatic vinyl (such as styrene), (meth) propylene Nitrile, α,β-ethylenically unsaturated monocarboxylic acid and dicarboxylic acid and maleic anhydride; - homopolymer and copolymer of vinyl acetal; - polyvinyl ester; - polycarbonate (PC); - polyesters such as polyalkylene terephthalate, polyhydroxyalkanoate (PHA), polybutylene succinate (PBS) and polybutylene succinate (PBSA); Polyether; - polyether ketone; - thermoplastic polyurethane (TPU); - polysulfide; - polyfluorene; and mixtures thereof.

Examples include polyacrylates, polymethyl methacrylates having the same or different alcohol residues as the C ₄ -C ₈ alcohols (especially butanol, hexanol, octanol and 2-ethylhexanol) PMMA), methyl methacrylate-butyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM), polyphenylene Ethylene (PS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymer (SBMMA), styrene-cis Butene hydride copolymer, styrene-methacrylic acid copolymer (SMA), polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), Polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polylactic acid (PLA), ethyl cellulose (EC), cellulose acetate (CA), cellulose propionate ( CP) or acetic acid/cellulose butyrate (CAB).

The at least one thermoplastic polymer present in the molding composition of the present invention preferably comprises polyvinyl chloride (PVC), polyvinyl butyral (PVB), homopolymer and copolymer of vinyl acetate, and styrene. Homopolymers and copolymers, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.

Depending on the thermoplastic polymer or thermoplastic polymer mixture present in the molding composition, varying amounts of plasticizer are required to achieve the desired thermoplastic properties. The appropriate amount of plasticizer can be determined by some routine experimentation. If the at least one thermoplastic polymer present in the molding composition is not PVC, the plasticizer content of the molding composition is typically from 0.5 to 300 phr (per hundred parts of resin, ie, per hundred parts by weight) The part by weight of the polymer is preferably from 1.0 to 130 phr, more preferably from 2.0 to 100 phr.

The at least one thermoplastic polymer present in the molding composition of the invention is especially polyvinyl chloride (PVC).

Polyvinyl chloride is obtained by homopolymerization of vinyl chloride. Polyvinyl chloride (PVC) used in accordance with the invention can be prepared, for example, by suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization. The production and composition of PVC prepared by polymerization of vinyl chloride and plasticized PVC are described, for example, in "Becker/Braun, Kunststoff-Handbuch, Vol. 2/1: Polyvinylchlorid", 2nd edition, Carl Hanser Verlag, Munich.

For the plasticized plastic according to the invention, the molar mass of the PVC is characterized and the K value determined according to DIN 53726 is generally in the range of 57 and 90, preferably in the range of 61 and 85, especially in the range of 64 and 80.

For the purposes of the present invention, the amount of PVC in the mixture is from 20% to 95% by weight, preferably from 40% to 90% by weight, and especially from 45% to 85% by weight.

In the case where the thermoplastic polymer in the molding composition of the present invention is polyvinyl chloride, the molding composition has a total plasticizer content of from 5.0 phr to 300 phr, preferably from 15 phr to 150 phr, and more preferably from 30 phr to 120 phr.

Another subject of the invention relates to a molding composition comprising an elastomer and a plasticizer composition according to the invention.

The elastomer present in the molding composition of the present invention may be natural rubber (NR) or a synthetically produced rubber or a mixture thereof. Examples of preferred synthetically produced rubbers are polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile-butadiene rubber (NBR) or Chloroprene rubber (CR).

Preferred rubber or rubber mixtures are those which can be sulfur vulcanized.

For the purposes of the present invention, the amount of elastomer in the molding composition of the present invention is from 20% to 95% by weight, preferably from 45% to 90% by weight, and especially from 50% by weight, based on the total weight of the molding composition. 85wt%.

For the purposes of the present invention, a molding composition comprising at least one elastomer may comprise other suitable adjuvants than the above ingredients. For example, reinforcing fillers such as carbon black or cerium oxide; other fillers such as phenolic resins; vulcanizing agents or crosslinking agents; vulcanization or crosslinking accelerators; activators; various types of oils; Inhibitors; and other various adjuvants incorporated into, for example, tire compounds and, for example, other rubber compounds.

The polymer in the molding composition of the present invention comprises an elastomer, especially rubber, and the total content of the plasticizer composition of the present invention as defined above in the molding composition is From 1.0 phr to 60 phr, preferably from 2.0 phr to 40 phr, more preferably from 3.0 phr to 30 phr.

Alternatively, the polymer in the molding composition can be a mixture of PVC and elastomer. With regard to suitable and preferred elastomers that can be used in such polymer blends, reference is made to the explanations mentioned above. The amount of elastomer in such polymer blends is typically from 1 wt.% to 50 wt.%, preferably from 3 wt.% to 40 wt.%, especially from 5 wt.% to 30 wt.%.

Depending on the fraction of the elastomer in the polymer mixture, the amount of the plasticizer composition of the present invention in such molding compositions necessary to achieve the desired properties can vary drastically.

The total content of the plasticizer composition of the present invention in such molding compositions is typically in the range of from 0.5 phr to 300 phr, preferably from 1.0 phr to 150 phr, more preferably from 2.0 phr to 120 phr.

Molding composition adjuvant

For the purposes of the present invention, a molding composition comprising at least one thermoplastic polymer can comprise other suitable adjuvants. Examples which may be present include stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact toughening agents, optical brighteners, antistatic agents or biostable Agent.

A variety of suitable adjuvants are described in more detail below. However, the examples given do not impose any limitation on the molding composition of the present invention, but are actually provided for the purpose of illustration only. The amount of detail is based on the weight percent of the molded composition as a whole.

Stabilizers encompassed include all conventional PVC stabilizers in solid and liquid form, examples being conventional Ca/Zn, Ba/Zn, Pb or Sn stabilizers and acid-bound phthalates.

The molding composition of the present invention may have a stabilizer content of from 0.05% to 7%, preferably from 0.1% to 5%, more preferably from 0.2% to 4%, and still more specifically from 0.5% to 3%.

The lubricant reduces the adhesion between the polymer to be treated and the metal surface and serves to counteract the friction during mixing, plasticizing and deformation.

The molding composition of the present invention may comprise all lubricants conventionally used for processing plastics as lubricants. Examples of lubricants covered by them include hydrocarbons (such as oils, paraffin and PE waxes), fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids (such as fatty acids and montanic acid), oxidized PE waxes, carboxylic acids. The metal salt, carboxyguanamine, and carboxylate are exemplified by those having an alcohol (ethanol, fatty alcohol, glycerol, ethylene glycol, pentaerythritol) and a long-chain carboxylic acid as an acid component.

The molding composition of the present invention may have a lubricant content of 0.01% to 10%, preferably 0.05% to 5%, more preferably 0.1% to 3%, and still more specifically 0.2% to 2%.

In a positive manner, the filler particularly affects the compressive strength, tensile strength and flexural strength, and hardness and thermal deformation resistance of the plasticized PVC.

For the purposes of the present invention, the molding composition may also contain fillers (such as carbon black) and other inorganic fillers such as natural calcium carbonate (e.g., chalk, limestone, and marble), synthetic calcium carbonate, dolomite, silicate. , cerium oxide, sand, diatomaceous earth, aluminum silicate (such as kaolin, mica and feldspar). Preferred fillers used are calcium carbonate, chalk, dolomite, kaolin, silicate, talc or carbon black.

The molding composition of the present invention may have a filler content of from 0.01% to 80%, preferably from 0.1% to 60%, more preferably from 0.5% to 50%, and still more specifically from 1% to 40%.

The molding compositions of the present invention may also comprise pigments to render the resulting products suitable for different possible applications.

For the purpose of the present invention, both inorganic pigments and organic pigments can be used. The inorganic pigment used may be, for example, a cobalt pigment such as CoO/Al ₂ O ₃ ; and a chromium pigment such as Cr ₂ O ₃ . The organic pigments covered include, for example, monoazo pigments, condensed azo pigments, methylimine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and pigment.

The molding composition of the present invention may have a pigment content of from 0.01% to 10%, preferably from 0.05% to 5%, more preferably from 0.1% to 3%, and still more specifically from 0.5% to 2%.

In order to reduce flammability and reduce the amount of smoke released upon combustion, the molding composition of the present invention may also contain a flame retardant.

Examples of the flame retardant which can be used include antimony trioxide, phosphoric acid ester, chlorite paraffin, aluminum hydroxide, and a boron compound.

The molding composition of the present invention may have a flame retardant content of from 0.01% to 10%, preferably from 0.1% to 8%, more preferably from 0.2% to 5%, and still more specifically from 0.5% to 2%.

In order to protect the surface area of the article produced by the molding composition of the present invention from damage due to light, the molding composition may also contain a light stabilizer such as a UV absorber.

For the purposes of the present invention, for example, hydroxybenzophenone, hydroxyphenylbenzotriazole, cyanoacrylate or hindered amine light stabilizer (HALS) can be used (such as 2, 2, 6, 6- A derivative of tetramethylpiperidine) as a light stabilizer.

The molding composition of the present invention may have a light stabilizer (e.g., UV absorber) content of from 0.01% to 7%, preferably from 0.1% to 5%, more preferably from 0.2% to 4%, and still more specifically from 0.5% to 3%. .

Preparation of a compound of the formula (I)

The polyester of the invention is prepared in a technically known manner by esterification of an aliphatic dicarboxylic acid with a diol in the presence of one of the capping groups and an esterification catalyst as described, for example, in EP 1113034 B1. Plasticizer. The chain length or average molar weight of the polyester plasticizer is controlled via the addition ratio of the dicarboxylic acid and the diol.

The dicarboxylic acid used for the preparation of the polyester plasticizer of the formula (I) is preferably an unbranched chain or a branched C ₂ -C ₆ alkyl dicarboxylic acid, more preferably an unbranched chain C ₂ -C ₅ alkyl group. Dicarboxylic acid. The dicarboxylic acids used for the preparation of the polyester plasticizers of the formula (I) are more particularly glutaric acid and/or adipic acid, in particular adipic acid.

The diol used for the preparation of the polyester plasticizer of the formula (I) is preferably an unbranched chain or a branched C ₂ -C ₈ alkyl diol, more preferably an unbranched chain and a branched chain C ₂ -C ₆ Alkyl glycols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,2-dimethyl -1,3-propanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2-methyl Base-1,3-pentanediol, 1,7-hexanediol, 2,2-dimethyl-1,3-pentanediol or a mixture of such glycols. More specifically, the diol used to prepare the polyester plasticizer of the formula (I) is 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,2-di Methyl-1,3-propanediol or a mixture of such diols.

The one used as the chain end of the polyester plasticizer of the formula (I) is preferably an unbranched chain or a branched C ₇ -C ₁₂ alkanol or an unbranched chain or a branched C ₇ -C ₁₂ alkane. a mixture of alcohols. It includes n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isodecyl alcohol, 2-propylhexanol, n-nonanol, isodecyl alcohol, 2- Propyl heptanol, n-undecyl alcohol, isoundecyl alcohol, n-dodecanol, isododecyl alcohol or a mixture of such alcohols. More preferably, one of the alcohols used as the chain end when preparing the polyester plasticizer of the formula (I) is n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isodecyl alcohol, 2 -propylhexanol, n-nonanol, isodecyl alcohol, 2-propylheptanol or a mixture of such alcohols, and especially n-octanol, isodecyl alcohol, 2-propylheptanol or a mixture of such alcohols .

The plasticizer composition of the present invention comprises, in particular, a compound of the formula (I) prepared using the following starting materials: adipic acid, 1,2-propanediol and n-octanol, or Adipic acid, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol and isodecyl alcohol, or adipic acid, 1,4-butanediol, 2,2-dimethyl-1 , 3-propanediol and isodecyl alcohol.

The esterification catalyst used is generally a catalyst conventionally used for the purpose, examples being inorganic acids such as sulfuric acid and phosphoric acid; organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid; amphoteric catalysts, more particularly titanium compounds, tin (IV) a compound or a zirconium compound such as titanium tetraalkoxide such as titanium tetrabutoxide and tin (IV) oxide.

An effective amount of the esterification catalyst is used, which is typically in the range of from 0.05% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight based on the total of the acid component and the alcohol component.

Other methods which are suitable for the production of the compounds of the formula (I) via esterification are described, for example, in US Pat. No. 6,310,235, US Pat. No. 5,324,853, DE-A 2612355 or DE-A 1 945 359.

Esterification can generally be carried out under ambient pressure or under reduced pressure or elevated pressure. The esterification is preferably carried out under ambient pressure or reduced pressure.

The esterification can be carried out in the absence of an added solvent or in the presence of an organic solvent which preferably forms an azeotropic mixture with water formed during the esterification reaction.

If the esterification is carried out in the presence of a solvent, the solvent in question is preferably an organic solvent which is inert under the reaction conditions. Such solvents include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers. The solvent is preferably selected from the group consisting of pentane, hexane, heptane, light gasoline, petroleum ether, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene. , dibutyl ether, THF, two Alkanes and mixtures thereof.

The esterification is usually carried out at a temperature ranging from 50 ° C to 250 ° C.

In the case where the esterification catalyst is selected from an organic acid or a mineral acid, the esterification is typically carried out at a temperature ranging from 50 ° C to 160 ° C.

In the case where the esterification catalyst is selected from the group consisting of amphoteric catalysts, the esterification is usually carried out at a temperature ranging from 100 ° C to 250 ° C.

Esterification can be carried out in the presence or absence of an inert gas. In general, an inert gas is a gas that does not react with the reactants or reagents or solvents involved in the reaction or the product formed under the existing reaction conditions.

In a preferred embodiment, as an esterification catalyst, for example, adipic acid, 1,4-butanediol, neopentyl glycol, isodecyl alcohol, and isopropyl butyl titanate are charged into a reaction vessel, initially Heat to 100 ° C to 140 ° C and homogenize by stirring. The reaction mixture is then heated at 160 ° C to 190 ° C under atmospheric pressure. Esterification with removal of water begins at about 150 °C. The water formed by the reaction is separated by distillation through a column. The distilled alcohol component is separated and returned. The reaction mixture is then further heated to 200 ° C to 250 ° C, a reduced pressure of 150 mbar to 300 mbar is applied, and the other water of the reaction is removed from the reaction mixture by passing nitrogen therethrough. The reaction mixture was stirred therethrough at 200 ° C to 250 ° C under reduced pressure with nitrogen transfer until the acid value of the reaction mixture reached a level of <15 mg KOH / g.

Subsequently, for the final esterification, the reaction mixture is pumped into a second vessel and stirred at a reduced pressure of 10 mbar to 150 mbar at 200 ° C to 250 ° C with concomitant transfer of the increased nitrogen stream The residual water and excess isodecyl alcohol were removed by the reaction mixture until the acid value of the reaction mixture reached a level of <1.0 mg KOH/g. Thereafter, the reaction product was also filtered at 100 ° C to 140 ° C.

The aliphatic dicarboxylic acids, diols and monohydric alcohols used to prepare the compounds of formula (I) are commercially available or can be prepared by synthetic routes known from the literature.

Commercially available polyester plasticizers can also be used as the polyester plasticizer of the formula (I). suitable Commercially available polyester plasticizers are, for example, the manufacturer BASF SE, Ludwigshafen under the trade name Palamoll® 638 (polyester plasticizer based on adipic acid, 1,2-propanediol and n-octanol), Palamoll® 652 (based on Acid, 1,2-propanediol, neopentyl glycol and isodecyl alcohol polyester plasticizer), Palamoll® 654 (based on adipic acid, 1,4-butanediol, neopentyl glycol and isodecyl alcohol) Polyester plasticizer) or Palamoll® 656 (polyester plasticizer based on adipic acid, 1,4-butanediol, neopentyl glycol and isodecyl alcohol).

Compound of formula (II)

Compounds of formula (II) are commercially available or can be prepared by methods known in the art as described in EP 1171413 B1.

In general, 1,2-cyclohexanedicarboxylates are generally obtained by ring hydrogenation of the corresponding phthalates. Ring hydrogenation can be carried out by the method described in WO 99/32427. A particularly suitable ring hydrogenation process is also described, for example, in WO 2011082991 A2.

Further, the 1,2-cyclohexanedicarboxylate can be obtained by esterification of 1,2-cyclohexanedicarboxylic acid or a suitable derivative thereof with a corresponding alcohol. Esterification can be carried out by conventional methods known to those skilled in the art.

A common feature of the process for the preparation of the compounds of the formula (II) is the esterification or transesterification starting from phthalic acid, 1,2-cyclohexanedicarboxylic acid or a suitable derivative thereof. Wherein the corresponding C ₇ -C ₁₂ alkanol is used as the reactant. These alcohols are generally not pure, but are actually mixtures of isomers, the composition and purity of which are determined by their particular method of preparation.

Preferred C ₇ -C ₁₂ alkanols for the preparation of the compounds (I) and (II) present in the plasticizer composition according to the invention may be linear or branched, or may be linear or branched. A mixture of C ₇ -C ₁₂ alkanols. It includes n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isodecyl alcohol, isodecyl alcohol, 2-propylheptanol, n-undecyl alcohol, Isopenecyl alcohol, n-dodecanol or isododecyl alcohol. Particularly preferred C ₇ -C ₁₂ alkanols are 2-ethylhexanol, isodecyl alcohol and 2-propylheptanol, especially isodecyl alcohol.

Heptanol

The heptanol used to prepare the compounds of formula (I) and (II) may be straight or branched, or may be composed of a mixture of linear and branched heptanols. It is preferred to use a mixture of branched chain heptanol (also known as isoheptanol) which can be prepared by ruthenium catalysis of dimerized propylene or preferably cobalt catalyzed hydrogen formazanization, for example by The Dimersol® process and subsequent hydrogenation of the resulting iso-heptanal used to obtain a mixture of isoheptanes are obtained. According to the preparation thereof, the isoheptanol mixture thus obtained consists of a plurality of isomers. Substantially linear heptanol can be obtained by ruthenium catalysis of 1-hexene or preferably cobalt catalyzed hydrogen formazanization and subsequent hydrogenation of n-heptanal to n-heptanol. The hydroformylation of 1-hexene or dimer propylene can be carried out according to a method known per se: in the case of hydroformylation in which the rhodium catalyst is uniformly dissolved in the reaction medium, it is possible to use not only the mismatched crucible a carbonyl compound which is formed in situ under the conditions of a hydroformylation reaction in a hydroformylation mixture under the action of a synthesis gas, for example from a phosphonium salt, also uses a miscible ruthenium carbonyl compound, more particularly with an organophosphine (such as three Phenylphosphine or an organic phosphate, preferably a complex of a chelated diphosphite (as described, for example, in US-A 5,288,918) as a catalyst. In the case of cobalt catalyzed hydroformylation of such olefins, cobalt carbonyl compounds are generally used, which are homogeneously soluble in the reaction mixture and which are formed from cobalt salts under the conditions of hydroformylation under the action of synthesis gas . In the case where cobalt-catalyzed hydroformylation is carried out in the presence of a trialkylphosphine or a triarylphosphine, the desired heptanol is formed directly as a hydroformylation product, meaning that no further hydrogenation of the aldehyde functionality is required.

Cobalt-catalyzed hydrogen formazanization of a mixture of 1-hexene or hexene isomers Examples of suitable methods are those recognized by Falbe, New Syntheses with Carbon Monoxide, Springer, Berlin, 1980, pages 162-168, such as the Ruhrchemie process, the BASF method ( BASF process), Kuhlmann process or Shell process. Although the Ruhr chemistry, the BASF and the Coulman process operate with a cobalt carbonyl compound that has not been modified with a ligand as a catalyst and produce a hexanal mixture, the Schell method (DE-A 1593368) uses a phosphine or phosphorous acid. The ester ligand-modified cobalt carbonyl compound acts as a catalyst which directly produces a hexanol mixture by means of its additionally higher hydrogenation activity. An advantageous example of the use of a cobalt carbonyl complex which is not modified with a ligand to achieve hydroformylation is described in detail in DE-A 2 139 630, DE-A 2 244 373, DE-A 2 404 855 and WO 01014297.

The ruthenium-catalyzed hydroformylation of a mixture of 1-hexene or hexene isomers may be carried out using an approved ruthenium carbonyl compound modified with a triphenylphosphine ligand, which is the subject of US-A 4,148,830. Industrial low pressure hydrazine hydroformylation method. The ruthenium carbonyl compound which is not modified with a ligand can be advantageously used as a catalyst for the hydrogenation of a long chain olefin (for example, a mixture of hexene isomers obtained by the process described above); The difference from the low pressure method is that a higher pressure of 80 to 400 bar is required. The implementation of this type of high pressure hydroquinone hydroformylation process is described, for example, in EP-A 695 734, EP-880 494 and EP-B 1047655.

The iso-heptanal mixture obtained after the hydroformylation of the hexene isomer mixture is catalytically hydrogenated in a manner known per se to give an isoheptane mixture. For this purpose, it is preferred to use a heterogeneous catalyst comprising a metal and/or a metal oxide of Group VI to Group VIII or Transition Group I of the Periodic Table of the Elements as a catalytically active component, in particular chromium, Molybdenum, manganese, cerium, iron, cobalt, nickel and/or copper are optionally deposited on a support material such as Al ₂ O ₃ , SiO ₂ and/or TiO ₂ . Catalysts of this type are described, for example, in DE-A 3,228,881, DE-A 2,628,987 and DE-A 2,445,303. It is especially preferred to use an excess of hydrogen in a stoichiometric amount of from 1.5% to 20% of the hydrogen required for the hydrogenation of isoheptanal, at a temperature of from 50 ° C to 200 ° C and at a hydrogen pressure of from 25 bar to 350 bar. Hydrogenation of heptanal, and in order to avoid side reactions, according to DE-A 2 628 987, a small amount of water is added during the hydrogenation process, preferably in the form of an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate, according to the teaching of WO 01087809.

Octanol

2-Ethylhexanol has been the most productive plasticizer alcohol for many years and it can be produced by the aldol condensation of n-butyraldehyde to 2-ethylhexanal followed by hydrogenation to give 2-ethylhexanol. Obtained (see Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A 10, pp. 137-140, VCH Verlagsgesellschaft GmbH, Weinheim 1987).

Substantially linear octanol can be obtained via hydrogenation of 1-heptene or preferably cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting n-octanal used to obtain n-octanol. The 1-heptene required for this purpose can be obtained from Fischer-Tropsch synthesis of hydrocarbons.

By means of the alcohol used to prepare the different ways octanol, 2-ethylhexanol compared with or octanol, an alcohol, isooctyl alcohol compound is not unitary, but is actually a different branched C ₈ alcohols (e.g. 2,3-Dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5 -Methyl-1-heptanol, depending on the preparation conditions and preparation methods used, such alcohols may be present in isomeric alcohol in varying proportions. Isooctanol is typically prepared via codimerization of propylene with butene (preferably n-butene) and subsequent hydroformylation of a mixture of the resulting heptene isomers. The octanal isomer mixture obtained in hydroformylation can then be hydrogenated in a manner known per se to give isooctanol.

The co-dimerization of propylene and butene to produce isomeric heptene is preferably obtained by means of the homogeneous catalytic Dimersol® method (Chauvin et al; Chem. Ind.; May 1974, pp. 375-378), which is in the ethyl group. A soluble nickel phosphine complex is used as a catalyst in the presence of an aluminum chloro compound such as ethyl aluminum dichloride. Examples of phosphine ligands which can be used in the nickel complex catalyst are tributylphosphine, triisopropylphosphine, tricyclohexylphosphine and/or tritylphosphine. The reaction is carried out at a temperature between 0 ° C and 80 ° C, and it is preferred here to set the pressure at which the olefin is present in the solution as a liquid reaction mixture (Cornils; Hermann: Applied Homogeneous Catalysis with Organometallic Compounds; 2nd Edition, Volume 1; Pp. 254-259, Wiley-VCH, Weinheim 2002).

In an alternative method using a Dimersol® process operated by a nickel catalyst uniformly dissolved in a reaction medium, co-dimerization of propylene with butene can also be carried out by a heterogeneous NiO catalyst deposited on a support; The heptene isomer distribution is similar to that obtained in the homogeneous catalytic process. Catalysts of this type are for example used in processes known as the Octol® process (Hydrocarbon Processing, February 1986, pages 31-33) and have specific properties for good suitability for olefin dimerization or olefin codimerization. Homogeneous nickel catalysts are disclosed, for example, in WO 9514647.

Instead of a nickel-based catalyst, heterodimerization of propylene and butene can also be carried out using heterogeneous Brine (Br Nsted-acid) catalyst; the heptene obtained here generally has a higher degree of branching than the nickel catalyzed process. Examples of catalysts suitable for this purpose are solid phosphoric acid catalysts, such as phosphoric acid impregnated diatomite or diatomaceous earth, which are used in the PolyGas® process for olefin dimerization or olefin oligomerization (Chitnis et al; Hydrocarbon Engineering 10, No. 6 - June 2005). A Brookfield catalyst having a very good suitability for the codimerization of propylene with butene to heptene is a zeolite which is used in the EMOGAS® process which is further developed based on the PolyGas® process.

By means of hydrazine or cobalt-catalyzed hydrogen formazanization, cobalt-catalyzed hydrogen formazanization is preferred, From the above known methods for the preparation of the mixture of n-heptanal and heptaldehyde isomers, a mixture of 1-heptene and heptene isomers is converted to a mixture of n-octanal and octanal isomers, respectively. Subsequently, these materials are hydrogenated to give the corresponding octanol, for example by means of one of the catalysts mentioned above for the preparation of n-heptanol and isoheptanol.

Sterol

Substantially linear sterols can be obtained via 1-octene or preferably cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting n-nonanal. The starting olefin 1-octene can be, for example, by means of a nickel complex catalyst which is homogeneously soluble in the reaction medium (1,4-butanediol) and, for example, diphenyl-phosphinoacetic acid or 2- as a ligand. The ethylene of diphenylphosphinobenzoic acid is obtained by oligomerization of ethylene. This method is also known as the Shell Higher Olefins Process or the SHOP process (see Weisermel, Arpe: Industrielle Organische Chemie [Industrial organic chemistry]; 5th edition, page 96; Wiley-VCH, Weinheim 1998).

The isodecyl alcohol used to synthesize the diisononyl esters of the general formulae (I) and (II) contained in the plasticizer composition of the present invention is not a mono-type compound, but is actually a heterogeneous C of a different branched chain. A mixture of ₉ alcohols which may have different degrees of branching depending on the manner of preparation and the starting materials used. Isodecyl alcohol is typically prepared via the hydrogenation of butenes for the isooctene mixture, the subsequent hydroformylation of the isooctene mixture, and the hydrogenation of the resulting isooctanal mixture used to obtain the isodecyl alcohol mixture, such as Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A1, pp. 291-292, VCH Verlagsgesellschaft GmbH, Weinheim 1995.

Mixtures of isobutylene, cis-2-butene and trans-2-butene and 1-butene or such butene isomers can be used as starting materials for the production of isodecyl alcohol. Dimerization of pure isobutylene (mainly by means of liquid Brinellic acid (such as sulfuric acid or phosphoric acid) or by means of solid state Brinellic acid (for example as a support material for the oxidation of diatomite, SiO ₂ or Al ₂ O ₃ ) or zeolite catalysis The predominantly highly branched compound 2,4,4-trimethylpentene, also known as diisobutylene, produces highly branched isodecyl alcohol after the hydroformylation and hydrogenation of the aldehyde.

Preferred are isodecyl alcohols having a low degree of branching. An isodecyl alcohol mixture of this type having very few branches is carried out by means of a straight chain butene 1-buter by means of the above-described route involving the dimerization of butene, the hydroformylation of isooctene and the hydrogenation of the resulting isooctanoyl mixture Preparation of alkenes, cis-2-butenes and/or trans-2-butenes (which may optionally also contain relatively small amounts of isobutylene). Preferred starting material is referred to as raffinate II of substances, which system a cracker, a steam cracker, for example, the C ₄ fraction obtained after the steps of: partially hydrogenated removed via propadiene, acetylene and dienes (especially 1,3-butadiene) to obtain linear butenes, or to remove them via extractive distillation, for example by means of N-methylpyrrolidone, and subsequently reacted with methanol or isobutanol via An approved large-scale industrial process in which a fuel additive methyl tert-butyl ether (MTBE) is formed for catalytic removal of the isobutylene contained therein, or by means of an isobutyl group for obtaining pure isobutylene Tributyl ether.

In addition to 1-butene and cis-2-butene and trans-2-butene, the raffinate II also contains n-butane and isobutane and up to 5% by weight of residual isobutene.

The dimerization of the linear butene or butene mixture contained in the raffinate II can be carried out by means of familiar methods used on a large industrial scale, such as the methods explained above for the preparation of the isoheptene mixture, for example by means of Heterogeneous Brookfield catalysts, such as those used in the PolyGas® process or the EMOGAS® process, by means of the Dimersol® process using a nickel complex catalyst homogeneously dissolved in the reaction medium, or by means of heterogeneous A catalyst containing nickel (II) oxide by the Octol® method or by the method of WO 9514647. By means of rhodium or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, by the above preparation of a mixture of heptaldehyde isomers The known method of interpreting the resulting isooctene mixture is converted to an isooctanal mixture. Subsequently, these materials are hydrogenated to give a suitable isodecyl alcohol mixture, for example by means of one of the catalysts mentioned above for the preparation of isoheptanol.

The resulting isodecyl alcohol isomer mixture can be characterized by its isomerization index, which can be multiplied by the degree of branching of the individual isomeric isodecyl alcohol components in the isodecyl alcohol mixture by the isodecyl alcohol mixture. Calculate the percentage ratio of the components: for example, the isomeric index contribution of n-nonanol to isodecyl alcohol mixture is 0, the contribution of methyl octanol (single branch) is 1, and the contribution of dimethyl heptanol (double branch) The value is 2. The higher the linearity, the lower the isomerization index of the relevant isodecyl alcohol mixture. Thus, the isomerization index of the isodecyl alcohol mixture can be determined by gas chromatography separation of the isodecyl alcohol mixture into its individual isomers, and the isodecyl alcohol mixture is determined by standard methods of gas chromatography analysis. Concomitant quantification of the percentage ratio of isomers. In order to increase the volatility of the isomeric sterols and to improve the gas chromatographic separation of such materials, it is preferred to alkylate them by means of standard methods prior to gas chromatography analysis, for example via N-methyl-N. - Trimethyldecyltrifluoroacetamide reaction. In order to obtain the maximum separation quality of the individual components during gas chromatography analysis, it is preferred to use a capillary column having polydimethyl siloxane as a stationary phase. Capillary columns of this type are commercially available, and those skilled in the art will be able to select a column having the desired suitability for this separation task from a variety of different commercially available products with minimal routine experimentation.

The diisononyl esters of the formulae (I) and (II) used in the plasticizer composition of the invention generally have a heterogeneous index of from 0.8 to 2, preferably from 1.0 to 1.8, and particularly preferably from 1.1 to 1.5. Isodecyl alcohol, which can be prepared by the above method, is esterified.

The possible compositions of the isodecyl alcohol mixtures useful in the preparation of the compounds of the general formulae (I) and (II) used according to the invention are set out below by way of example only, and it should be noted here, The proportion of the individual isomers listed in the isodecyl alcohol mixture can be determined by the composition of the starting material (eg, raffinate II, wherein the butene composition can vary with the method of preparation) and the preparation conditions used (eg, utilized The life of the catalyst must be varied according to its appropriately adjusted temperature and pressure conditions.

For example, a mixture of isodecyl alcohol produced via hydrogenation of cobalt-catalyzed hydroformylation and subsequent isooctene mixture (using raffinate II as a starting material by means of a catalyst and process according to WO 9514647) may have the following composition : - 1.73% by weight to 3.73% by weight, preferably 1.93% by weight to 3.53% by weight, particularly preferably 2.23% by weight to 3.23% by weight of 3-ethyl-6-methyl-hexanol; - 0.38% by weight to 1.38 % by weight, preferably from 0.48% by weight to 1.28% by weight, particularly preferably from 0.58% by weight to 1.18% by weight of 2,6-dimethylheptanol; from 2.78% by weight to 4.78% by weight, preferably from 2.98% by weight to 4.58% % by weight, particularly preferably from 3.28% by weight to 4.28% by weight, of 3,5-dimethylheptanol; from 6.30% by weight to 16.30% by weight, preferably from 7.30% by weight to 15.30% by weight, particularly preferably from 8.30% by weight to 14.30% by weight of 3,6-dimethylheptanol; - 5.74% by weight to 11.74% by weight, preferably 6.24% by weight to 11.24% by weight, particularly preferably 6.74% by weight to 10.74% by weight of 4,6-dimethyl Heptoheptanol; - 1.64% by weight to 3.64% by weight, preferably 1.84% by weight to 3.44% by weight, particularly preferably 2.14% by weight to 3.14% by weight of 3,4,5-trimethylhexanol; - 1.47% by weight Up to 5.47 wt%, preferably from 1.97 wt% to 4.97 wt%, particularly preferably from 2.47 wt% to 4.4 wt% of 3,4,5-trimethylhexanol, 3-methyl-4-ethylhexanol and 3-ethyl-4-methylhexanol; - from 4.00% by weight to 10.00% by weight, preferably from 4.50% by weight to 9.50% by weight, particularly preferably from 5.00% by weight to 9.00% by weight of 3,4-dimethylheptanol; - from 0.99% by weight to 2.99% by weight, Preferably from 1.19% by weight to 2.79% by weight, particularly preferably from 1.49% by weight to 2.49% by weight of 4-ethyl-5-methylhexanol and 3-ethylheptanol; from 2.45% by weight to 8.45% by weight, preferably 2.95% by weight to 7.95% by weight, particularly preferably 3.45% by weight to 7.45% by weight of 4,5-dimethylheptanol and 3-methyloctanol; -1.21% by weight to 5.21% by weight, preferably 1.71% by weight Up to 4.71% by weight, particularly preferably 2.21% by weight to 4.21% by weight of 4,5-dimethylheptanol; -1.55% by weight to 5.55% by weight, preferably 2.05% by weight to 5.05% by weight, particularly preferably 2.55 by weight % to 4.55% by weight of 5,6-dimethylheptanol; -1.63% by weight to 3.63% by weight, preferably 1.83% by weight to 3.43% by weight, particularly preferably 2.13% by weight to 3.13% by weight of 4-methyl group Octanol; - 0.98 wt% to 2.98 wt%, preferably 1.18 wt% to 2.78 wt%, particularly preferably 1.48 wt% to 2.48 wt% of 5-methyloctanol; - 0.70 wt% to 2.70 wt%, Preferably from 0.90% by weight to 2.50% by weight, particularly preferably 1.20% by weight 2.20% by weight of 3,6,6-trimethylhexanol; -1.96% by weight to 3.96 % by weight, preferably 2.16% by weight to 3.76 % by weight, particularly preferably 2.46% by weight to 3.46 % by weight of 7-methyl group Octanol; - 1.24% by weight to 3.24% by weight, preferably 1.44% by weight to 3.04% by weight, particularly preferably 1.74% by weight to 2.74% by weight of 6-methyl octanol; - 0.1% by weight to 3% by weight, Preferably from 0.2% by weight to 2% by weight, particularly preferably from 0.3% by weight to 1% by weight of n-nonanol; - 25% by weight to 35% by weight, preferably 28% by weight to 33% by weight, particularly preferably 29% by weight to 32% by weight, of other alcohols having 9 and 10 carbon atoms; the limitation is the group mentioned The total is 100% by weight.

According to the above, depending on the composition of the raw materials and the reaction conditions used, hydrogen hydroformylation and subsequent hydrogenation via cobalt catalysis (using the PolyGas® method or EMOGAS® by means of a mixture of butene containing ethylene) The isodecyl alcohol mixture produced by the process of the isooctene mixture can vary within the following composition range: - 6.0% by weight to 16.0% by weight, preferably 7.0% by weight to 15.0% by weight, particularly preferably 8.0% by weight to 14.0% by weight % n-nonanol; - 12.8 wt% to 28.8% by weight, preferably 14.8% to 26.8% by weight, particularly preferably 15.8 wt% to 25.8% by weight of 6-methyl octanol; - 12.5 wt% to 28.8 wt% %, preferably 14.5 wt% to 26.5% by weight, particularly preferably 15.5 wt% to 25.5% by weight of 4-methyl octanol; - 3.3 wt% to 7.3 wt%, preferably 3.8 wt% to 6.8 wt%, especially Preferably from 4.3% to 6.3 % by weight of 2-methyl octanol; - from 5.7 % by weight to 11.7% by weight, preferably from 6.3 % by weight to 11.3% by weight, particularly preferably from 6.7 % by weight to 10.7% by weight of 3-B Heptoheptanol; -1.9% to 3.9% by weight, preferably 2.1% to 3.7% by weight, particularly preferably 2.4% to 3.4% by weight 2-ethylheptanol; - from 1.7% by weight to 3.7% by weight, preferably from 1.9% by weight to 3.5% by weight, particularly preferably from 2.2% by weight to 3.2% by weight of 2-propylhexanol; - 3.2% by weight to 9.2% % by weight, preferably from 3.7 to 8.7 % by weight, particularly preferably 4.2 % by weight to 8.2% by weight of 3,5-dimethylheptanol; - 6.0% by weight to 16.0% by weight, preferably 7.0% by weight to 15.0% by weight, particularly preferably 8.0% by weight to 14.0% by weight of 2,5 - dimethylheptanol; - 1.8% by weight to 3.8% by weight, preferably 2.0% by weight to 3.6% by weight, particularly preferably 2.3% by weight to 3.3% by weight of 2,3-dimethylheptanol; - 0.6 weight % 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; - 2.0% by weight to 4.0% by weight, preferably 2.2% by weight to 3.8% by weight, particularly preferably 2.5% by weight to 3.5% by weight of 2-ethyl-4-methylhexanol; - 0.5% by weight to 6.5% by weight, preferably 1.5% by weight to 6% by weight, Particular preference is given to from 1.5% by weight to 5.5% by weight of other alcohols having 9 carbon atoms; the limitation is that the components mentioned are in total 100% by weight.

Sterol

The isodecyl alcohol used to synthesize the diisononyl esters of the general formulae (I) and (II) contained in the plasticizer composition of the present invention is not a mono-type compound but is actually a different branched chain isomer A mixture of alcohols.

These materials are usually prepared by the trimming of propylene catalyzed by nickel or Buchholic acid, for example by the PolyGas® or EMOGAS® process as explained above, followed by means of a homogeneous ruthenium or cobalt carbonyl catalyst, preferably The resulting isodecene isomer mixture is hydroformylated with a cobalt carbonyl catalyst, and the resulting isoindolaldehyde isomer mixture is hydrogenated, for example by means of the catalysts mentioned above for the preparation of the C ₇ -C ₉ alcohol and Method (Ullmann's Encyclopedia of Industrial Chemistry; 5th Edition, Vol. A1, p. 293, VCH Verlagsgesellschaft GmbH, Weinheim 1985). The resulting isodecyl alcohol typically has a high degree of branching.

The 2-propylheptanol used in the synthesis of the plasticizer composition of the present invention comprising the bis-(2-propylheptyl)-ester of the formula (I) and (II) may be pure 2-propane. The hexaheptanol may be a mixture of propyl heptyl isomers of the type typically formed during industrial production of 2-propylheptanol and is also commonly referred to as 2-propylheptanol.

Pure 2-propylheptanol can be obtained via aldol condensation of n-pentanal and subsequent hydrogenation of the resulting 2-propylheptanal, for example according to US-A 2,921,089. By means of this preparation, in addition to the main component 2-propylheptanol, commercially available 2-propylheptanol typically comprises one or more of the following 2-propyl heptam isomers: 2- Propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-isopropyl-4-methyl-hexanol, 2-isopropyl- 5-methylhexanol and / or 2-propyl-4,4-dimethylpentanol. Other isomers of 2-propylheptanol may be present in 2-propylheptanol, such as 2-ethyl-2,4-dimethyl-hexanol, 2-ethyl-2-methylheptanol, and / or 2-ethyl-2,5-dimethylhexanol, but because of the lower formation rate of aldehyde precursors of such isomers in aldol condensation, the amount of such substances in 2-propylheptanol It is only a trace amount if it is completely present, and it does not actually affect the plasticizer properties of the compound produced by the mixture of such 2-propylheptanol isomers.

Different hydrocarbon sources can be used as starting materials for the preparation of 2-propylheptanol, such as 1-butene, 2-butene, raffinate I (alkane/olefin mixture), the raffinate I is moving In addition to propadiene, acetylene and diene, it is obtained from the C ₄ fraction of the cracker and it contains a large amount of isobutylene or raffinate II in addition to 1-butene and 2-butene, and the raffinate II is self-extracted. Residue I is obtained by removing isobutylene and thus contains only a small amount of isobutylene as an olefin component except 1-butene and 2-butene. Of course, it is also possible to use a mixture of raffinate I and raffinate II as a raw material for the preparation of 2-propylheptanol. These olefin or olefin mixtures can be hydroformylated by a conventionally known method using a cobalt or rhodium catalyst, and here 1-butene produces a mixture of n-pentanal and isovaleraldehyde, and the term isovaleraldehyde means a compound 2-methyl Butanal, the normal/iso ratio can vary within relatively wide limits depending on the catalyst used and the hydroformylation conditions. For example, when a homogeneous ruthenium catalyst (Rh/TPP) modified with triphenylphosphine is used, n-pentanal and isoprene are usually formed from 1-butene at a positive/iso ratio of 10:1 to 20:1. An aldehyde, and when a hydroquinone hydroformylation catalyst modified with a phosphite ligand is used, for example, according to US-A 5,288,918 or WO 05028407, or when a hydroformyl group modified with an amino phosphate ligand is used In the case of deuteration of the catalyst, for example, according to WO 0283695, almost only n-pentanal is formed. Although the Rh/TPP catalyst system converts only 2-butene very slowly in hydroformylation, and thus most of the 2-butene can be recovered from the hydroformylation mixture, 2-butene is referred to by the The ruthenium phosphate ligand or the phosphonium amine ligand modified rhodium catalyst successfully hydroformylated, and the main product formed is n-pentanal. In contrast, the isobutylene contained in the olefin feedstock is hydroformylated to 3-methylbutanal at different rates by virtually all catalyst systems, and in the case of some catalysts, to a lesser extent Valeraldehyde.

If necessary, the starting materials and catalysts can be used, either completely or to some extent by distillation, prior to the aldol condensation, depending on the starting materials and the isovaleraldehyde, 3-methylbutanal and/or pivalaldehyde. The C ₅ aldehyde obtained from n-pentanal is separated into individual components, and thus it is also possible here to influence and control the isomer composition of the C ₁₀ alcohol component of the ester mixture used in the process of the invention. Also, it is possible to introduce a C ₅ aldehyde mixture formed during hydroformylation into the aldol condensation without previously separating the individual isomers. If n-valeraldehyde is used for the aldol condensation, it can be carried out by means of a basic catalyst, such as an aqueous solution of sodium hydroxide or potassium hydroxide, for example by EP-A 366089, US-A 4426524 or US-A 5434313. the described method, 2-propyl heptanal condensate produced in the form of a unique, and if a mixture of isomers of C ₅ aldehyde used, the product comprising a homogeneous cross alcohols aldehydes same molecule aldol condensation products and isomers of different pentanal A mixture of isomers of an aldehyde condensation product. Of course, the aldol condensation can be controlled via a targeted reaction of the individual isomers in such a way that the single aldol condensation isomer is formed predominantly or completely. The relevant aldol condensate can then be hydrogenated using conventional hydrogenation catalysts (such as those mentioned above for the hydrogenation of aldehydes) to provide the corresponding alcohol or mixture of alcohols, usually in the foregoing, preferably separated from the reaction mixture by distillation and necessary At the time, after distillation and purification.

As mentioned above, the compounds of the formulae (I) and (II) contained in the plasticizer composition of the invention may be esterified with pure 2-propyl-heptanol. However, the preparation of such esters usually employs a mixture of the 2-propyl-heptanol and propylheptanol isomers mentioned, wherein the content of 2-propylheptanol is at least 50% by weight, preferably 60% by weight. From 98 to 98% by weight, and particularly preferably from 80% to 95% by weight, in particular from 85% to 95% by weight.

Suitable mixtures of 2-propylheptanol and propylheptanol isomers comprise, for example, from 60% to 98% by weight of 2-propylheptanol, from 1% to 15% by weight of 2-propyl-4 a mixture of methyl hexanol and 0.01% to 20% by weight of 2-propyl-5-methylhexanol and 0.01% to 24% by weight of 2-isopropylheptanol, wherein the individual components are The sum of the ratios does not exceed 100% by weight. Preferably, the proportion of the individual ingredients is 100% by weight in total.

Further suitable mixtures of 2-propylheptanol and propylheptanol isomers comprise, for example, from 75% to 95% by weight of 2-propylheptanol and from 2% to 15% by weight of 2-propyl- 4-methylhexanol, 1% to 20% by weight of 2-propyl-5-methylhexanol, 0.1% to 4% by weight of 2-isopropylheptanol, 0.1% to 2% by weight a mixture of 2-isopropyl-4-methylhexanol and 0.1% by weight to 2% by weight of 2-isopropyl-5-methylhexanol, wherein the sum of the individual components does not exceed 100% by weight . Preferably, the proportion of the individual ingredients is 100% by weight in total.

A preferred mixture of 2-propylheptanol and propylheptanol isomers comprises from 85% to 95% by weight of 2-propylheptanol, from 5% to 12% by weight of 2-propyl-4- Methyl hexanol and 0.1% to 2% by weight of 2-propyl-5-methylhexanol and 0.01% to 1% by weight of 2-isopropylheptanol, wherein the sum of the individual components does not exceed 100% by weight %. Preferably, the proportion of the individual ingredients is 100% by weight in total.

When the mentioned 2-propyl heptanol isomer mixture is used in place of pure 2-propylheptanol for the preparation of the compounds of the formulae (I) and (II), the alkyl ester groups and, individually, The isomer composition of the alkyl ether group corresponds in actual terms to the composition of the mixture of propylheptanol isomers used for esterification.

Undecyl alcohol

The undecyl alcohol used to prepare the compound of the formula (I) and (II) contained in the plasticizer composition of the present invention may be linear or branched, or may be linear or branched undecane. A mixture of alcohols. A mixture of branched chain undecyl alcohol (also known as is undecyl alcohol) is preferably used as the alcohol component.

Substantially linear undecyl alcohol can be obtained via 1-decene or preferably cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting n-undecaldehyde. The starting olefin 1-decene was produced by means of the previously mentioned SHOP process for the preparation of 1-octene.

For the preparation of the branched chain isoundecanool, the 1-decene obtained in the SHOP process can be subjected to skeletal isomerization, for example by means of an acidic zeolite molecular sieve, as described in WO 9823566, in which case heterogeneity is formed A mixture of terpenes, or a preferred cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting isoprene-aldehyde mixture produces a branched chain undecyl alcohol. This branched chain isoundecanoic alcohol is used to prepare the compounds of the formulae (I) and (II) used in the present invention. 1-decene or a mixture of iso-decene catalyzed by means of a rhodium or cobalt hydrosilyl acylated as previously may be C ₇ -C ₁₀ alcohols synthesis of the described implementations. Similar considerations apply to the hydrogenation of a mixture of n-undecaldehyde or isopentenal to give n-undecyl alcohol and isoundecanoic alcohol, respectively.

After the distillation purification of the hydrogenation product, the obtained C ₇ -C ₁₁ alkanol or a mixture thereof can be used as described above for the preparation of the compound (I) or the diester compound of the formula (II) used in the present invention.

Dodecanol

Substantially linear dodecanol can advantageously be obtained by means of the Alfol® process or the Epal® process. These methods include the oxidation and hydrolysis of linear linear trialkylaluminum compounds starting from triethylaluminum using Ziegler-Natta catalysts (Ziegler-Natta) The catalyst is gradually constructed by means of a plurality of ethylation reactions. N-dodecanol can be required resulting a different mixture of a substantially linear alcohol chain length of C ₁₂ obtained after distillation of the alkanol portion is discharged.

Alternatively, n-dodecanol can also be produced via hydrogenation of a natural fatty acid methyl ester (eg, from coconut oil).

The branched chain isododecyl alcohol can be similarly hydrolyzed and hydrogenated by a previous co-dimerization and/or oligomerization of an olefin (as described, for example, in WO 0063151) with a mixture of isececenes (eg eg The method described is obtained as described in DE-A 4339713. After the distillation purification of the hydrogenated product, the resulting isododecyl alcohol or a mixture thereof can be used as described above for the preparation of the compound (I) or the diester compound of the formula (II) used in the present invention.

Molding composition application

The molding composition of the present invention is preferably used for the production of molded articles and foils. Among them are outer casings and computer casings of electrical devices (such as kitchen appliances); tools; equipment; pipes; cables; hoses, such as plastic hoses, water hoses and irrigation hoses, industrial rubber hoses or chemical hoses; Wire sheath; window profile; conveyor profile, such as belt conveyor profile; vehicle construction component, such as body component, engine vibration damper; tire; furniture, such as chair, table or shelf; cushion foam and mattress Foam; tarpaulin, such as truck tarpaulin or tent cloth; roofing sheet; gasket; composite foil, such as foil for laminating safety glass, especially vehicle window and/or window pane; self-adhesive foil Sheet; laminated foil; recording disc; synthetic leather; packaging container; tape foil or coating.

The molding compositions of the present invention are also suitable for use in the production of molded articles and foils that are in direct contact with humans or food. They are mainly medical products, hygiene products, food or beverage packaging, indoor products, toys and child care items, sports and leisure products, clothing or textile fibers and the like.

Medical products that can be produced from the molded compositions of the present invention are, for example, tubing for enteral nutrition and hemodialysis, breathing tubes, infusion tubes, infusion bags, blood bags, catheters, trachea, disposable syringes, gloves or masks.

The package for food or drink that can be produced from the molded composition of the present invention is, for example, a frying foil, a food or drink hose, a drinking water pipe, a container for storing or freezing food or drink, a cover seal, a sealing cover, For crown stoppers or synthetic stoppers for wine.

Products for use in the interior sector that may be produced from the molded compositions of the present invention are, for example, floor coverings (which may have a homogeneous structure or may be constructed of a plurality of layers (e.g., at least one foamed layer), examples of which are floor coverings, sports flooring Or luxury vinyl tile (LVT), synthetic leather, wall covering or foamed or unfoamed wallpaper in a building or may be a cladding or console covering in a vehicle.

Examples of toys and childcare items that can be produced from the molded composition of the present invention Such as dolls, inflatable toys (such as balls), toy people, toy animals, educational anatomical models, modeling clays, swimming aids, baby carriage covers, baby replacement pads, warm beds, molar rings or bottles.

Sports and leisure products that can be produced from the molded compositions of the present invention are, for example, gymnastic balls or other balls, sports mats, cushions, massage balls and massage rollers, shoes and soles, air cushions or beverage bottles.

The garments that can be produced from the molded compositions of the present invention are, for example, (coated) woven fabrics, such as latex garments, protective garments; or rain gears, such as raincoats or rubber boots.

Non-PVC application

The present invention also includes the plasticizer composition of the present invention as an auxiliary agent selected from and/or used therein: calendering aid; rheological aid; surfactant composition such as a glidant and a film former , defoamers, defoamers, wetting agents, coalescents and emulsifiers; lubricants such as lubricating oils, greases and lubricating pastes; quenchers for chemical reactions; insensitive agents; pharmaceutical products; adhesives or Plasticizer in sealant; impact modifier, and standardized additives.

The embodiments and the figures described below provide further explanation of the invention. The embodiments and the drawings are not to be construed as limiting the invention.

The following examples are used in the following examples and figures: 638 for Palamoll® 638 and DINCH for Hexamoll® DINCH® (diisononyl cyclohexanedicarboxylate) phr representing parts by weight per 100 parts by weight of polymer.

figure 1:

Figure 1 shows a flexible PVC foil comprising 100 phr of a plasticizer composition for use according to the invention and (for comparison) comprising only commercially available plasticizers Hexamoll® DINCH® (DINCH) or Palamoll® 638 (638) Plasticizer compatibility for flexible PVC foils. The variables shown are the loss [percentage] of the dry weight as a function of test duration (storage time) [days].

The ingredients used in the examples are as follows:

I) Preparation Example

I.a) Preparation of polymeric plasticizer Palamoll® 638 (polymer plasticizer based on adipic acid, 1,2-propanediol and n-octanol)

6500 kg of adipic acid (commercially available product, for example, available from the manufacturer BASF SE, Ludwigshafen), 3207 kg of 1,2-propanediol (commercially available product, for example, available from the manufacturer BASF SE, Ludwigshafen), 1170 kg of n-octanol (commercially available) Products, such as available from the manufacturer Sasol, Johannesburg, South-Africa, and 0.5 kg of isopropyl n-butyl titanate (commercially available, for example, available from the manufacturer DuPont, Wilmington, US), are placed in a 15 m ³ reactor vessel. Heat to 130 ° C and homogenize by stirring. The reaction mixture was then heated to 175 ° C and stirred at standard pressure for 4 hours. The esterification in the case of removal of water begins at a temperature of about 150 °C. Water formed during the reaction is separated from the reaction mixture via distillation. The 1,2-propanediol and n-octanol distilled during the removal of distilled water are separated from the water and recycled back to the reaction vessel. The reaction mixture was then heated to 230 ° C, a pressure of 200 mbar was applied, and residual water was removed by passing a stream of nitrogen (2 m ³ /h) through the reaction mixture. After a total of 22 hours of stirring under these reaction conditions, the acid value of the reaction mixture dropped to a value of <15 mg KOH/g. The reaction mixture was then stirred at 230 ° C and 100 mbar while increasing the flow rate of the nitrogen stream to 30 m ³ /h and passing it through the reaction mixture to remove residual water and excess n-octanol. After stirring for 10 hours under these reaction conditions, the acid value of the reaction mixture dropped to a value of <1 mg KOH/g. Thereafter, the reaction product was filtered at 120 ° C to remove, in particular, the insoluble catalyst by-product.

The polymeric plasticizer produced in this manner contained 49 mol% of adipic acid unit, 42 mol% of 1,2-propanediol unit, and 9 mol% of n-octanol unit. The polymeric plasticizer had a density of 1.12 g/cm ³ at 20 ° C, a dynamic viscosity of 9000 mPa*s at 20 ° C, and a refractive index nD 20 of 1.467.

II) Preparation and testing of a flexible PVC foil formulation produced using the plasticizer composition of the present invention and using a commercially available plasticizer:

Formulation:

II.a) Preparation of flexible PVC foil

150 g of PVC (homopolymeric suspension PVC, trade name Solvin® 271 SP), 150 g of plasticizer composition and 2 g of Ba/Zn stabilizer (trade name Reagens® SLX/781) were mixed using a hand mixer at room temperature. The mixture was then plasticized onto an oil heated laboratory mixing roll bed (Collin, automatic roll type 150, diameter: 252 mm, width: 450 mm) and processed into a grinding plate. The temperature of the two rolls was in each case 180 ° C; rotation speed of 15 rev / min (front roll) and 12 rev / min (rear roll); rotation time of 5 minutes. This gives a thickness of 0.53mm of the grinding plate. After cooling, at 190 ° C temperature After 180 seconds under 150 bar pressure The polishing plate was pressed from a press of Collin type "Laboratory Plate Press 400 P" to obtain a flexible PVC foil having a thickness of 0.50 mm.

II.b) Testing the compatibility of plasticizers in flexible PVC foils

Research purposes

This test is used to quantify the compatibility of plasticizers in flexible PVC formulations. It is carried out at high temperature (70 ° C) and 100% relative humidity. Information obtained from the storage time assessment.

Test sample:

This test was carried out using a test sample (foil) having a size of 75 x 110 x 0.5 mm. The foil is perforated, engraved (soldered iron) and weighed on the wider side.

Test Equipment:

A Testotherm thermometer with a sensor for indoor measurement in a Heraeus drying oven, analytical balance, and drying oven at 70 °C.

program:

The temperature inside the drying oven was set to the required 70 °C. The prepared weighed foil was suspended on a wire frame and inserted into a glass tank (fully demineralized water) filled with about 5 cm of water. It should be noted that it is ensured that the foils do not touch each other. The lower edge of the foil should not be suspended into the water. The glass tank is sealed with a polyethylene foil to make the water vapor impermeable so that the water vapor generated in the subsequent glass tank cannot escape. The water content in the glass pool is monitored daily and any water lost is replaced.

Storage time

After day 7, day 14, and day 28, two foils were removed from the glass tank and conditioned in air for one hour in free suspension. The foil surface is then cleaned using methanol. The foil was then dried in free suspension at 70 ° C for 16 hours in a dry box with forced convection. After removal from the drying oven, the foil was adjusted in free suspension for one hour and then weighed. The data reported in each case is the arithmetic mean of the weight loss of the foil.

result

Figure 1 shows the results of the compatibility test using the plasticizer compositions of the present invention (Examples 1 to 3) and the PVC foil produced using the pure polymer or monomer plasticizer (Comparative Examples 1 to 2). . The parameters shown are the loss [percentage] of the dry weight as a function of test duration (storage time) [days].

As can be clearly seen in Figure 1, the pure polymer plasticizer, Palamoll® 638, has an extremely poor compatibility with PVC. The weight loss in the compatibility test after 28 days was almost 18%. For the same total plasticizer content of 100 phr, the addition of just 20 phr of Hexamoll® DINCH® resulted in a significant reduction in the weight loss of the plasticizer by almost half, so the compatibility was significantly improved. By further increasing the amount of Hexamoll® DINCH® added, the weight loss in the compatibility test can be further reduced in greater proportions for the same total plasticizer content.

Claims (23)

A plasticizer composition comprising: a) one or more compounds of formula (I), Wherein X is independently of each other an unbranched chain or a branched chain C ₂ -C ₈ alkyl group or an unbranched chain or a branched chain C ₂ -C ₈ extending alkenyl group containing at least one double bond, and Y is an unbranched chain or branch chain C ₂ -C ₁₂ alkylene containing at least one double bond or unbranched or branched C ₂ -C ₁₂ alkenylene group, a is an integer of from 1 to 100, and, R ¹ each independently selected from unbranched a chain or branched C ₄ -C ₁₂ alkyl radical, wherein the groups X present in the compound (I) may be the same or different, and wherein the compound (I) contains more than one group Y The groups may be the same or different; b) one or more compounds of the formula (II), Wherein R ² and R ³ are independently of each other selected from the group consisting of a branched chain and an unbranched chain C ₇ -C ₁₂ alkyl radical. The plasticizer composition of claim 1, wherein the weight of the compound (I) The average molar mass is in the range of 500 to 15,000. The plasticizer composition according to any one of claims 1 to 2, wherein in the compound of the formula (I), X is independently of each other a branched or unbranched chain C ₂ -C ₆ An alkyl group, and Y is a branched or unbranched chain C ₂ -C ₅ alkyl. The plasticizer composition of claim 1 to 3, wherein the groups X present in the compound (I) are the same, and the compounds (I) comprise more than one group Y, which may Same or different. A plasticizer composition according to any one of the preceding claims, wherein R ^{1 in} the compound of the formula (I) is independently n-octyl, isooctyl, 2-ethylhexyl, n-decyl , isodecyl, 2-propylhexyl, n-decyl, isodecyl or 2-propylheptyl. A plasticizer composition according to any one of the preceding claims, wherein the two groups R ¹ in the compound of the formula (I) are all n-octyl, are isodecyl or both are 2-prop. Gheptylene. A plasticizer composition according to any one of the preceding claims, wherein R ² and R ³ in the compound of the formula (II) are both 2-ethylhexyl, are isodecyl or both are 2- Propyl heptyl. A plasticizer composition according to any one of the preceding claims, wherein the plasticizer composition may optionally comprise other plasticizers different from the compounds (I) and (II), and is selected from the group consisting of: Alkyl aralkyl phthalate, trialkyl trimellitate, alkyl benzoate, dibenzoate of diol, 1,2-cyclohexane in addition to compound (II) Carboxylic acid ester, 1,3-cyclohexanedicarboxylate, 1,4-cyclohexanedicarboxylate, hydroxybenzoate, saturated monocarboxylic acid ester, unsaturated monocarboxylic acid ester, saturated dicarboxylic acid Acid esters, unsaturated dicarboxylic acid esters, decylamines and esters of aromatic sulfonic acids, alkyl sulfonates, glycerol esters, isosorbide esters, phosphate esters, citrate triesters, alkyl pyrrolidone Derivative, 2,5-furandicarboxylate, 2,5-tetrahydrofuran dicarboxylate, ring A monoalkyl ester of an oxidized vegetable oil and an epoxidized fatty acid and a polyester of an aliphatic and/or aromatic polycarboxylic acid and at least a glycol other than the compound (I). A plasticizer composition according to any one of the preceding claims, wherein the amount of the compound of the formula (I) in the plasticizer composition is from 10% by weight to 99% by weight. A plasticizer composition according to any one of the preceding claims, wherein the amount of the compound of the formula (II) in the plasticizer composition is from 1% by weight to 90% by weight. A plasticizer composition according to any one of the preceding claims, wherein the weight ratio of the compound of the formula (II) to the compound of the formula (I) is in the range of 1:100 to 10:1. A molding composition comprising at least one polymer and a plasticizer composition according to any one of claims 1 to 11. The molding composition of claim 12, wherein the polymer is a thermoplastic polymer selected from the group consisting of homopolymers or copolymers comprising at least one copolymerized monomer selected from the group consisting of C ₂ - C ₁₀ monoolefin, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and C ₂ -C ₁₀ alkyl ester thereof, vinyl chloride, vinylidene chloride, vinylidene fluoride, Tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylate and methacrylate of C ₁ -C ₁₀ alcohol, arylethylene, (meth)acrylonitrile, maleic anhydride and α,β - olefinically unsaturated monocarboxylic acids and dicarboxylic acids, homopolymers and copolymers of vinyl acetals, polyvinyl esters, polycarbonates, polyesters, polyethers, polyether ketones, thermoplastic polyurethanes, Polysulfides, polyfluorenes, polyether oximes, cellulose alkyl esters, and mixtures thereof. The molding composition of claim 13, wherein the thermoplastic polymer is selected from the group consisting of polyvinyl chloride (PVC), polyvinyl butyral (PVB), homopolymers and copolymers of vinyl acetate, and styrene. Homopolymers and copolymers, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides. The molding composition according to any one of claims 13 to 14, wherein the thermoplastic polymer is polyvinyl chloride (PVC). The molding composition of claim 15, wherein the plasticizer composition is in an amount of from 5.0 phr to 300 phr. The molding composition according to any one of claims 13 to 14, comprising at least one thermoplastic polymer other than polyvinyl chloride, wherein the amount of the plasticizer composition in the molding composition It is from 0.5 phr to 300 phr. The molding composition of claim 12, wherein the polymer is an elastomer, preferably selected from the group consisting of natural rubber, synthetic rubber, and mixtures thereof. The molding composition of claim 18, wherein the amount of the plasticizer composition in the molding composition is from 1.0 phr to 60 phr. A use of a plasticizer composition according to any one of claims 1 to 11, which is used as a plasticizer for thermoplastic polymers and elastomers. A use of a molding composition according to any one of claims 12 to 19 for producing a molded article and a foil, such as an outer casing of an electric device, a computer casing, a tool, a pipe, a cable, Hose, wire sheath, window profile, conveyor profile, vehicle construction component, tire, furniture, gasket foam and mattress foam, tarpaulin, roofing sheet, gasket, composite foil, self-adhesive Foil, laminated foil, recording disc, synthetic leather, packaging container, tape foil or coating. A use of a molding composition according to any one of claims 12 to 19 for producing a molded article and a foil which are in direct contact with a person or a food. For example, the application of the scope of claim 22, wherein the molded articles and foils directly in contact with humans or foods are medical products, sanitary products, food or beverage packaging, indoor products, toys and childcare articles, sports and leisure. Product, clothing or textile fibers.