EP1749050A1

EP1749050A1 - In-situ production of stabilizer compositions, stabilizer compositions produced in this manner, and use thereof

Info

Publication number: EP1749050A1
Application number: EP05744541A
Authority: EP
Inventors: Jürgen HAUK; Stefan Fokken
Original assignee: Baerlocher GmbH
Current assignee: Baerlocher GmbH
Priority date: 2004-05-19
Filing date: 2005-05-19
Publication date: 2007-02-07
Also published as: DE102004024891A1; WO2005113662A1

Abstract

The invention relates to the production of stabilizer compositions for organic polymers by the in situ reaction of polyol fatty acid esters with alkaline metal salts in the presence of water, to stabilizer compositions produced in this manner and to the use thereof.

Description

In-situ production of stabilizer compositions, stabilizer compositions prepared in this way and their use

The invention relates to the production of stabilizer compositions for organic polymers by in-situ reaction of polyol fatty acid esters with basic metal salts in the presence of water, stabilizer compositions prepared in this way and their use.

As is known, halogen-containing plastics tend to undergo undesired decomposition and degradation reactions when subjected to thermal stress during processing or in long-term use. When halogenated polymers are broken down, particularly in the case of PVC, hydrochloric acid is formed, which is eliminated from the polymer strand, which results in a discolored, unsaturated plastic with coloring polyene sequences.

It is particularly problematic that halogen-containing polymers only have the rheological framework necessary for processing at a relatively high processing temperature. At such temperatures, however, a noticeable decomposition of the polymer already begins in the case of unstabilized polymers, which leads both to the undesired color change described above and to a change in the material properties. In addition, the hydrochloric acid released from unstabilized, halogen-containing polymers at such a processing temperature can lead to noticeable corrosion of the processing plants. This process plays a role in particular if, during the processing of such halogenated polymers to give shaped articles, for example by extrusion, production is interrupted and the polymer mass remains in the extruder for a longer period of time. During this time, the above-mentioned decomposition reactions can occur the batch in the extruder becomes unusable and the extruder may be damaged.

Furthermore, polymers which are subject to such a decomposition tend to form adhesions on the processing plants which are difficult to remove again. The problems mentioned are usually solved by the use of stabilizers which are added to the halogen-containing polymer before or during processing.

In order to avoid this, halogen-containing polymers are usually added for processing as so-called stabilizers, which are intended to prevent the above-mentioned decomposition reactions as far as possible. As a rule, such stabilizers are solids which are added to the polymer to be processed before it is processed.

In addition to such solid stabilizer components, which counteract a color change in the polymer to be processed, stabilizer compositions for halogen-containing polymers often also contain liquid or at least pasty compounds. Such compounds can, for example, also counteract a change in color of the polymer due to decomposition. However, it is also frequently the case that suitable stabilizer compositions are added to compounds which bring about an improvement in the processability of the polymer, in particular in the production of moldings. Such compounds often also have a liquid or pasty consistency.

Particularly popular as constituents of compositions which serve to stabilize halogen-containing polymers, tion of the metal soaps of polyvalent metal ions, in particular the soaps of calcium and zinc, for example the soaps of calcium and zinc with fatty acids. However, the processing properties of such soaps are often problematic with regard to their use as stabilizer components for stabilizing polymers. Calcium stearate, for example, has a softening point of approx. 145 to 160 ° C. For this reason, calcium stearate can usually only be mixed in finely divided form with PVC in extruders at appropriate temperatures, so that there is a sufficiently homogeneous digestion. Other devices, for example heating / cooling mixers, are not suitable for producing a corresponding mixture of calcium stearate and other additives and PVC due to the lower temperatures (often around 130 ° C).

The stabilizer compositions known from the prior art, which were produced before using calcium stearate, therefore often have inhomogeneities or require high processing temperatures in order to achieve a mixture which is as homogeneous as possible. However, these high processing temperatures are undesirable in many applications or lead to an avoidable thermal load on the materials to be processed. To improve the rheological properties during the processing of halogen-containing polymers, stabilizer compositions are often added to lubricants. These lubricants are often polyol esters of fatty acids with up to about 44 carbon atoms. In the course of producing a corresponding stabilizer composition, the above-mentioned soaps, polyol esters and, if appropriate, other additives are usually mixed as intimately as possible, made up and brought to the customer.

However, the above procedure has some drawbacks. The manufacture of the individual components is usually complex. Furthermore it has It has been shown that the mixing of the individual components often cannot take place as completely as would be desirable in the sense of a stabilizing effect which is as uniform as possible. Ingredients of appropriate stabilizer compositions often tend to clump together. On the one hand, this can lead to a locally different stabilization effect. Especially when using stabilizers for transparent products, it is also necessary that the transparency of the products is maintained even after stabilization and that no clouding occurs. However, this is often not the case with conventional stabilizers. Due to the incomplete mixing of the individual components of a stabilizer composition, local clumping can occur, which can have a lasting effect on the visual impression, in particular of transparent products made from halogen-containing polymers.

For example, the production of overbased zinc soaps is known from the prior art. For this purpose, WO 00/46173 converts basic zinc carbonate with organic carboxylic acids having 6 to 22 carbon atoms at temperatures in the range from 100 to 200 ° C. in the absence of organic solvents, the water of reaction formed being continuously distilled off. The compounds thus obtained are said to be suitable as additives for processing plastics and in particular for stabilizing halogen-containing plastics against thermal and / or photochemical degradation. However, the problem here is that the mixing of such compounds with corresponding liquid or pasty further constituents of the stabilizer composition often leads to incomplete or sufficiently homogeneous mixtures. This entails the disadvantages already described above.

The present invention was therefore based on the object of providing a stabilizer composition which is that of the prior art does not have known disadvantages. In particular, the object of the present invention was to provide a stabilizer composition which has a particularly homogeneous distribution of the ingredients as a result of the production. Furthermore, the object of the present invention was to provide a method for producing a stabilizer composition which, on the one hand, significantly reduces the effort involved in producing a stabilizer composition and, on the other hand, improves the product quality with regard to the disadvantages mentioned above.

The above-mentioned objects and other objects, as they are obvious to a person skilled in the art from the invention itself and the present text, are achieved by a stabilizer composition and a method for its production, as are described in the context of the text below.

The present invention therefore relates to a stabilizer composition for stabilizing halogen-containing polymers, obtainable by reacting a reaction mixture of at least one polyol fatty acid ester with at least two ester bonds, water and a basic salt of an at least divalent metal to give a product, the temperature during the reaction being at least 120 ° C and water is present in an amount of 2 to 20 wt .-%, based on the polyol fatty acid ester with at least two ester bonds.

In the context of the present invention, a “stabilizer composition” is understood to mean a composition which can be used to stabilize halogen-containing polymers. To achieve this stabilization effect, a stabilizer composition according to the invention is generally mixed with a halogen-containing polymer provided for stabilization and then processed. However, it is also possible to use a state according to the invention. Mix the bilizer composition with the halogen-containing polymer to be stabilized during processing.

To produce the stabilizer compositions according to the invention, a reaction mixture is reacted which has at least one polyol fatty acid ester with at least two ester bonds. In the context of the present invention, a “polyol fatty acid ester” is understood to mean a compound which has at least two ester bonds, at least one ester bond being present between a polyol and a fatty acid.

Suitable polyols, such as are present in the context of a polyol fatty acid ester which can be used according to the invention, are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lactitol, lycasin , Tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylol cycloheptanol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0-α-D-dehydro-mannopyritosyl ,

In principle, all organic linear or branched, saturated or unsaturated carboxylic acids having 6 to about 44, in particular about 8 to about 22, carbon atoms are suitable as fatty acids. In a polyol fatty acid ester which can be used according to the invention, the corresponding fatty acids can be present either individually or as a mixture of two or more of the fatty acids mentioned. Examples of suitable organic carboxylic acids having 6 to 22 carbon atoms are caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachonic acid, hhenic acid, hendic acid , 10- undecenoic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, Petroselinic acid, elaidic acid, ricinoleic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, 9,10,11,12-tetrahydroxystearic acid, linoleic acid, linoleic acid, linolenic acid, elaostearic acid, gadoleic acid, arachidonic acid, erucic acid, brassidic acid or clupanodonic acid two or more of them. Compounds which have any proportion of linear or branched, saturated or unsaturated fatty acids are suitable in principle as a constituent of the polyol fatty acid esters according to the invention. In a preferred embodiment of the present invention, however, polyol fatty acid esters are used whose proportion of linear fatty acids is at least about 50, in particular at least about 80 or at least about 90% by weight, based on the total amount of carboxylic acids used. The proportion of saturated carboxylic acids is preferably in a range of at least about 40, preferably at least about 50, 60, 70, 80 or at least about 90% by weight.

In the context of the present invention, however, it is also suitable to use polyol fatty acid esters as a constituent of the reaction mixture which have a content of at least about 50, for example at least about 80 or at least about 90% by weight of C-2 branched acids, based on the total amount of carboxylic acids used. In the context of a particularly preferred embodiment of the present invention, a polyol fatty acid ester is used in this case which has at least a portion of 2-ethyl-hexanoic acid residues.

In principle, polyol fatty acid esters which have two or more ester bonds can be used in the context of the present invention. For example, polyol fatty acid esters with 2, 3, 4, 5 or 6 ester bonds are suitable. In a preferred embodiment of the present invention, however, polyol fatty acid esters are used which have 2, 3 or 4, but in particular 3, ester bonds. In principle, polyol fatty acid esters of the above-mentioned polyols are equally suitable as part of the reaction mixture. In the context of the present invention, however, it has proven to be advantageous if a glycerol fatty acid ester is present at least in part in the reaction mixture as the polyol fatty acid ester. In the context of a preferred embodiment of the present invention, the proportion of glycerol fatty acid ester in the reaction mixture is at least about 30% by weight. The proportion of glycerol fatty acid ester is preferably at least about 50, at least about 60, at least about 70, at least about 80, or at least about 90% by weight. In a particularly preferred embodiment of the present invention, the reaction mixture contains 95% by weight or more of glycerol fatty acid ester. The number of ester bonds is preferably more than two on average, for example at least about 2.5. In the context of a particularly preferred embodiment of the present invention, glycerin fatty acid esters which essentially have three ester bonds per molecule are used as part of the reaction mixture.

Vegetable or animal fats or oils as are obtainable from the corresponding natural sources are suitable according to the invention as a particularly suitable source for such glycerol fatty acid esters. Corresponding compounds such as are obtainable by suitable synthesis methods are also suitable as glycerol trifatty acid esters. The following fats or oils are particularly suitable:

Avocado oil, cottonseed oil, peanut oil, cocoa butter, pumpkin seed oil, linseed oil, corn oil, olive oil, palm oil, rapeseed oil, canola oil, rice oil, rapeseed oils, safflower oil, Se Samoel, soybean oil, linseed oil, fish oil, castor oil, sunflower oil, grapeseed oil, wheat germ oil, coconut oil, macadamia nut oil, Beef tallow, pork tallow, borneo tallow, fulwatalg, hemp oil, Illipebutter, lupine oils, candel nut oil, cashew nut oil, kapok oil, katia fat, kenaf seed oil, kekuna oil, poppy seed oil, mowrah butter, okra oil, perillaol, sage butter, shea butter and tung oil.

In a preferred embodiment of the present invention, triglycerides from natural sources are used which either have a high content of saturated fatty acid residues or have been hardened before use. Suitable hardened fats are considered to be those whose iodine number (measured according to the DGF C-V 11 b standard) is less than 20. Fats whose iodine number is less than 5 are particularly preferred.

The implementation of fat hardening is described, for example, in "Ulimann's Encyclopedia of Industrial Chemistry", 4th edition, volume 11, p. 469. Mixtures of these naturally occurring fats and artificially produced fats such as Softisan 154 or Dynasan 118 (from Hüls) can also be used. The preparation of such artificial triacylglycerides is known to the person skilled in the art and can be carried out, for example, from glycerol and the corresponding fatty acid methyl esters. Such esterification reactions are u. a. in "Houben-Weyl, Methods of Organic Chemistry", Vol. E5 / Part 1, pp. 659 ff.

Preferred triacylglycerides correspond to the formula:

R ² -O-CH ₂ -CH (OR ¹ ) -CH ₂ -OR ^{3 '}

wherein R ¹ , R ² and R ³ independently of one another are CnH ₂₃ CO, C ₁₃ H ₂₇ CO, C ₁₅ H ₃ ιCO or Cι ₇ H ₃₅ CO. Mixtures of two or more such triacylglycerides are also suitable. The distribution of fatty acid residues can correspond to the distribution pattern of fats or oils from natural sources. chen. However, it is also provided according to the invention that the distribution pattern of the fatty acids has no equivalent in nature but corresponds to any technical fatty acid mixture.

In the context of the present invention, preference is given to using natural or artificial fats with a steaoryl content of more than 65% by weight of the triglyceride as part of the reaction mixture.

In addition to at least one polyol fatty acid ester, as described above, a reaction mixture which can be used according to the invention also contains at least one basic salt of an at least divalent metal. In the context of the present invention, any salt of at least a divalent metal which has a pH of more than 7 in contact with water is basically suitable as the basic salt of an at least divalent metal.

In the context of the present invention, particular preference is given to using basic salts of at least divalent metals which are capable of effecting ester hydrolysis (saponification), preferably saponification, of a polyol ester present in the context of a reaction mixture according to the invention. Basically, the basic salts of the metals of the second or third main group of the periodic table, such as the first to eighth subgroups of the periodic table, and the lanthanides are particularly suitable. In a particularly preferred embodiment of the present invention, however, the basic salts of beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, manganese, iron, cobalt, nickel, copper or zinc are used as basic salts of at least divalent metals. The basic salts of calcium or zinc are particularly preferred in the context of the present invention. Suitable basic salts can be water-soluble salts in the context of the present invention. However, it is also possible within the scope of the present invention to use basic salts which only assume a corresponding basic form when they come into contact with water. Corresponding salts can be water-soluble. However, it is also possible to use salts which are only water-dispersible but which have a basic action in contact with the water.

Salts of the abovementioned metals with weak acids, in particular oxides, hydroxides, carbonates, oxide hydrates, hydroxycarbonates, oxychlorides, phosphites or phosphates or mixtures of two or more thereof are particularly suitable.

In a particularly preferred embodiment of the present invention, the basic salt of an at least divalent metal is calcium oxide, calcium hydroxide, zinc oxide or zinc carbonate or a mixture of two or more thereof.

It has been found in the context of the present invention that a reaction mixture as used in the context of the present invention to obtain a product contains water in addition to at least one polyol ester with at least two ester bonds and at least one basic salt of an at least divalent salt got to. The suitable amount of water can be within a range of about 2 to about 20% by weight based on the amount of polyol fatty acid ester having at least two ester bonds in the reaction mixture. Particularly suitable levels of water are, for example, within a range from about 2.5 to about 19.5, about 3 to about 19, about 4 to about 18, about 5 to about 17, about 6 to about 16, about 7 to about 15 , about 8 to about 14, about 9 to about 13 or about 10 to about 12 weight percent. For example, the amount of water present in the reaction mixture can be more than 2.5% by weight, in particular more than 8% by weight, based on the polyol fatty acid ester with at least two ester bonds.

A reaction mixture according to the invention contains a polyol fatty acid ester with at least two ester bonds, or a mixture of two or more thereof and a basic salt of at least a divalent metal or a mixture of two or more such salts in an essentially arbitrary ratio. However, it has been found in the context of the present invention that the selection of certain ratios of polyol fatty acid esters to basic salts of an at least divalent metal or mixtures of two or more thereof have particularly good properties with regard to the later properties of a stabilizer composition. In the context of the present invention, it is particularly advantageous to select the ratio of polyol fatty acid esters to basic salts such that the polyol fatty acid esters are not completely saponified. It is particularly advantageous if the ratio of polyol fatty acid ester to basic salt is selected so that, at least theoretically, no polyol is released during the reaction.

For example, it is preferred in the context of the present invention that, for example, in a reaction of a diester with a basic salt according to the invention, the ratio of ester to salt is selected such that essentially (starting from the molar ratio of basic salt to ester bonds) is a mixture Monoesters and salt of the corresponding released acid are formed. If, for example, a triester is used as the polyol ester, the ratio of polyol ester to basic salt can be set such that, after the reaction in the product, a mixture of diester and salt of the liberated acid or monoester and salt of the liberated acid or monoester and diester and salt the acid released is present. The ingredients of the reaction product preferred according to the invention, based on the conversion products of polyol fatty acid ester and basic metal salt, are explained below using the example of a reaction of basic zinc salt and glycerol tristearate or a basic calcium salt and glycerol tristearate or a mixture of a basic calcium salt and basic zinc salt with glycerol tristearate. With an appropriate choice of the ratio of glycerol tristearate to basic metal salt, the following compositions can be obtained, for example:

Zinc steara GMS

Zinc steara GDS

Zinc stearate: GMS: GDS

Zinc stearate: GMS: GDS: GTS Calcium stearate: GMS

Calcium stearate: GD S

Calcium stearafcGMS: GDS

Calcium: GMS: GDS: GTS

Calcium stearate: zinc stearate: GMS calcium stearate: zinc stearate: GDS

Calcium stearate: Zinc stearate: GMS: GDS

Calcium stearate: Zinc stearate: GMS: GDS: GTS.

The abbreviation GMS stands for glycerol monostearate, the abbreviation GDS for glycerol distearate and the abbreviation GTS for glycerol tristearate. In the context of a preferred embodiment of the present invention, the ingredients of the reaction mixture are preferably selected in such a way that the molar ratio of ester groups in the polyol fatty acid ester to the molar amount of basic salt, the molar amount of basic salt having the value of the total amount of basic salt must be multiplied by the metal or metal mixture present in the basic salt or salt mixture (normality), at a value of 1 or less, in particular at a value from about 0.2 to about 0.95 or about 0.4 to about 0.8 or about 0.5 to about 0.7.

Only the proportions of basic metal salt that are available for a reaction with an acid released from an ester group are included in the above calculation. If a reaction mixture according to the invention contains, for example, compounds which are themselves capable of reacting with the basic metal salt, the correspondingly reacting portions of the basic metal salt are not included in the calculation of the ratio of polyol fatty acid ester or ester groups to basic metal salt.

The reaction itself is carried out in the context of the present invention at a temperature of about 100 to about 180 ° C., in particular at a temperature of about 110 to about 170, or about 120 to about 160 or about 130 to about 150 ° C. In the context of a particularly preferred embodiment of the present invention, the temperature during the reaction is about 135 to about The reaction time is generally about 30 minutes to about 5 hours. However, it has been shown that a reaction time of about 45 minutes to about 3 hours, for example 1 hour to about 2 hours, is often sufficient to achieve a result.

The reaction can be carried out continuously or in a batch process with the aid of reactors known to the person skilled in the art.

In the context of the present invention, it is particularly preferred if the reaction mixture contains at least 30% by weight of polyol fatty acid ester. It is further preferred if the reaction mixture contains at least one glycerol ester as the polyol fatty acid ester.

A basic calcium salt or a basic zinc salt or a mixture of two or more such salts are particularly preferred as basic salts. Correspondingly preferred reaction mixtures therefore contain, for example, a mixture of two or more calcium salts or a mixture of two or more zinc salts or a mixture of a calcium salt and a zinc salt or a mixture of two or more calcium salts and a zinc salt or a mixture of two or more zinc salts and a calcium salt or a mixture of two or more calcium salts and two or more zinc salts.

It has been found in the context of the present invention that in many cases the implementation can be improved by adding an emulsifier. Improvements can be made either with regard to the product quality, for example with regard to the homogeneity of the product or with regard to the stabilizing effect of the product or with regard to the implementation itself, for example the time, temperature or the like required for the implementation or the yield achieved in the implementation or the product purity influence. In principle, all surfactants are suitable as emulsifiers which do not have a negative or no longer tolerable negative effect on the reaction. For example, anionic, cationic or nonionic surfactants are suitable.

Examples of nonionic surfactants used are alkoxylated, advantageously ethoxylated, aliphatic or aromatic alcohols having preferably 8 to 44 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. Alcohols are suitable, for example, in which the alcohol radical may be linear or methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. For example, alkylphenol alkoxylates can be used, for example nonylphenol ethoxylate with 2 to 20 alkoxide units.

Alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are also preferred. Such alcohols include, for example, C _12- ι ₄ alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, Cι _3-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{2 - 18} - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, as well as mixtures of C _12-14 alcohol with 3 EO and with 5 EO.

All degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides. The polyhydric fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkyl laminate or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

If, in the context of the present invention, nonionic surfactants are used in the reaction according to the invention, they preferably have a proportion of the reaction mixture of approximately 0.01 to approximately 5% by weight, for example a proportion of approximately 0.1 to approximately 1.5% by weight .-%, based on the amount of polyol fatty acid ester.

Surprisingly, it has been found that the presence of amino alcohols can have a positive influence on the course of the reaction. It is therefore within the scope of a further embodiment of the present invention preferred if a reaction mixture according to the invention contains an amino alcohol or a mixture of two or more amino alcohols.

Suitable amino alcohols in the context of the present invention are in principle all compounds which have at least one OH group and a primary, secondary or tertiary amino group or a combination of two or more of the amino groups mentioned. In principle, both solid and liquid amino alcohols are suitable as part of the stabilizer compositions according to the invention in the context of the present invention.

In the context of a further preferred embodiment of the present invention, a reaction mixture for producing a stabilizer composition according to the invention contains a total of at most about 5% by weight of amino alcohol or a mixture of two or more amino alcohols.

Suitable for this purpose are, for example, OH groups, in particular at least 2 OH groups, of derivatives of primary mono- or polyamino compounds having 2 to about 40, for example 6 to about 20, C atoms. For example, these are corresponding OH group-bearing derivatives of ethylamine, n-propylamine, i-propylamine, n-propylamine, sec-propylamine, tert-butylamine, 1-aminoisobutane, substituted amines with two to about 20 C atoms, such as 2 - (N, N-Dimethylamino) -l-aminoethane. Suitable OH group-bearing derivatives of diamines are, for example, those based on diamines with a molecular weight of about 32 to about 200 g / mol, the corresponding diamines having at least two primary, two secondary or one primary and one secondary amino group. Examples include diaminoethane, the isomeric diaminopropanes, the isomeric diaminobutanes, the isomeric diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4, 4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as the diethylenetriamine or 1,8-diarnino-4-aminomethyloctane. Triethylamine, tributylamine, dimethylbenzylamine, N-ethyl, N-methyl, N-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodiethyl ether, 1,4-diazabicyclo [2,2,2] octane, 1-azabicyclo [3,3,0] octane, N, N, N ', N'

Tetramethylethylenediamine, N, N, N ', N' -tetramethylbutanediamine, N, N, N ', N' - tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, N, N'-dimethylpiperazine , 1,2-dimethylimidazole or di- (4-N, N-dimethylaminocyclohexyl) methane.

Aliphatic amino alcohols having 2 to about 40, preferably 6 to about 20, carbon atoms, for example l-amino-3,3-dimethyl-pentan-5-ol, 2-aminohexane-2 ', 2 "-diethanolamine, l are particularly suitable -Amino-2,5-dimethylcyclohexan-4-ol- 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, l-amino-2-propanol, 2-amino-2-methyl-l-propanol, 5-aminopentanol, 3 -Aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propanediol, 2- (dimethylaminoethoxy) ethanol, aromatic-aliphatic or aromatic -cycloaliphatic amino alcohols with 6 to about 20 C atoms, the aromatic structures being heterocyclic or isocyclic ring systems such as naphthalene or, in particular, benzene derivatives such as 2-aminobenzyl alcohol, 3- (hydroxymethyl) aniline, 2-amino-3-phenyl-l- propanol, 2-amino-l-phenylethanol, 2-phenylglycinol or 2-amino-l-phenyl-l, 3-propanediol and mixtures of two or more such compounds.

In a particularly preferred embodiment of the present invention, for example, amino alcohols are used which have a linear or branched aliphatic hydrocarbon chain with at least about 10 carbon atoms, for example dodecylbis (2-hydroxyethyl) amine, tridecylbis (2-hydroxyethyl) amine, pentadecylbis (2-hydroxyethyl) amine, hexadecylbis (2- hydroxyethyl) amine, heptadecylbis (2-hydroxyethyl) amine or octadecylbis (2-hydroxyethyl) amine. Octadecylbis (2-hydroxyethyl) amine is particularly suitable.

In a further embodiment of the present invention, heterocyclic compounds which have a cyclic ring system containing amino groups are used as amino alcohols, the OH groups being connected to the ring either directly on the ring or preferably via spacers.

In a preferred embodiment of the present invention, heterocyclic amino alcohols are used which have at least 2, preferably at least 3, amino groups in the ring. The trimerization products of isocyanates are particularly suitable as the central ring component of the amino alcohols which can be used according to the invention.

Hydroxyl group-containing isocyanurates of the general formula are particularly preferred

CHYOH (CH ₂ ) _m

wherein the groups Y and the indices m are each the same or different and m is an integer from 0 to 20 and Y is a hydrogen atom or a linear re or branched, saturated or unsaturated alkyl group having 1 to about 10 carbon atoms. For example, the use of tris (hydroxyethyl) isocyanurate (THEIC) as part of the reaction mixture according to the invention is suitable within the scope of the present invention.

A stabilizer composition according to the invention can, for example, contain only one amino alcohol. However, it is also provided in the context of the present invention that a reaction mixture according to the invention contains a mixture of two or more different amino alcohols.

The use of amino alcohols of the type mentioned above is particularly advantageous when a reaction mixture according to the invention contains a basic zinc salt.

The present invention also relates to a process for the preparation of a stabilizer composition according to the invention, in which a polyol ester having at least two ester linkages is reacted with water and a basic salt of an at least divalent metal to give a product, the temperature during the reaction being at least 120 ° C. and water is present in an amount of from 2 to about 20% by weight, based on the polyol fatty acid ester having at least two ester bonds.

It has also proven to be expedient in the context of the present invention if, in the course of the reaction according to the invention, which leads to a stabilizer composition according to the invention, ingredients are already included in the reaction mixture which, on the one hand, are essentially inert during the reaction itself or which Do not adversely affect implementation or no longer as avoidable and the properties of the product did not affect the stabilizing effect or the other product properties or no longer adversely.

In this context, the presence of further lubricants or plasticizers during the reaction is particularly advantageous.

Lubricants such as montan wax, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metal soaps are particularly suitable for this purpose. Lubricants that can be used as additives are also described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pp. 478-488. Also suitable as additives are, for example, fat ketones as described in DE 4,204,887 and silicone-based lubricants as described for example in EP-A 0 259 783 or combinations thereof as described in EP-A 0 259 783. Reference is hereby expressly made to the documents mentioned, the disclosure of which relates to lubricants is considered to be part of the disclosure of the present text.

Furthermore, during the reaction, for example, pigments such as titanium dioxide, zeolites or hydrotalcites or other inorganic acid scavengers, chalk, β-diketones or their salts or other costabilizers such as perchlorates, uracils, aminouracils, antioxidants, UV stabilizers and the like can be reacted to under the reaction conditions other ingredients are essentially inert ingredients of stabilizer combinations.

In the context of a further embodiment of the present invention, it has also turned out to be advantageous if secondary reactions are carried out in the course of the reaction, which likewise lead to products which achieve an improvement in the stabilizing effect. For example, it has been found possible to add N-cyanoacetyl-N, N; -dimethylurea to the reaction mixture during a reaction according to the invention or to add this constituent to the reaction mixture before the reaction is carried out. This compound reacts to aminouracil under the influence of bases. Carrying out corresponding experiments has shown that parallel production of aminouracil is possible in the context of the present inventive implementation. The proportion of cyanoacetylureas is preferably selected such that the amount of aminouracil in the product is about 0.1 to about 25% by weight.

The individual substances present in the reaction mixture can be added to the reaction mixture as a whole before the start of the temperature increase in the process according to the invention for producing the stabilizer compositions according to the invention. The individual substances can be added simultaneously or in succession. If substances which have a melting point below about 200 ° C. are added before the start of the temperature increase, these substances can be added to the reaction mixture in solid form or in the molten state.

However, it is also possible within the scope of the present invention to add the individual compounds to the reaction mixture in part only during or after heating to the desired reaction temperature. In this case, the addition can take place, for example, in the solid state or, if the material to be added has a suitable melting point, in molten form.

A stabilizer composition according to the invention can, in addition to the above-described constituents resulting from the reaction according to the invention, len still contain other ingredients that contribute to the stabilizing effect or positively influence the stabilizer composition itself.

Additives such as those named below are suitable, for example.

Suitable additives are, for example, compounds which have a mercapto-functional sp ² -hybridized carbon atom. Such connections are described for example in DE 101 09 366 AI on pages 4 and 5. The disclosure of this document with regard to such compounds is understood to be part of the disclosure of the present document. Particularly suitable components of a stabilizer composition according to the invention are, for example, thiourea, phenylthiourea or N, N'-diphenylthiourea or a mixture thereof.

Also suitable as additives are, for example, compounds having a structural element of the following general formula

R ² wherein n is a number from 1 to 100,000, the radicals R ^a , R ^b , R ¹ and R ² each independently of one another for hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical with 1 to 44 C. -Atoms, an optionally substituted saturated or unsaturated cycloalkyl radical with 6 to 44 C atoms or an optionally substituted aryl radical with 6 to 44 C atoms or an optionally substituted aralkyl radical with 7 to 44 C atoms or the radical R ^{1 is} one if necessary substituted acyl radical having 2 to 44 carbon atoms or the radicals R ¹ and R ² are linked to form an aromatic or heterocyclic system and in which the radical R ^{3 is} hydrogen, an optionally substituted, linear or branched, saturated or unsaturated aliphatic alkyl or Alkylene radical or oxyalkyl or oxyalkylene radical or mercaptoalkyl or mercaptoalkylene radical or aminoalkyl or aminoalkylene radical with 1 to 44 C atoms, an optionally substituted saturated or unsaturated cycloalkyl or cycloalkylene radical or oxycycloalkyl or oxycycloalkylene radical or mercaptocycloalkyl or cycloalkyl or cycloalkyl or cycloalkyl or cycloalkyl or cycloalkylene or aminocycloalkyl or aminocycloalkylene radical having 6 to 44 carbon atoms or an optionally substituted aryl or arylene radical having 6 to 44 carbon atoms or an ether or thioether radical having 1 to 20 O or S atoms or O and S -Atoms or for a polymer that has O, S, NH, NR ^a or CH ₂ C (O) with the in brackets rn is attached to the structural element, or the radical R is connected to the radical R in such a way that an optionally substituted, saturated or unsaturated heterocyclic ring system having 4 to 24 carbon atoms is formed, the radical R ¹ in a ring system with R ³ does not represent NH or NR ^a , or a mixture of two or more of the compounds mentioned.

Halogen-containing salts of oxyacids, in particular the perchlorates, are suitable as additives for a stabilizer composition according to the invention. Examples of suitable perchlorates are those of the general formula M (ClO) _n , where M represents Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. The index n represents the number 1, 2 or 3 depending on the valency of M. The perchlorate salts mentioned can be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The polyol partial esters are also to be counted among the ester alcohols. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers are also suitable, such as di-, tri-, tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various polymerization and saponification degrees. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial esters. Sugar alcohols or thio sugar are also suitable.

The perchlorate salts can be used in various common forms of administration, for example as a salt or aqueous solution applied to a suitable carrier material such as PVC, calcium silicate, zeolites or hydrotalcites or incorporated into a hydrotalcite by chemical reaction. A combination of Na perchlorate and calcium silicate which is suitable as a constituent of the stabilizer composition according to the invention can be obtained, for example, by combining an aqueous solution of Na perchlorate (content of Na perchlorate about 60% or more) with calcium silicate, for example a synthetic, amorphous calcium silicate , respectively. Suitable particle sizes for the calcium silicate that can be used are, for example, about 0.1 to about 50, for example about 1 to about 20 μm. Suitable perchlorate-containing dosage forms are described, for example, in US Pat. No. 5,034,443, the disclosure of which perchlorate-containing dosage forms is expressly referred to and which disclosure is regarded as part of the disclosure of the present text.

Further suitable dosage forms are mentioned, for example, in EP-A 394,547, EP-A 457,471 and WO 94/24200, to the disclosure of which suitable dosage forms are expressly referred, and which disclosure is regarded as part of the disclosure of the present text.

The salts of halogen-containing oxyacids in a particularly finely divided form are also suitable. With such a fine distribution, less than 10% by weight of the salts of the halogen-containing oxyacid or of the mixture of two or more such salts have crystallites with a size of more than 3 μm. from that it follows that at least about 90% by weight of the salts have crystallites with a size of less than 3 μm. Correspondingly finely divided perchlorates are described, for example, in DE 10124734.6-43, to which express reference is made here. The part of the disclosure of the latter document relating to finely divided perchlorates and their production is understood to be part of the disclosure of the present text.

In a further embodiment of the present invention, a stabilizer composition according to the invention can also contain additives.

Examples of suitable additives are epoxy compounds. Examples of such epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized cottonseed oil and glycidyl compounds.

Glycidyl compounds contain a glycidyl group attached directly to a carbon, oxygen, nitrogen or sulfur atom. Glycidyl or methyl glycidyl esters can be obtained by reacting a compound with at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or methyl epichlorohydrin. The reaction is conveniently carried out in the presence of bases. Glycidyl ether or methyl glycidyl ether can be obtained by reacting a compound with at least one free alcoholic OH group or a phenolic OH group and a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst and subsequent alkali treatment. Corresponding compounds and their preparation are described for example in DE 101 09 366 AI, p. 9. Reference is expressly made to the publication mentioned and its disclosure in connection with glycidyl compounds is regarded as part of the disclosure of the present text. Also suitable are N-glycidyl compounds, such as are obtainable by dehydrochlorination of the editorial products of epichlorohydrin with amines which contain at least one amino hydrogen atom. Such amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.

S-glycidyl compounds, for example di-S-glycidyl ether derivatives derived from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether, are also suitable. Particularly suitable epoxy compounds are described, for example, in EP-A 1 046 668 on pages 3 to 5, reference being expressly made to the disclosure contained therein, which is considered to be part of the disclosure of the present text.

Also suitable as additives in the context of the present invention are 1,3-dicarbonyl compounds, in particular the β-diketones and β-keto esters. Suitable for the purposes of the present invention are dicarbonyl compounds of the general formula RC (O) CHR -C (O) R, as described, for example, on page 5 of EP-1 046 668, to which, in particular with regard to the radicals R ′, R "and R '" is expressly referred to and the disclosure of which is considered to be part of the disclosure of the present text. Particularly suitable β-diketones are described, for example, in DE 101 09 366 AI on p. 9. Reference is expressly made to the last-mentioned publication and the disclosure content of the publication with regard to β-diketones is regarded as part of the disclosure of the present publication.

Polyols are also suitable as additives in the context of the stabilizer composition according to the invention. Suitable polyols are, for example Pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimetylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxymethyl) isocyanurylamethyl, isocyanurate, tris (hydroxymethyl) isocyanurate, isocyanurate, tris (hydroxymethyl) isocyanurate, tri (methyl) isocyanurate Tetramethylolcyclopentanol, teframethylolcycloheptanol, glycerin, diglycerin, polyglycerol, thiodiglycerol or 1-0-α-D-glycopyranosyl-D-mannitol dihydrate.

The polyols suitable as additives can be present in an inventive stabilizer composition in an amount of up to about 30% by weight, for example up to about 10% by weight.

Also suitable as ^additives' hindered amines are for example sterically nen as they are mentioned in EP-A 1 046 668 pages 7 to 27th Reference is expressly made to the sterically hindered amines disclosed therein, the compounds mentioned there are considered to be part of the disclosure of the present text.

The sterically hindered amines suitable as additives can be present in an inventive stabilizer composition in an amount of up to about 30% by weight, for example up to about 10% by weight.

Also suitable as additives in the stabilizer compositions according to the invention are hydrotalcites, zeolites and alkali alumocarbonates. Suitable hydrotalcites, zeolites and alkali alumocarbonates are, for example, in EP-A 1 046 668 on pages 27 to 29, EP-A 256 872 on pages 3, 5 and 7, and DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 on page 2 and 3. Reference is expressly made to these publications and their disclosure at the specified points is regarded as part of the disclosure of the present text. The hydrotalcites, zeolites and alkali alumocarbonates suitable as additives can be contained in an inventive stabilizer composition in an amount of up to about 50% by weight, for example up to about 30% by weight.

Also suitable in the context of the stabilizer compositions according to the invention as additives are, for example, hydrocalumites of the general formula

M ²⁺ ₍₂₊ χ ₎ Al ³⁺ (i _{+ y} ) (OH) _{(6 + z} ) A ^k - _a [B _n ] ^nl _b * m H ₂ O,

wherein M stands for calcium, magnesium or zinc or mixtures of two or more thereof, A for a k-valued inorganic or organic acid anion, k for 1, 2 or 3, B for a different inorganic or organic acid anion, n for one is an integer> 1 and, if n is> 1, indicates the degree of polymerization of the acid anion and 1 represents 1, 2 3 or 4 and indicates the valency of the acid anion, where n = 1 1 represents 2, 3 or 4 and n> 1 1 indicates the valency of the individual monomer units of the polyanion and stands for 1, 2, 3 or 4 and nl indicates the valency of the polyanion and the following rules for the parameters x, y, a, b, n, z, and k apply: 0 <x <0.6,

0 <y <0.4, where either x = 0 or y = 0,

0 <a <0.8 / n and z = 1 + 2x + 3y - ka - n / b.

In a preferred embodiment of the present invention, compounds of the above general formula are used as additives, in which M represents calcium, which may optionally be present in a mixture with magnesium or zinc or magnesium and zinc. Compounds of the above general formula and their preparation are particularly suitable in DE 101 09 366 AI described on pages 10 and 11. Reference is expressly made to the last-mentioned document and the disclosure content of the document with regard to compounds having the general formula M ²⁺ _{(2 + x)} Al ³⁺ _{(1 + y)} (OH) _{(6 + z)} A ^{k "} _a [B "] ^Nl _b * m H ₂ O is regarded as part of the disclosure of the present publication.

Compounds of the general formula M ²⁺ _{(2 + x} > Al ³⁺ (i _{+ y} ) (OH) _{(6 + z)} A ^{k "} _a [B _n ] ^nl _b * m H ₂ O can be used in the stabilizer compositions according to the invention in an amount of up to about 50% by weight, for example up to about 30 or up to about 15% by weight.

A stabilizer composition according to the invention can furthermore contain an organotin compound or a mixture of two or more organotin compounds as a thermostabilizer component. Suitable organotin compounds are, for example, methyltin tris (isooctyl thioglycolate), methyltin tris (isooctyl 3-mercaptopropionate), methyltin tris (isodecyl thioglycolate), dimethyltin bis (isooctyl thioglycolate), dibutyl bis- (isooctyl-thioglycolate), monobutyltin-tris (isooctyl-thioglycolate), dioctyltin-bis- (isooctyl-thioglycolate), monooctyltin-tris- (isooctyl-thioglycolate) or dimethyl-tin-hex-bis- (2 mercaptopropionate).

In addition, the organotin compounds mentioned in EP-A 0 742 259 on pages 18 to 29 and described in their preparation can be used in the context of the stabilizer compositions according to the invention. Reference is expressly made to the above-mentioned disclosure, the compounds mentioned there and their preparation being understood as part of the disclosure of the present text. A stabilizer composition according to the invention can contain the organotin compounds described in an amount of up to about 20% by weight, in particular up to about 10% by weight.

In the context of a further embodiment of the present invention, a stabilizer composition according to the invention can contain organic phosphite esters with 1 to 3 identical, pairwise identical or different organic radicals. Suitable organic radicals are, for example, linear or branched, saturated or unsaturated alkyl radicals having 1 to 24 carbon atoms, optionally substituted alkyl radicals having 6 to 20 carbon atoms or optionally substituted aralkyl radicals having 7 to 20 carbon atoms. Examples of suitable organic phosphite esters are tris (nonylphenyl), trilauryl, tributyl, trioctyl, tridecyl, tridodecyl, triphenyl, octyldiphenyl, dioctylphenyl, tri (octylphenyl), tribenzyl, butyldikresyl -, octyl-di (octylphenyl) -, tris- (2-ethylhexyl) -, tritolyl-, tris- (2-cyclohexylphenyl) -, tri-α-naphthyl-, tris- (phenylphenyl) -, tris- (2- phenylethyl), tris (dimethylphenyl), tricresyl or tris (p-nonylphenyl) phosphite or tristearyl sorbitol triphosphite or mixtures of two or more thereof.

A stabilizer composition according to the invention can contain the phosphite compounds described in an amount of up to about 30% by weight, in particular up to about 10% by weight.

A stabilizer composition according to the invention may also contain blocked mercaptans as additives, as mentioned on pages 4 to 18 of EP-A 0 742 259. The disclosure in the cited document is expressly referred to and is understood to be part of the disclosure of the present. A stabilizer composition according to the invention can contain the blocked mercaptans described in an amount of up to about 30% by weight, in particular up to about 10% by weight.

A stabilizer composition according to the invention may also contain lubricants such as montan wax, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metal soaps. Lubricants that can also be used are also described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pp. 478-488. Also suitable as lubricants are, for example, fatty ketones as described in DE 4,204,887 and silicone-based lubricants as described for example in EP-A 0 259 783, or combinations thereof as described in EP-A 0259 783. Reference is hereby expressly made to the documents mentioned, the disclosure of which relates to lubricants is considered to be part of the disclosure of the present text.

A stabilizer composition according to the invention can contain the described lubricants in an amount of up to about 70% by weight, in particular up to about 40% by weight.

Organic plasticizers are also suitable as additives for stabilizer compositions according to the present invention. Suitable plasticizers are, for example, polymer plasticizers, as described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, chapter 5.9.6, pages 412-415, or "PVC Technology", WV Titow, 4th edition, Elsevier Publishers, 1984, pages 165-170. The other suitable plasticizers DE 101 09 366 AI on S 12, paragraphs [0108] to [0114]. Reference is expressly made to the disclosure mentioned. The disclosure content of the publication in relation to plasticizers and their production and the amount used is understood to be part of the disclosure of the present text.

Pigments are also suitable as part of the stabilizer compositions according to the invention. Examples of suitable inorganic pigments are titanium dioxide, carbon black, Fe ₂ O ₃ , Sb ₂ O ₃ , (Ba, Sb) O ₂ , Cr ₂ O ₃ , spinels such as cobalt blue and cobalt green, Cd (S, Se) or ultramarine blue. Suitable organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, pearl pigments, diketopyrrolopyrrole pigments or anthaquinone pigments.

A stabilizer composition according to the invention can also contain fillers as described in the "Handbook of PVC Formulating", EJ Wickson, John Wiley & Sons, Inc., 1993, pages 393-449 or reinforcing agents as described in the "Taschenbuch der Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 1990, pages 549-615. Particularly suitable fillers or reinforcing agents are, for example, calcium carbonate (chalk), dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, chalk, carbon black or graphite, wood flour or other renewable raw materials. In the context of a preferred embodiment of the present invention, a stabilizer composition according to the invention contains chalk.

In the context of a further embodiment of the present invention, the stabilizer compositions according to the invention may contain antioxidants, UV absorbers and light stabilizers or propellants. Suitable antioxidants are described, for example, on pages 33 to 35 of EP-A 1 046 668. Suitable UV absorbers and light stabilizers are listed on pages 35 and 36. Both disclosures are expressly referred to here. men, the revelations being considered part of the present text.

Suitable blowing agents are, for example, organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, salts of citric acid, for example ammonium citrate, and soda and sodium bicarbonate. For example, ammonium citrate, azodicarbonamide or sodium bicarbonate or mixtures of two or more thereof are particularly suitable.

A stabilizer composition according to the invention can also contain impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, flame retardants and anti-fogging compounds. Suitable compounds of these classes of compounds are described, for example, in "Kunststoff Additive", R. Kessler / H. Müller, Carl Hanser Verlag, 3rd edition, 1989 and in the "Handbook of PVC Formulating", E.J. Wilson, J. Wiley & Sons, 1993.

A stabilizer composition according to the invention can have a complex composition in the context of preferred embodiments of the present invention. Basically, the compounds already mentioned in the context of this text can essentially be used as part of the compositions according to the invention. A stabilizer composition according to the invention can therefore, for example, only contain compounds which are effective with regard to the initial color or the color stability. However, a stabilizer composition according to the invention can also contain further of the above-mentioned compounds, in particular additives, which influence the processability of halogen-containing plastics or the properties of moldings produced from such plastics. A stabilizer composition according to the invention is generally suitable for improving the properties of synthetic polymers or polymer mixtures, for example polyolefins, in particular halogen-containing organic polymers.

Examples of such halogen-containing organic polymers are polymers of vinyl chloride, vinyl resins which contain vinyl chloride units in the polymer backbone, copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid or acrylonitrile or mixtures of two or more thereof , Copolymers of vinyl chloride with diene compounds or unsaturated dicarboxylic acids or their anhydrides, for example copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, such as ketones and other compounds , Crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like, polymers and copolymers of vinylidene chloride with vinyl chloride and other polymerizable compounds, as already mentioned were mentioned above, polymers of vinyl chloroacetate and dichlorodivinyl ether, chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and of α-substituted acrylic acids, chlorinated polystyrenes, for example polydichlorostyrene, chlorinated polymers of ethylene, polymers and post-chlorinated polymers of chlorobutadiene and the like Copolymers with vinyl chloride and mixtures of two or more of the polymers mentioned or polymer mixtures which contain one or more of the polymers mentioned above.

The graft polymers of PVC with EVA, ABS or MBS are also suitable for stabilization with the stabilizer compositions according to the invention. Preferred substrates for such graft copolymers are also The aforementioned homopolymers and copolymers, in particular mixtures of vinyl chloride homopolymers with other thermoplastic or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE; MBAS, PAA (polyalkyl acrylate), PAMA (polyalkyl methacrylate), EPDM, polyamides or polylactones.

Mixtures of halogenated and non-halogenated polymers, for example mixtures of the abovementioned non-halogenated polymers with PVC, in particular mixtures of polyurethanes and PVC, are also suitable for stabilization with the stabilizer compositions according to the invention.

Furthermore, recyclates of chlorine-containing polymers can also be stabilized with the stabilizer compositions according to the invention, in principle all recyclates of the above-mentioned halogenated polymers being suitable for this. PVC recyclate, for example, is suitable in the context of the present invention.

Another object of the present invention therefore relates to a polymer composition containing at least one halogenated polymer and a stabilizer composition according to the invention or a stabilizer composition produced according to the invention.

The present invention also relates to a method for stabilizing halogen-containing polymers, in which a halogen-containing polymer or a mixture of two or more halogen-containing polymers or a mixture of one or more halogen-containing polymers and one or more halogen-free polymers is mixed with a stabilizer composition according to the invention. The mixing of polymers or polymers and the stabilizer composition according to the invention can in principle take place at any time before or during the processing of the polymer. For example, the stabilizer composition can be mixed with the polymer in powder or granule form before processing. However, it is also possible to add the stabilizer composition to the polymer or the polymers in the softened or melted state, for example during processing in an extruder, as an emulsion or as a dispersion, as a pasty mixture, as a dry mixture, as a solution or as a melt.

A polymer composition according to the invention can be brought into a desired shape in a known manner. Suitable processes are, for example, calendering, extruding, injection molding, sintering, extrusion blowing or the plastisol process. A polymer composition according to the invention can also be used, for example, for the production of foams. In principle, the polymer compositions according to the invention are suitable for the production of hard or soft PVC.

A polymer composition according to the invention can be processed into moldings. The present invention therefore also relates to moldings containing at least one stabilizer composition according to the invention or a polymer composition according to the invention.

In the context of the present invention, the term “shaped body” basically includes all three-dimensional structures that can be produced from a polymer composition according to the invention. In the context of the present invention, the term “molded body” encompasses, for example, wire sheaths, automotive components, for example automotive components as used in the interior of the automobile, in the engine compartment or on the outer surfaces, cable insulation lations, decorative foils, agricultural foils, hoses, sealing profiles, office foils, hollow bodies (bottles), packaging foils (thermoformed foils), blown foils, pipes, foams, heavy profiles (window frames), light wall profiles, building profiles, sidings, fittings, panels, foam panels., coextrudates with recycled core or housings for electrical equipment or machines, for example computers or household appliances. Further examples of moldings which can be produced from a polymer composition according to the invention are synthetic leather, floor coverings, textile coatings, wallpapers, coil coatings or underbody protection for motor vehicles.

The invention further relates to the use of a product obtainable by reacting a reaction mixture of at least one polyol fatty acid ester with at least two ester bonds, water and a basic salt of an at least divalent metal, the temperature during the reaction being at least 120 ° C. and water in one Amount of 2 to 20 wt .-%, based on the polyol fatty acid ester with at least two ester bonds, is present as a stabilizer composition for organic polymers.

The invention is explained in more detail below by examples.

Examples:

1. Implementation and production of sample 1

600 g of glycerol tristearate were introduced into an unheated stirred reactor. After the stirrer was set to a speed of 250 / min, the reactor heating was switched on. When an internal temperature of 60 ° C was reached, a suspension of 51.6 g Ca (OH) ₂ in 70 g water was added. The reactor was then closed, the temperature was set to 140 ° C. and

10. The speed of the stirrer is increased to 500 / min. After 120 min the heating was switched off, the reactor was cooled and let down. The product was removed.

15 comparison sample 1:

Physical mixture of calcium stearate, glycerol distearate and glycerol monostearate in a molar ratio of 1: 1: 1

20 Table 1: Recipes 1 and 2

The above-mentioned recipes were mixed and, on the one hand, processed into skins on a laboratory rolling mill, on which the thermal stability was measured according to DIN, on the other hand the stability in the Mathis test and the plasticizing time at 180 ° C in the Brabender measuring mixer. The following results were obtained:

This shows that, with unchanged rheology, better stabilization is measured for the material produced in-situ.

Claims

claims

Stabilizer composition for stabilizing halogen-containing polymers, obtainable by reacting a reaction mixture of at least one polyol fatty acid ester with at least two ester bonds, water and a basic salt of at least one divalent metal to a product, the temperature during the reaction being at least 120 ° C. and water in an amount of 2 to 20% by weight, based on the polyol fatty acid ester with at least two ester bonds, is present.

Stabilizer composition according to claim 1, characterized in that the content of the reaction mixture of basic salt of an at least divalent metal is chosen before the reaction so that the product contains at least 30% by weight of polyol fatty acid monoester.

Stabilizer composition according to one of claims 1 or 2, characterized in that the reaction mixture contains at least one glycerol ester as polyol fatty acid ester.

4. Stabilizer composition according to one of claims 1 to 3, characterized in that the reaction mixture contains a basic calcium salt or a basic zinc salt or a mixture of two or more such salts.

5. Stabilizer composition according to one of claims 1 to 4, characterized in that the product contains at least one glycerol fatty acid ester with a fatty acid having at least 12 carbon atoms.

6. Stabilizer composition according to one of claims 1 to 4, characterized in that the product contains at least one emulsifier.

7. A process for the preparation of a stabilizer composition, in which a polyol ester having at least two ester bonds is reacted with water and a basic salt of an at least divalent metal to give a product, the temperature during the reaction being at least 120 ° C. and water in an amount of 2 up to 20% by weight, based on the polyol fatty acid ester with at least two ester bonds, is present.

8. The method according to claim 7, characterized in that the content of the reaction mixture of basic salt of an at least divalent metal is chosen before the reaction so that the product contains at least 30% by weight of polyol fatty acid monoester.

9. The method according to any one of claims 7 or 8, characterized in that the reaction is carried out with a reaction mixture which contains at least one glycerol ester as polyol fatty acid ester.

10. The method according to any one of claims 7 to 9, characterized in that the reaction is carried out with a reaction mixture which contains at least one basic calcium salt or a basic zinc salt or a mixture of two or more such salts

11. The method according to any one of claims 7 to 10, characterized in that the reaction mixture is selected so that the product at least contains at least one glycerin fatty acid ester with a fatty acid with at least 12 carbon atoms

12. The method according to any one of claims 7 to 11, characterized in that the reaction is carried out in the presence of an emulsifier.

13. Polymer composition, characterized in that it contains a stabilizer composition according to one of claims 1 to 6 or a stabilizer composition produced according to one of claims 7 to 12.

14. A method for stabilizing organic polymers, in which an organic polymer or a mixture of two or more organic polymers is mixed with a stabilizer composition according to one of claims 1 to 6 or a stabilizer composition prepared according to one of claims 7 to 12

15. Use of a product obtainable by reacting a reaction mixture of at least one polyol fatty acid ester with at least two ester bonds, water and a basic salt of an at least divalent metal, the temperature during the reaction being at least 120 ° C. and water in an amount of 2 to 20 % By weight, based on the polyol fatty acid ester with at least two ester bonds, is present as a stabilizer composition for organic polymers.