DE102015206645A1 - Use of modified fatty acid esters as plasticizer - Google Patents

Abstract

Compounds of the general formula (I) are useful as plasticizers for thermoplastic polymers such as PVC and elastomers such as rubber, wherein Q is the radical of an n-valent alcohol, where n has a value of 1 to 6 and m has a value of 1 to n R1 is a hydrocarbon radical of 8 to 30 carbon atoms and R2 is a hydrocarbon radical of 8 to 30 carbon atoms wherein at least one CC bond is fused to a butyrolactone moiety.

Description

The invention relates to the use of modified fatty acid esters as plasticizers for thermoplastic polymers, in particular for polyvinyl chloride, and a molding composition containing at least one modified fatty acid ester.

Polyvinyl chloride (PVC) is one of the most widely used thermoplastic polymers. It is flame retardant, resistant to chemicals and corrosion resistant. The properties of PVC can be varied with the help of plasticizers within wide limits. Depending on the amount of plasticizer, a distinction is made between rigid PVC (less than 10% plasticizer) and soft PVC (more than 10% plasticizer). The plasticizers are mainly phthalic acid esters, in particular di-n-butyl phthalate (DBP), diisobutyl phthalate (DIBP), di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and benzyl butyl phthalate (BBP). In addition, cyclohexanedicarboxylic be used for some time because of their toxicological favorable properties, such as Diisononylcyclohexandicarboxylat (BASF "Hexamoll ^® DINCH ^®"). Of minor importance are esters of adipic acid and other organic acids as well as esters of phosphoric acid.

For the use of plasticizers in particular their gelling behavior for PVC is important. Gelling behavior is the ability of a plasticizer to penetrate the polymeric structure of the PVC and to cause a softening effect by reducing the interactions between the polymer chains. A measure of the gelling behavior of a plasticizer is the dissolving temperature for PVC, which after DIN 53408 is determined. The lower the dissolution temperature, the better the gelling behavior. Plastisols are initially a suspension of fine-powdered plastics in liquid plasticizers. The rate of dissolution of the polymer in the plasticizer at ambient temperature is very low. Only when heated to higher temperatures, the polymer dissolves noticeably in the plasticizer. The individual isolated plastic aggregates swell and fuse to a three-dimensional highly viscous gel. This process is referred to as gelling and takes place at a certain minimum temperature, referred to as the gelling or dissolving temperature. The gelation step is not reversible.

Since plastisols are in liquid form, they are very often used to coat a wide variety of materials, such as e.g. Textiles, glass fleeces, etc. used. The coating is very often composed of several layers. In practice, when plastisol products are processed, therefore, a layer of plastisol is often applied, and the plastic, in particular PVC, is directly gelated with the plasticizer above the dissolution temperature, ie a solid layer consisting of a mixture of gelled, partially gelled and ungelled plastic particles. The next layer is then applied to this gelled layer and, after application of the last layer, the entire structure is completely processed by heating to higher temperatures to form the completely gelled plastic product.

In addition to plastisols, dry powdery mixtures of plasticizers and plastics can also be produced. Such dry blends, especially based on PVC, can then be used at elevated temperatures e.g. be further processed by extrusion into a granulate or processed by conventional molding processes, such as injection molding, extrusion or calendering to fully gelled plastic product.

In particular, in the production and processing of PVC plastisols, for example for the production of PVC coatings, it is among other things desirable to have available a plasticizer with the lowest possible gelling temperature and low viscosity as a gelling aid. In addition, a high storage stability of the plastisol is desired, i. the ungelled plastisol should have no or only a slight increase in viscosity with time at ambient temperature. If possible, these properties should be achieved by adding a suitable plasticizer with rapid gelation properties, which should eliminate the need for further viscosity-reducing additives and / or solvents.

To set the desired properties is also known to use mixtures of plasticizers, for. At least one plasticizer which imparts good thermoplastic properties but poorly gelled, in combination with at least one gelling aid.

The object of the invention is to provide alternative plasticizers and plasticized molding compositions for replacing the phthalate plasticizers, since these are toxicologically unobjectionable are. This is especially true for sensitive applications such as children's toys, food packaging or medical items. In particular, the invention is directed to plasticizers with good gelling behavior and low dissolution temperature. The processing temperatures can be chosen lower in the production of flexible PVC, the better the gelling behavior or the lower the dissolving temperature of the plasticizer. Low temperatures save energy and time.

Various alternative plasticizers for various plastics and especially for PVC are known in the prior art.

A plasticizer class known from the prior art which can be used as an alternative to phthalates is based on cyclohexanepolycarboxylic acids as described in US Pat WO 99/32427 are described. In contrast to their unhydrogenated aromatic analogues, these compounds are toxicologically harmless and can also be used in sensitive applications. The corresponding lower alkyl esters generally have fast gelling properties.

The WO 00/78704 describes selected dialkylcyclohexane-1,3- and 1,4-dicarboxylic acid esters for use as plasticizers in synthetic materials.

The US Pat. No. 7,973,194 B1 teaches the use of dibenzylcyclohexane-1,4-dicarboxylate, benzylbutylcyclohexane-1,4-dicarboxylate and dibutylcyclohexane-1,4-dicarboxylate as fast-gelling plasticizers for PVC.

The use of fatty acid esters as plasticizing additives is described in US Pat US 08/0139702 A1 describe. Often, the fatty acid esters are modified to obtain better product properties. The US 6,797,753 and the US 06/0135666 A1 describe the use of epoxidized fatty acid esters as plasticizers for PVC polymers. Other modified fatty acids are used in the US 2,969,339 and in the US 4,289,668 described.

worin
Q für den Rest eines n-wertigen Alkohols steht, wobei n einen Wert von 1 bis 6 und m einen Wert von 1 bis n hat,
R¹ für einen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen steht,
R² für einen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen steht, worin wenigstens eine C-C-Bindung mit einer Butyrolactoneinheit der allgemeinen Formel (II) anelliert ist,

worin
- - - - für die anellierte Bindung steht,
eines der Symbole X, Y für ein Sauerstoffatom und das andere für eine CHR-Gruppe steht, worin R für H oder einen unsubstituierten oder substituierten C₁-C₁₃-Alkylrest steht.The invention relates to the use of a compound of general formula (I) as a plasticizer for thermoplastic polymers and elastomers,

wherein
Q is the radical of an n-valent alcohol, where n has a value of 1 to 6 and m has a value of 1 to n,
R ^{1 is} a hydrocarbon radical having 8 to 30 carbon atoms,
R ^{2 is} a hydrocarbon radical having 8 to 30 carbon atoms, wherein at least one CC bond is fused with a butyrolactone unit of the general formula (II),

wherein
- - - - stands for the fused bond,
one of the symbols X, Y is an oxygen atom and the other is a CHR group, wherein R is H or an unsubstituted or substituted C ₁ -C ₁₃ alkyl radical.

Preferably, the concentration of butyrolactone units of the formula (II) in the compound of the formula (I) is 0.2 to 5.0 mmol / g, preferably 1.0 to 5.0 mmol / g, particularly preferably 1.5 to 5 , 0 mmol / g, based on the mass of the compound of formula (I).

Another object of the invention are molding compositions containing at least one thermoplastic polymer, and at least one compound of general formula (I), as defined above and hereinafter.

Because of their physical properties, compounds of the formula (I) are suitable as plasticizers or as components of a plasticizer composition for thermoplastic polymers, in particular for PVC.

Compounds of formula (I) allow due to the low dissolution temperatures DIN 53408 the use as gelling aid. Compounds of formula (I) are thus useful for reducing the temperature required to gel a thermoplastic polymer and / or increasing the gelling rate.

Compounds of the formula (I) are distinguished by a very good compatibility of the compound (I) with a large number of different plasticizers. The compounds of the formula (I) are particularly suitable in combination with conventional plasticizers for improving the gelling behavior.

Compounds of formula (I) allow the preparation of plastisols.

The use according to the invention of the compounds of the formula (I) enables the production of moldings and films for sensitive fields of application, such as medical products, food packaging, products for the interior sector, for example of apartments and vehicles, toys, childcare articles, etc.

For the preparation of the compounds of the formula (I) used according to the invention readily accessible starting materials can be used. A particular economic and ecological advantage of the present invention lies in the possibility of being able to use both available in large quantities petrochemical raw materials, as well as renewable raw materials in the production of the compounds used in the invention. Thus, for example, the starting materials of the fatty acid esters are available from naturally occurring carbohydrates, such as fats and oils, whereas the carboxylic acids used to introduce the butyrolactone units are available from industrial processes. So on the one hand, the need for "sustainable" products can be covered, on the other hand, however, an economical production is possible.

The processes for the preparation of the compounds of the formula (I) used according to the invention are simple and efficient, whereby they can easily be provided on a large scale.

Surprisingly, as mentioned above, it has been found that the compounds of the general formula (I) have very low dissolving temperatures and excellent gelling properties in the production of plastisols, in particular of PVC plastisols. Thus, their dissolution temperatures are below the dissolution temperatures of the corresponding dialkyl esters of cyclohexanedicarboxylic acid or phthalic acid and have at least equal fast-gelling properties. Thus, for example, the 1,2-cyclohexanedicarboxylic acid diisononylester with a solution temperature of 151 ° C after DIN 53408 and diisononyl phthalate having a dissolution temperature of 132 ° C higher values.

In the context of the present invention, a gelling aid is understood as meaning a plasticizer which gives a dissolving temperature DIN 53408 of less than 120 ° C. Such gelling aids are used in particular for the production of plastisols.

In the general formula (I), Q represents the residue of an n-valent alcohol. By "n-valent alcohol" is meant a molecule having n hydroxyl groups. Q stands for the remainder of the molecule without the hydroxyl groups of the alcohol. In the general formula (I), n has a value of 1 to 6, preferably 1 to 3.

Suitable monohydric alcohols (n = 1) are, for example, C ₁ -C ₁₃ -alkanols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, ethylhexyl alcohol, dodecyl alcohol or stearyl alcohol; C ₁ -C ₁₃ alkoxy C ₂ -C ₁₃ alkanols such as ethylene glycol monomethyl ether; or aromatic alcohols, such as benzyl alcohol or phenol.

Suitable dihydric alcohols (n = 2) are, for example, C ₂ -C ₈ -alkanediols, such as ethylene glycol, propylene glycol or 1,4-butanediol.

A particularly preferred trihydric alcohol (n = 3) is glycerin.

At least one hydroxyl group of the n-valent alcohol carries an acyl radical (CO) R ² , the remaining hydroxyl groups optionally carry acyl radicals (CO) R ¹ or (CO) R ² .

R ¹ is a hydrocarbon radical having 8 to 30 carbon atoms. In addition to carbon and hydrogen atoms, the radical R ^{1 may} comprise oxygen atoms.

Preferably, the radical (CO) R ^{1 is} a natural fatty acyl radical. The fatty acyl radical may comprise a saturated, monounsaturated, polyunsaturated, epoxy group-substituted and / or hydroxy-substituted hydrocarbon chain. In certain embodiments, the fatty acyl radical is selected from oleic acid and rapeseed oil fatty acids.

worin
- - - - für die anellierte Bindung steht,
eines der Symbole X, Y für ein Sauerstoffatom und das andere für eine CHR-Gruppe steht, worin R für H oder einen unsubstituierten oder substituierten C₁-C₁₃-Alkylrest steht. Wenn R für einen substituierten C₁-C₁₃-Alkylrest steht, kann dieser einen, zwei oder drei Substituenten tragen, die unter Hydroxyl, Hydroxycarbonyl und C₁-C₁₃-Alkoxycarbonyl ausgewählt sind.R ² is a hydrocarbon radical having 8 to 30 carbon atoms, wherein at least one CC bond is fused with a butyrolactone unit of the general formula (II),

wherein
- - - - stands for the fused bond,
one of the symbols X, Y is an oxygen atom and the other is a CHR group, wherein R is H or an unsubstituted or substituted C ₁ -C ₁₃ alkyl radical. When R is a substituted C ₁ -C ₁₃ alkyl radical, it may bear one, two or three substituents selected from hydroxyl, hydroxycarbonyl and C ₁ -C ₁₃ alkoxycarbonyl.

By "fused bond" is meant a C-C bond which is simultaneously part of the hydrocarbon chain of R ² and the butyrolactone moiety of formula (II). The carbon atom number of 8 to 30 of the radical R ² is understood as including the two carbon atoms of the fused bond, but excluding the remaining atoms of the butyrolactone unit of the formula (II). In addition to carbon and hydrogen atoms, the radical R ^{2 may} comprise oxygen atoms.

Preferably, the radical (CO) R ^{2 is} obtainable by reacting an unsaturated fatty acyl radical with an enolizable carboxylic acid in the presence of a transition metal salt. For this purpose, a precursor compound of the compound of the formula (I) which comprises an unsaturated fatty acyl radical instead of the radical (CO) R ^{2 is} expediently reacted with an enolizable carboxylic acid in the presence of a transition metal salt. Suitable precursor compounds are esters of the fatty acids mentioned below, such as natural triglycerides or their transesterification products.

Suitable unsaturated fatty acyl radicals are radicals of mono- or polyunsaturated fatty acids, such as, for example, of: undecenylic acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid; Linoleic acid, α-linolenic acid, γ-linolenic acid, calendic acid, punicic acid, α-elinostatin acid, arachidonic acid, eicosa-pentaenoic acid, docosapentaenoic acid, docosahexaenoic acid; Vernolic acid, or ricinoleic acid.

By "enolizable carboxylic acid" is meant a carboxylic acid having a CH-acidic H atom in the α-position to the carboxy group. As the carboxylic acid, α-unsubstituted or α-mono- substituted mono- and dicarboxylic acids, such as: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, lignoic acid, cerotic acid, montanic acid, Melissinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, the already mentioned monounsaturated or polyunsaturated fatty acids or mixtures of these carboxylic acids. Acetic acid is a preferred enolizable carboxylic acid. Partial esters of polycarboxylic acids are also suitable.

The transition metal salt is suitably selected from salts, e.g. Carboxylates, of manganese (III), cerium (IV) and vanadium (V), e.g. under manganese (III) acetate, cerium (IV) acetate and vanadium (V) acetate. The transition metal salt is usually used in at least a stoichiometric amount, for example 1.5 to 5 times the molar amount, based on the compound comprising at least one unsaturated fatty acyl group.

Suitable reaction temperatures are e.g. from 80 to 180 ° C.

The reaction of the C-C double bonds contained in the fatty acyl group is preferably complete but may be incomplete. In this case, the product still has C-C double bonds. These unreacted C-C double bonds can be hydrogenated in a conventional manner.

The compounds of the formula (I) can be prepared by the addition of carboxylic acids to fatty acid esters or to mixtures of different fatty acid esters analogously to those disclosed in the publication of EI Heiba, RM Dessau and PG Rodewald (J. Am. Chem. Soc. 1974, 7977) be prepared method described. Since the radical butyrolactone synthesis has no clear regioselectivity, mixtures of different products are formed. These product mixtures are defined by the carbon skeleton positions indicated by X and Y in the general formula (II).

The reaction is illustrated below by the reaction of oleic acid methyl ester with acetic acid:

If a triglyceride (3) is reacted instead of oleic acid methyl ester, a triglyceride mixture is obtained in which the unsaturated fatty acid units have been converted to the corresponding β, γ-disubstituted γ-butyrolactones, as illustrated below:

Preferably, the product of the metal salt-mediated reaction is used without further chemical modification as a plasticizer for thermoplastic polymers.

In all cases, the product obtained may occur as a mixture of different compounds. Especially when using vegetable oils as starting material, which consist of several fatty acid units, mixtures of different triglycerides are obtained. Such blends can be used without further purification as plasticizers for thermoplastic polymers.

Another object of the present invention relates to a molding composition containing at least one polymer and at least one compound of general formula (I).

• – Homo- und Copolymeren, die in einpolymerisierter Form wenigstens ein Monomer enthalten, das ausgewählt ist unter C₂-C₁₀ Monoolefinen, wie beispielsweise Ethylen oder Propylen, 1,3-Butadien, 2-Chlor-1,3-Butadien, Vinylalkohol und dessen C₂-C₁₀-Alkylestern, Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid, Tetrafluorethylen, Glycidylacrylat, Glycidylmethacrylat, Acrylaten und Methacrylaten mit Alkoholkomponenten von verzweigten und unverzweigten C₁-C₁₀-Alkoholen, Vinylaromaten wie beispielsweise Polystyrol, (Meth)acrylnitril, α,β-ethylenisch ungesättigten Mono- und Dicarbonsäuren, und Maleinsäureanhydrid;
• – Homo- und Copolymere von Vinylacetalen;
• – Polyvinylestern;
• – Polycarbonaten (PC);
• – Polyestern, wie Polyalkylenterephthalaten, Polyhydroxyalkanoaten (PHA), Polybutylensuccinaten (PBS), Polybutylensuccinatadipaten (PBSA);
• – Polyethern;
• – Polyetherketonen;
• – thermoplastischen Polyurethanen (TPU);
• – Polysulfiden;
• – Polysulfonen;

und Mischungen davon.Suitable thermoplastic polymers are all thermoplastically processable polymers. In particular, these thermoplastic polymers are selected from:

• Homo- and copolymers containing in copolymerized form at least one monomer selected from C ₂ -C ₁₀ monoolefins, such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C ₂ -C ₁₀ -alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched and unbranched C ₁ -C ₁₀ -alcohols, vinylaromatics such as polystyrene, (meth) acrylonitrile, α, β-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride;
• - Homo- and copolymers of vinyl acetals;
• - polyvinyl esters;
• - polycarbonates (PC);
• Polyesters, such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA);
• - polyethers;
• - polyether ketones;
• - thermoplastic polyurethanes (TPU);
• - polysulfides;
• - polysulfones;

and mixtures thereof.

Examples include polyacrylates having identical or different alcohol radicals from the group of C ₄ -C ₈ alcohols, especially butanol, hexanol, octanol and 2-ethylene hexanol, polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrile-butadiene-styrene Copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene Methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMA), polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), polycaprolactone (PCL), polyhydroxybutyric acid (PHB ), Polyhydroxyvaleric acid (PHV), polylactic acid (PLA), ethylcellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose acetate / butyrate (CAB).

The at least one thermoplastic polymer contained in the molding composition according to the invention is preferably polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides ,

In particular, the at least one thermoplastic polymer contained in the molding composition according to the invention is polyvinyl chloride (PVC).

Polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl chloride (PVC) used in the present invention can be prepared by, for example, suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization. The production of PVC by polymerization of vinyl chloride and the preparation and composition of plasticized PVC are described, for example, in US Pat "Becker / Braun, Plastics Handbook, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Munich ,

The K value, which characterizes the molecular weight of the PVC and after DIN 53726 is determined, is for the plasticized PVC according to the invention usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 75.

In the context of the invention, the content (% by weight) of PVC of the mixtures is from 20 to 99%, preferably 45 to 95%, particularly preferably 50 to 90% and in particular 55 to 85%.

Another object of the present invention relates to molding compositions comprising at least one elastomer and at least one compound of general formula (I).

The elastomer contained in the molding compositions according to the invention is preferably at least one natural rubber (NR), at least one synthetic rubber or mixtures thereof. Preferred synthetically prepared rubbers are, for example, polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile-butadiene rubber (NBR) or chloroprene rubber (CR).

Preference is given to rubbers or rubber mixtures which can be vulcanized with sulfur.

In the context of the invention, the content (% by weight) of elastomer in the molding compositions is 20 to 99%, preferably 45 to 95%, particularly preferably 50 to 90% and in particular 55 to 85%.

In addition to at least one thermoplastic polymer or an elastomer and at least one compound of general formula (I), at least one plasticizer other than compounds of formula (I) may be present in the molding composition of the invention.

Suitable plasticizers other than compounds of formula (I) are selected from phthalic acid alkyl esters, phthalic acid alkylaralkyl esters, terephthalic acid dialkyl esters, trialkyl trimellitates, dialkyl adipates, alkyl benzoates, glycol dibenzoates, hydroxybenzoic esters, esters of saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids, amides and esters of aromatic sulfonic acids, alkyl sulfonic acid esters, glycerol esters, isosorbide esters, phosphoric acid esters, citric acid triesters, alkylpyrrolidone derivatives, 2,5-furandicarboxylic esters, epoxidized vegetable oils based on triglycerides and saturated or unsaturated fatty acids, polyesters of aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols.

The content of compounds of the formula (I) in the molding compositions according to the invention - stated in phr - may generally be from 5 to 100 phr, preferably from 10 to 60 phr and more preferably from 20 to 50 phr. The formulation recipe "phr" common for polymer compositions is the abbreviation for "parts per hundred resin" and means that additives are not weighed, measured and reported in terms of their percentage in the total mass, but as parts by weight per 100 parts by weight of polymer. For example, if the compound of formula (I) is present in the PVC / plasticizer mixture in the weight ratio PVC: plasticizer of 80:20, then the content of ester mixture is 25 phr, since 20 parts make up 25% of 80 parts.

Depending on which thermoplastic polymer or thermoplastic polymer mixture is contained in the molding composition, different amounts of plasticizer are used. In general, the total plasticizer content in the molding composition is 0.5 to 300 phr (per hundred resin = parts by weight per hundred parts by weight polymer), preferably 0.5 to 130 phr, particularly preferably 1 to 35 phr.

If the thermoplastic polymer in the molding compositions according to the invention is polyvinyl chloride, the total plasticizer content in the molding compound is 1 to 400 phr, preferably 5 to 130 phr, more preferably 10 to 100 phr and in particular 15 to 85 phr.

If the polymer in the molding compounds according to the invention is rubbers, the total plasticizer content in the molding compound is 1 to 60 phr, preferably 1 to 40 phr, particularly preferably 2 to 30 phr.

In the context of the invention, the molding compositions containing at least one elastomer may contain, in addition to the above ingredients, other suitable additives. For example, reinforcing fillers such as carbon black or silica, other fillers, a methylene donor such as hexamethylenetetramine (HMT), a methylene acceptor such as cardanol (cashew nut) modified phenolic resins, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, activators , various types of oil, anti-aging agents and other various additives blended into, for example, tire and other rubber compounds.

In the context of the invention, the molding compositions containing at least one thermoplastic polymer may contain other suitable additives. For example, stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents or biostabilizers may be included.

In the following, some suitable additives are described in more detail. However, the examples listed do not represent a restriction of the molding compositions according to the invention, but are merely illustrative.

Stabilizers, for example, neutralize the hydrochloric acid split off from PVC during and / or after processing, or counteract PVC degradation as free-radical scavengers.

Suitable stabilizers are all customary PVC stabilizers in solid and liquid form, for example customary Ca / Zn, Ba / Zn, Pb or Sn stabilizers and also acid-binding phyllosilicates such as hydrotalcite. Preference is given to Ba / Zn stabilizers, tribasic lead sulfate (3 PbO.PbSO ₄ .H ₂ O) and lead phosphite, particularly preferably tribasic lead sulfate and lead phosphite. Radical scavengers exemplified dibutyltin maleate.

The molding compositions according to the invention may have a content of stabilizers of from 0.05 to 7 phr, preferably from 0.1 to 5 phr, more preferably from 0.2 to 4 phr and in particular from 0.5 to 3 phr.

Lubricants should be effective in the processing between the PVC pastilles and the hot machine parts and counteract frictional forces in mixing, plasticizing and deforming.

As a lubricant, the molding compositions according to the invention may contain all the lubricants customary for the processing of plastics, in particular thermoplastic polymers. For example, hydrocarbons such as oils, paraffins and polyethylene waxes, fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids such as fatty acids and montanic acid, oxidized polyethylene wax, metal salts of carboxylic acids, carboxylic acid amides and carboxylic acid esters, for example, with the alcohols ethanol, Fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as the acid component.

The molding compositions according to the invention may have a content of lubricant of from 0.01 to 10 phr, preferably from 0.05 to 5 phr, more preferably from 0.1 to 3 phr and in particular from 0.2 to 2 phr.

In particular, fillers have a positive influence on the compressive, tensile and flexural strength as well as the hardness and heat resistance of plasticized PVC.

In the context of the invention, the molding compositions fillers such as carbon black and other organic fillers such as natural calcium carbonates such as chalk, limestone and marble, synthetic calcium carbonates, dolomite, silicates, silica, sand, diatomaceous earth, aluminum silicates such as kaolin, mica and feldspar. Preference is given to using as fillers, calcium carbonates, chalk, dolomite, kaolin, silicates, talc or carbon black.

The molding compositions according to the invention may have a content of fillers of from 0.01 to 100 phr, preferably from 0.1 to 60 phr, more preferably from 0.5 to 50 phr and in particular from 1 to 40 phr.

The molding compositions according to the invention may also contain pigments in order to adapt the product obtained to different possible uses.

In the context of the present invention, both inorganic pigments and organic pigments can be used. As inorganic pigments, for example, titanium pigments such as TiO ₂ , cadmium pigments such as CdS, cobalt pigments such as CoO / Al ₂ O ₃ , and chromium pigments such as Cr ₂ O ₃ can be used. Suitable organic pigments are, for example, monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine pigments and aniline pigments.

The molding compositions according to the invention may have a content of pigments of from 0.01 to 10 phr, preferably from 0.05 to 5 phr, more preferably from 0.1 to 3 phr and in particular from 0.5 to 2 phr.

In order to reduce the flammability and reduce the smoke during combustion, the molding compositions according to the invention may also contain flame retardants.

For example, antimony trioxide, phosphoric acid esters, chloroparaffin, aluminum hydroxide, boron compounds, molybdenum trioxide, calcium carbonate, magnesium carbonate or ferrocene can be used as flame retardants. Preferably, antimony trioxide or phosphoric acid esters are used, particularly preferably phosphoric acid esters, in particular bisphenyl cresyl phosphate, diphenyl octyl phosphate or tricresyl phosphate

The molding compositions according to the invention may have a content of flame inhibitors of from 0.01 to 10 phr, preferably from 0.1 to 8 phr, more preferably from 0.2 to 5 phr and in particular from 0.5 to 2 phr.

In order to protect articles produced from the molding compositions according to the invention from damage in the surface region by the influence of light, the molding compositions may also contain light stabilizers.

For example, hydroxybenzophenones, cyano-phenylacrylates or hydroxyphenylbenzotriazoles can be used in the context of the present invention.

Cyanophenyl acrylates are preferred, more preferably 2-ethylhexyl-2-cyano-3,3-diphenylacrylate

The molding compositions according to the invention may have a content of light stabilizers of from 0.01 to 7 phr, preferably from 0.1 to 5 phr, more preferably from 0.2 to 4 phr and in particular from 0.5 to 3 phr.

The production of plasticized PVC using the plasticizers according to the invention is usually carried out by mixing the individual components with stirring at elevated temperatures. The preparation of mixtures of polyvinyl chlorides, plasticizers and other additives is generally described, for example, in "Becker / Braun, Plastics Handbook, Volume 2/1: Polyvinyl chloride", 2nd ed. Carl Hanser Verlag, Munich ,

In a preferred preparation, the polyvinyl chloride and all other solid constituents are first prepared by stirring at a stirring speed of 500 to 5000 rpm (revolutions per minute), preferably 1000 to 3000 rpm, more preferably 2000 to 2500 rpm, at a temperature of 30 to 150 ° C, preferably 40 to 100 ° C, particularly preferably 50 to 70 ° C, mixed. Subsequently, the plasticizers according to the invention and all other liquid constituents are added and mixed by stirring at a stirring speed of 500 to 5000 rpm (revolutions per minute), preferably 1000 to 3000 rpm, more preferably 2000 to 2500 rpm, the temperature to a final value of 70 to 190 ° C, preferably 80 to 160 ° C, particularly preferably 90 to 130 ° C, is increased. Subsequently, the mixture is cooled to room temperature and can be further processed to finished articles.

As already stated, the compounds used according to the invention are suitable, in particular, for the preparation of plastisols, owing to their good gelling properties.

Plastisols can be made from a variety of plastics. The plastisols according to the invention are, in a preferred embodiment, a PVC plastisol.

PVC plastisols usually contain a total amount of plasticizer from 5 to 400 phr, preferably from 50 to 200 phr

Plastisols are usually brought into the form of the finished product at ambient temperature by various methods, such as brushing, casting, such as the shell casting or spin casting, dipping, spraying, and the like. Subsequently, the gelation is carried out by heating, after cooling a homogeneous, more or less flexible product is obtained.

PVC plastisols are particularly suitable for the production of PVC films, for the production of seamless hollow bodies, gloves and for use in the textile sector, such. B. for textile coatings.

The molding composition according to the invention is preferably used for the production of moldings and films. These include in particular housings of electrical appliances, such as kitchen appliances and computer cases; tools; cameras; Pipelines; Electric wire; Hoses, such as Plastic hoses, water and irrigation hoses, industrial rubber hoses or chemical hoses; Wire sheathing; Window profiles; Components for vehicle construction, such as body components, vibration dampers for engines; Tires; Furniture, such as chairs, tables or shelves; Foam for upholstery and mattresses; To plan; seals; Composite films, such as films for laminated safety glass, in particular for vehicle and window panes; records; Leatherette; Packaging containers; Adhesive tape or coatings.

The plasticizers used according to the invention are suitable, for example, for the production of PVC films. The plasticizers according to the invention are particularly suitable for the production of self-adhesive films, automotive films, furniture and office films, agricultural films, food films (cling film), roofing membranes, oil tank inner foils, water reservoir foils, pool foils, building protection foils, raincoats, swing doors, shower curtains, dinghies, water wings.

The plasticizers used in the invention are also suitable for the production of PVC cables. The plasticizers according to the invention are particularly suitable for the production of installation cables, power cables, communication cables, helical cords, computer cables, automobile cables.

The plasticizers used according to the invention are also suitable for the production of PVC coatings. The plasticizers according to the invention are particularly suitable for the production of artificial leather (for use in automobile or tannery), truck and tarpaulins, tablecloths, protective clothing, vinyl wallpaper, conveyor belts.

The plasticizers used in the invention are also suitable for the production of PVC floor coverings. The plasticizers according to the invention are particularly suitable for the production of foamed floor coverings (cushion vinyl), heterogeneous compact coverings, homogeneous compact coverings, carpet coatings.

The plasticizers used according to the invention are also suitable for the production of PVC profiles. The plasticizers according to the invention are particularly suitable for the production of industrial hoses and garden hoses, seals (for use, for example, in refrigerators), medical hoses, stair handrails.

The plasticizers used in the present invention are also particularly useful in the manufacture of shoes, including boots and sandals, toys, including dolls and footballs, gloves, including industrial and medical gloves, underbody protection, end caps, bellows, erasers.

The preparation of these finished articles can be done by calendering, extrusion, coating, casting, dipping, Rotomoulding or injection molding. Further details of these processing methods can be found in, for example, "Becker / Braun, Plastics Handbook, Volume 2/1: Polyvinyl chloride", 2nd ed. Carl Hanser Verlag, Munich ,

In addition, the novel molding compositions are additionally suitable for the production of moldings and films which come into direct contact with humans or foodstuffs. These are mainly medical devices, hygiene products, food packaging, indoor products, toys and childcare articles, sports and leisure products, clothing and fibers for fabrics and the like.

The medical products which can be produced from the molding composition according to the invention are, for example, hoses for enteral nutrition and hemodialysis, respiratory hoses, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or respiratory masks.

The food packaging that can be produced from the molding composition according to the invention is, for example, cling films, food hoses, drinking water hoses, containers for storing or freezing foods, lid seals, caps, bottle caps or artificial wine corks.

The products for the interior area that can be produced from the molding composition according to the invention are, for example, floor coverings, wall coverings or wallpapers in buildings or panels or console covers in vehicles.

The toys and child care articles which can be produced from the molding composition according to the invention are, for example, dolls, inflatable toys such as balls, game figures, play dough, buoyancy aids, children's clothing covers, changing mattresses or vials.

The sports and leisure products which can be produced from the molding composition according to the invention are, for example, exercise balls, exercise mats, seat cushions, massage balls and rollers, shoes or shoe soles, balls, air mattresses or drinking surfaces.

The clothing which can be produced from the molding compositions according to the invention is, for example, latex clothing, protective clothing, raincoats or rubber boots.

In addition, the present invention includes the use of the compounds according to the invention as or / and in adjuvants selected from among: calendering auxiliaries; rheological; Surface-active compositions such as flow, film-forming aids, defoamers, foam inhibitors, wetting agents, coalescing agents and emulsifiers; Lubricants, such as lubricating oils, greases and lubricating pastes; Quenchers for chemical reactions; desensitizing agents; pharmaceutical products; Plasticizers in adhesives; Impact modifiers and adjusters.

The invention is further illustrated by the following examples.

Example 1: Preparation of the β, γ-disubstituted γ-butyrolactone W1 from oleic acid methyl ester

Methyl oleate (3.5 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were combined with acetic acid (50 mL) and the appropriate suspension heated to reflux. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated.

The oily residue (4.4 g) was purified by Kugelrohr distillation (230 ° C, 1 mbar). The resulting distillate (W1) was characterized by IR (smart orbital ATR unit, absorption band: 1780-1776 cm ^-1 (lactone), 1737-1734 cm ^-1 (ester)) and had a lactone concentration of 2 , 1 mmol / g.

Example 2: Preparation of the β, γ-disubstituted γ-butyrolactone W2 from oleic acid butyl ester

Oleic acid butyl ester (5.0 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were added with acetic acid (50 mL) and the appropriate suspension heated to reflux. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated. The oily residue (5.1 g) was purified by Kugelrohr distillation (230 ° C, 1 mbar). The resulting distillate (W2) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 2.5 mmol / g.

Example 3: Preparation of the β, γ-disubstituted γ-butyrolactone W3 from oleic acid 2-propylheptyl ester

Oleic acid 2-propylheptyl ester (5.0g), Mn (OAc) ₃ .2H ₂ O (10.4g) and KOAc (1.9g) were added with acetic acid (50mL) and the appropriate suspension to reflux heated. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated. The oily residue (5.4 g) was purified by Kugelrohr distillation (250 ° C, 1 mbar). The resulting distillate (W3) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 1.8 mmol / g.

Example 4: Preparation of the β, γ-disubstituted γ-butyrolactone W4 from rapeseed oil methyl ester.

• – Palmitinsäuremethylester (C16:0) 8,5 Gew.%
• – Stearinsäuremethylester (C18:0) 1,5 Gew.%
• – Ölsäuremethylester (C18:1) 62,2 Gew.%
• – Linolsäuremethylester (C18:2) 18,3 Gew.%
• – Linolensäuremethylester (C18:3) 6,8 Gew.%

Rapeseed oil (88.5 g) was added with MeOH (32.0 g) and NaOMe (30% in MeOH, 0.81 g) and the mixture heated to 120 ° C. After 3 h at 120 ° C, the mixture was cooled, with methyl tert. butyl ether diluted. Subsequently, the mixture was washed successively with a saturated ammonium chloride solution and with water, dried with MgSO ₄ and concentrated. The residue obtained was subsequently purified by distillation. The resulting distillate (rapeseed oil-methyl ester mixture, 76.0 g) was analyzed by GC (PBFFAP, 25 m × 0.25 mm × 0.25 μm, 110 ° C (3 min) → 180 ° C (5 ° C / min ) → 230 ° C (3 ° C / min, 15 min), rt = 20.2 min (palmitic acid methyl ester), 25.1 min (methyl stearate), 25.7 min (methyl oleate), 26.6 min (methyl linoleic acid), 28.1 min (linolenic acid methyl ester)) and consisted inter alia of:

• - Palmitic acid methyl ester (C16: 0) 8.5% by weight
• Methyl stearate (C18: 0) 1.5% by weight
• Oleic acid methyl ester (C18: 1) 62.2% by weight
• Methyl linoleate (C18: 2) 18.3% by weight
• Methylene linolenate (C18: 3) 6.8% by weight

The rapeseed oil methyl ester mixture (3.5 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were added with acetic acid (50 mL) and the appropriate suspension heated to reflux , After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated. The oily residue (6.5 g) was purified by Kugelrohr distillation (230 ° C, 1 mbar). The resulting distillate (W4) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 2.1 mmol / g.

Example 5: Dissolution temperature of the plasticizers according to the invention

To characterize the gelling behavior of plasticizers for PVC, the first test is the determination of the dissolution temperature DIN 53408 ,

To DIN 53408 For example, a drop of a slurry of 1 g of PVC in 19 g of plasticizer is observed under the translucent light microscope equipped with a heatable microscope stage. The temperature increase is adjusted from 60 ° C to 2 ° C per minute.

The dissolution temperature is the temperature at which the entire PVC particles become invisible and contours and contrasts are no longer recognizable.

For comparison, the dissolution temperature of the fatty acid esters used as starting materials was also determined. softener Dissolving temperature for PVC ( DIN 53408 ) (° C) W1 (Example 1) 107 methyl oleate > 215 W2 (Example 2) 116 butyl oleate > 215 W3 (example 3) 118 Oleic acid-2-propylheptyl > 215 W4 (Example 4) 104 Rapeseed oil Methylestergemisch > 215

The results show that the lactone-containing products W1, W2, W3 and W4 have a low dissolution temperature for PVC DIN 53408 and thus have a "softening effect". On the other hand, the fatty acid esters used as starting material did not dissolve PVC and therefore have no "softening effect".

Example 6: Preparation of the β, γ-disubstituted γ-butyrolactone W5 from rapeseed oil

Rapeseed oil (5.0 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were treated with acetic acid (50 mL) and the appropriate suspension was heated to reflux. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water washed, dried with MgSO ₄ and concentrated. The oily residue (W5, 5.6 g) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 1.2 mmol / g.

Example 7: Preparation of the β, γ-disubstituted γ-butyrolactone W6 from olive oil

Olive oil (5.0 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were added with acetic acid (50 mL) and the appropriate suspension heated to reflux. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated. The oily residue (W6, 6.0 g) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 1.4 mmol / g.

Example 8: Preparation of β, γ-disubstituted γ-butyrolactone W7 from sunflower oil (high oleic)

Sunflower oil (5.0 g), Mn (OAc) ₃ .2H ₂ O (10.4 g) and KOAc (1.9 g) were added with acetic acid (50 mL) and the appropriate suspension heated to reflux. After 18 h at 120 ° C, the suspension was cooled, washed with water and methyl tert. Butyl ether diluted and the resulting phases were separated. Subsequently, the organic phase was washed successively with an aqueous saturated NaHCO ₃ solution and water, dried with MgSO ₄ and concentrated. The oily residue (W7, 6.1 g) was characterized by IR (smart orbital ATR unit) and had a lactone concentration of 1.2 mmol / g.

Example 9: Dissolution temperature of the plasticizers according to the invention

For comparison, the dissolution temperature of the modified vegetable oils W5, W6 and W7 was after DIN 53408 certainly. The results are compared in the following table. softener Dissolving temperature for PVC ( DIN 53408 ) (° C) W5 (Example 6) 165 W6 (Example 7) 161 W7 (example 8) 172 rapeseed oil > 215 olive oil > 215 Sunflower oil (high oleic) > 215

The results show that the plasticizers W1, W2, W3, W4 according to the invention, whose concentration of butyrolactone units of the formula (II) is 1.5 to 5.0 mmol / g, have significantly lower dissolution temperatures than the modified vegetable oils W5, W6 and W7 ,

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 99/32427 [0010]
• WO 00/78704 [0011]
• US 7973194 B1 [0012]
• US 08/0139702 A1 [0013]
• US Pat. No. 6797753 [0013]
• US 06/0135666 A1 [0013]
• US 2,969,339 [0013]
• US 4289668 [0013]

Cited non-patent literature

• DIN 53408 [0003]
• DIN 53408 [0018]
• DIN 53408 [0024]
• DIN 53408 [0025]
• EI Heiba, RM Dessau and PG Rodewald (J. Am. Chem. Soc. 1974, 7977) [0041]
• "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Munich [0051]
• DIN 53726 [0052]
• "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl Chloride", 2nd ed. Carl Hanser Verlag, Munich [0086]
• "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl Chloride", 2nd ed. Carl Hanser Verlag, Munich [0100]
• DIN 53408 [0116]
• DIN 53408 [0117]
• DIN 53408 [0119]
• DIN 53408 [0120]
• DIN 53408 [0124]
• DIN 53408 [0124]

Claims (24)

Use of a compound of the general formula (I) as plasticizer for thermoplastic polymers and elastomers,

wherein Q is the radical of an n-valent alcohol, wherein n has a value of 1 to 6 and m has a value of 1 to n, R ^{1 is} a hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} a hydrocarbon radical having 8 to 30 carbon atoms, in which at least one CC bond is fused to a butyrolactone unit of the general formula (II),

wherein - - - - is the fused bond, one of the symbols X, Y is an oxygen atom and the other is a CHR group, wherein R is H or an unsubstituted or substituted C ₁ -C ₁₃ alkyl radical. Use according to Claim 1, characterized in that the concentration of butyrolactone units of the formula (II) in the compound of the formula (I) is 0.2 to 5.0 mmol / g, based on the mass of compound of the formula (I). Use according to claim 1 or 2, characterized in that the radical (CO) R ^{1 is} a natural fatty acyl radical. Use according to claim 3, characterized in that the fatty acyl radical comprises a saturated, monounsaturated, polyunsaturated, substituted by epoxy groups and / or substituted by hydroxyl groups hydrocarbon chain. Use according to claim 4, characterized in that the fatty acyl radical is selected from oleic acid and rapeseed oil fatty acids. Use according to any one of claims 1 to 4, characterized in that the radical (CO) R ^{2 is} obtainable by reacting an unsaturated fatty acyl radical with an enolizable carboxylic acid in the presence of a transition metal salt. Use according to claim 6, characterized in that the enolizable carboxylic acid is acetic acid. Use according to claim 6 or 7, characterized in that the transition metal salt is selected from manganese (III) acetate, cerium (IV) acetate and vanadium (V) acetate. Use according to one of claims 1 to 8, characterized in that the thermoplastic polymer contains polyvinyl chloride or consists of polyvinyl chloride. Use according to one of claims 1 to 8, characterized in that the elastomer contains a natural and / or synthetic rubber or consists of a natural and / or synthetic rubber. Use according to one of Claims 1 to 8, characterized in that the compound of the formula (I) is used as plasticizer or gelling agent in a plastisol. Use according to one of claims 1 to 8 as a plasticizer for reducing the temperature required for gelling a thermoplastic polymer and / or for increasing the gelling speed. Molding composition comprising at least one polymer and at least one compound of the general formula (I)

wherein Q is the radical of an n-valent alcohol, wherein n has a value of 1 to 6 and m has a value of 1 to n, R ^{1 is} a hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} a hydrocarbon radical having 8 to 30 carbon atoms, in which at least one CC bond is fused to a butyrolactone unit of the general formula (II),

wherein - - - - is the fused bond, one of the symbols X, Y is an oxygen atom and the other is a CHR group, wherein R is H or an unsubstituted or substituted C ₁ -C ₁₃ alkyl radical. A molding composition according to claim 13, further comprising at least one plasticizer other than compounds of formula (I). Molding composition according to Claim 14, in which the plasticizer other than compounds (I) is chosen from phthalic acid alkyl esters, phthalic acid alkylaralkyl esters, terephthalic acid dialkyl esters, trimellitic trialkyl esters, dialkyl adipic acid esters, alkyl benzoates, glycolic dibenzoic acid esters, Hydroxybenzoic acid esters, esters of saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids, amides and esters of aromatic sulfonic acids, alkylsulfonic acid esters, glycerol esters, isosorbide esters, phosphoric acid esters, citric acid triesters, alkylpyrrolidone derivatives, 2,5-furandicarboxylic esters, epoxidized vegetable oils based on triglycerides and saturated or unsaturated Fatty acids, polyesters of aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols. A molding composition according to any one of claims 13 to 15, characterized in that the polymer is a thermoplastic polymer which is selected from - homopolymers and copolymers containing at least one monomer in copolymerized form, which is selected from C ₂ -C ₁₀ monoolefins, 1 , 3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C ₂ -C ₁₀ -alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C ₁ -C ₁₀ -alcohols, Vinylaromatics, (meth) acrylonitrile, maleic anhydride and α, β-ethylenically unsaturated mono- and dicarboxylic acids, - homo- and copolymers of vinyl acetals, - polyvinyl esters, - polycarbonates, - polyesters, - polyethers, - polyether ketones, - thermoplastic polyurethanes, - polysulfides, - Polysulfones, - Polyethersulfonen, - Cellulosealkylestern, and mixtures thereof. Molding composition according to claim 16, wherein the thermoplastic polymer is selected from polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides. A molding composition according to claim 17, wherein the thermoplastic polymer is polyvinyl chloride (PVC). Molding composition according to one of claims 13 to 18, characterized in that the content of compound of the formula (I) is 5.0 to 100 phr. Molding composition according to claim 13, wherein the polymer is an elastomer, preferably selected from natural rubbers, synthetic rubbers and mixtures thereof. A molding composition according to any one of claims 13 to 20, further comprising at least one additive selected from stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents and biostabilizers. Use of a molding composition according to any one of claims 13 to 20 for the production of moldings and films, such as housings of electrical appliances, computer housings, tools, pipelines, cables, hoses, wire sheathing, window profiles, components for vehicle construction, tires, furniture, foam for Upholstery and mattresses, tarpaulins, gaskets, composite films, agricultural films, food films, protective films, records, artificial leather, protective clothing, conveyor belts, wallpapers, packaging containers, adhesive tape, coatings or floor coverings. Use of a molding composition according to any one of claims 13 to 20 for the production of shaped articles and films which come into direct contact with humans or foodstuffs. Use according to claim 23, characterized in that the moldings and films which come into direct contact with humans or food are medical devices, Hygiene products, food packaging, indoor products, toys and childcare articles, sports and leisure products, clothing and fibers for fabrics.