EP1453905A2

EP1453905A2 - Stabilizer composition, production and use thereof

Info

Publication number: EP1453905A2
Application number: EP02795118A
Authority: EP
Inventors: Stefan Fokken; Juergen Hauk
Original assignee: Baerlocher GmbH
Current assignee: Baerlocher GmbH
Priority date: 2001-12-11
Filing date: 2002-12-06
Publication date: 2004-09-08
Also published as: US20050040367A1; DE10160662A1; AU2002361023A1; WO2003054072A3; CN1289584C; WO2003054072A2; CN1602337A

Abstract

The invention relates to a stabilizer composition for polymers that preferably contain halogen, said composition comprising at least one onium perchlorate and at least one organic solvent.

Description

Stabilizer composition, its manufacture and use

The present invention relates to a stabilizer composition for halogen-containing polymers, their production and their use.

As is known, halogen-containing plastics tend to undergo undesirable decomposition and degradation reactions when subjected to thermal stress during processing or in long-term use. The degradation of halogenated polymers, especially PVC, produces hydrochloric acid, 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 when, 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, rendering the batch in the extruder unusable and possibly damaging the extruder.

Furthermore, polymers which are subject to such decomposition tend to form attachments to the processing plants which are difficult to remove.

In order to solve the above-mentioned problems, halogen-containing polymers for processing are usually added 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. Perchlorates are suitable as stabilizers, for example, the perchlorates according to the prior art generally being used as inorganic perchlorates, for example as sodium perchlorate. However, the problem with these connections is that they do not always meet the requirements placed on them.

In addition, solid stabilizers often have the disadvantage that they can lead to undesirable cloudiness in the end product, particularly in the case of transparent processing forms. However, such opacities restrict the acceptance of such end products by users who process them further and prevent the end products from being used in applications in which the greatest possible transparency is important.

To counter this problem, liquid stabilizers containing sodium perchlorate, for example, have been proposed. However, a disadvantage of these stabilizers is that the stabilizer properties leave something to be desired in terms of improving the initial color.

The object of the present invention was therefore to provide a stabilizer composition which can be used in the production of halogen-containing polymers and which leads to an improvement in the initial color. Furthermore, it was an object of the present invention to provide a liquid stabilizer composition which can be used in the production of halogen-containing polymers and which reduces the haze in transparent end products, for example made of hard or soft PVC. The invention was also based on the object of providing a stabilizer composition which shows an improvement in the initial color when processing halogen-containing polymers in comparison with stabilizers known from the prior art.

It has now been found that solid and liquid stabilizer compositions which contain at least one organic onium perchlorate achieve the above-mentioned objects.

A first object of the present invention is therefore a stabilizer composition comprising an organic onium salt of perchloric acid or a mixture of two or contains more organic onium salts of perchloric acid and at least one organic solvent.

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 mix a stabilizer composition according to the invention with the halogen-containing polymer to be stabilized during processing.

In the context of the present invention, the term “liquid” means the physical state of a stabilizer composition according to the invention at least within a temperature range from approximately 45 to approximately 100 ° C., preferably within a temperature range from approximately 30 to approximately 120 ° C., for example within a temperature range from about 15 to about 150 ° C. and in particular within a temperature range of about 0 to about 200 ° C.

In the context of the present text, the term “solvent” is understood to mean a compound which can dissolve an organic onium salt of perchloric acid or a mixture of two or more organic onium salts of perchloric acid in an amount of at least 0.1% by weight.

In the context of the present text, an "onium salt" is a compound which is an ammonium, sulfonium or phosphonium salt. An "onium salt" according to the present invention is an organic onium salt. This means that the ammonium, sulfonium or phosphonium group of the onium salt carries at least one organic radical. An onium salt according to the present invention can, depending on the type of onium group, carry 1, 2, 3 or 4 organic radicals. The organic radicals can be connected to the onium radical, for example via a CX linkage, where X stands for S, N or P. However, it is also possible that the organic residues are connected to the onium residue via a further heteroatom, for example an O atom.

An onium perchlorate which can be used in the context of the present invention has at least one positively charged N, P or S atom or two or more such positively charged N, P or S atoms or mixtures of two or more of the positively charged atom types mentioned on.

In the context of the present invention, compounds are used as onium perchlorates which carry at least one organic radical on the N, S or P atom and at most the maximum possible number of organic radicals. If an onium perchlorate which can be used according to the invention carries fewer organic residues than are necessary for the formation of a positively charged onium ion, the positive charge is generated in a conventional manner known to the person skilled in the art by protonation using a suitable acid, so that the corresponding onium perchlorate in this case in addition to an organic residue carries at least one proton.

It is therefore possible according to the invention to use compounds as onium perchlorates which have a positive charge due to protonation reactions. However, it is also possible in the context of the stabilizer combinations according to the invention to use onium perchlorates which have a positive charge as a result of a peralkylation reaction. Examples of such compounds are tetraalkylammonium, trialkylsulfonium or tetraalkylphosphonium perchlorates. However, it is also provided in the context of the present invention that a peralkylated onium perchlorate which can be used according to the invention has an aryl, alkaryl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl radical. It is also possible and provided according to the invention that an onium salt which can be used in the context of a stabilizer composition according to the invention has two or optionally more different types of substituents, for example an alkyl and a cycloalkyl radical or an alkyl and an aryl radical. It is also possible and envisaged in the context of the present invention that an onium salt which can be used in the context of a stabilizer composition according to the invention has substituents which in turn are substituted by one or more functional groups are. In this context, “functional groups” are groups which improve the effects of the stabilizer composition or at least not or only slightly deteriorate them. Corresponding functional groups can be, for example, NH groups, NH ₂ groups, OH groups, SH groups, ester groups, ether groups, thioether groups, isocyanurate groups or keto groups or mixtures of two or more thereof.

In principle, all compounds which lead to a phosphonium perchlorate by appropriate reaction of suitable reactants can be used as phosphonium perchlorates in the context of the present invention. Phosphonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of tetraalkyl, tetracycloalkyl or tetraaryl phosphorus halides. Suitable phosphonium perchlorates are therefore derived, for example, from tetraalkylphosphorus salts such as tetra-n-ethylphosphonium bromide, tetra-n-propylphosphonium bromide, tetra-n-butylphosphonium bromide, tetra-n-isobutylphosphonium bromide, tetra-n-pentylphylbromidium, and the like Tetraalkyl phosphorus salts. Furthermore, phosphonium perchlorates which are derived, for example, from tetracycloalkyl phosphorus salts or tetraaryl phosphorus salts are suitable in principle for use in the stabilizer compositions according to the invention. Suitable phosphonium perchlorates are therefore based, for example, on tetracycloalkyl or tetraaryl phosphorus salts such as tetracyclohexylphosphonium bromide or tetraphenylphosphonium bromide and the like tetracycloalkyl or tetraaryl phosphorus salts. The abovementioned compounds can be unsubstituted in the context of the present invention, but they can also have one or more of the abovementioned substituents, provided that these substituents have no adverse effects in the context of the stabilizer composition and do not adversely affect the intended use of the stabilizer composition.

Organic phosphonium perchlorates which carry different types of organic substituents on a phosphorus atom, which can optionally be substituted differently, can also be used in the context of the present invention. In a preferred embodiment of the present invention, tetra-n-butylphosphonium perchlorate or triphenylbenzylphosphonium perchlorate are used as phosphonium perchlorates.

In principle, all compounds which lead to a sulfonium perchlorate by appropriate reaction of suitable reactants can be used as sulfonium perchlorates in the context of the present invention. Sulfonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of sulfides such as alkyl monosulfides, alkyl disulfides, dialkyl sulfides or polyalkyl sulfides. Suitable sulfonium perchlorates are therefore derived, for example, from dialkyl sulfides such as ethylbenzyl sulfide, allylbenzyl sulfide or alkyl disulfides such as hexane disulfide, heptane disulfide, octane disulfide and the like alkyl disulfides. Furthermore, sulfonium perchlorates which are derived, for example, from tricycloalkylsulfonium salts or triarylsulfonium salts are suitable in principle for use in the stabilizer compositions according to the invention. Suitable sulfonium perchlorates are therefore based, for example, on tricycloalkyl or triarylsulfonium salts such as tricyclohexylsulfonium bromide or triphenylsulfonium bromide and the like tricycloalkyl or triarylsulfonium salts. Trialkyl, triaryl or tricycloalkylsulfoxonium salts such as trimethylsulfoxonium perchlorate are also suitable. The abovementioned compounds can be unsubstituted in the context of the present invention, but they can also have one or more of the abovementioned substituents, provided that these substituents have no adverse effects in the context of the stabilizer composition and do not adversely affect the intended use of the stabilizer composition.

Organic sulfonium perchlorates which carry different types of organic substituents on a sulfur atom, which can optionally be substituted differently, can also be used in the context of the present invention.

In a preferred embodiment of the present invention, trimethyl sulfoxonium perchlorate is used as the sulfonium perchlorate.

Within the scope of the present invention, all compounds which can be used as ammonium perchlorates in principle by appropriate reaction of suitable reactants lead ammonium perchlorate. Ammonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of amines or amides such as alkylmonoamines, alkylenediamines, alkylpolyamines, secondary or tertiary amines or dialkylamines. Suitable ammonium perchlorates are therefore derived, for example, from primary mono- or polyamino compounds having 2 to about 40, for example 6 to about 20, carbon atoms. For example, these are ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, tert-butylamine, substituted amines with 2 to about 20 C atoms, such as 2- (N, N-dimethylamino) -l- aminoethane. Suitable diamines have, for example, two primary, two secondary two tertiary or one primary and one secondary or one primary and one tertiary or one secondary and one tertiary amino group. Examples include diaminoethane, the isomeric diaminopropanes, the isomeric diamino-butanes, the isomeric diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4 ' -Diamino- dicyclohexylmethane, 1, 4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as the diethylenetriamine or l, 8-diamino-4-aminomethyloctane or tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, 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, pentamethyl-diethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, N, N'-dimethylpiperazine, 1, 2-dimethylimidazole or di- (4-N, N-dimethylaminocyclohexyl) methane.

Also suitable are aliphatic amino alcohols with 2 to about 40, preferably 6 to about 20, carbon atoms, for example triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, l-amino-3,3-dimethyl-pentan-5-ol, 2-aminohexane -2 ', 2 "-diethanolamine, 1-amino-2,5-dimethylcyclohexan-4-ol-2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-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-l, 3-propanediol, 2- (dimethylaminoethoxy) -ethanol, aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols with 6 to about 20 C atoms, 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 are used.

In a further embodiment of the present invention, the perchlorates of heterocyclic compounds which have a cyclic ring system having amino groups are used as ammonium perchlorates.

For example, the perchlorates of 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 ammonium perchlorates which can be used according to the invention.

For example, hydroxyl-containing isocyanurates of the general formula I are suitable

CHYOH

(CH V ₂ ),

HOYHC-

wherein the grapples Y and the indices m are each the same or different and m represents an integer from 0 to 20 and Y represents a hydrogen atom or a linear or branched, saturated or unsaturated alkyl grappe having 1 to about 10 C atoms. In the context of the present invention, particular preference is given to the use of tris (hydroxymethyl) isocyanurate (THEIC) as a constituent of the stabilizer compositions according to the invention. Also suitable as ammonium perchlorates are, for example, compounds in which the amino group is bound to a substituted aromatic or heteroaromatic system. which is present, for example aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and their suitable derivatives.

In a preferred embodiment of the present invention, the ammonium perchlorates used are 2-ethylcarboxypyridinium perchlorate, formamidinium perchlorate, tetra-n-butylphosphonium perchlorate, trimethylsulfoxonium perchlorate, the perchlorate salt of trishydroxyethyl isocyanurate, the perchlorate salt of 2- (diethylamino) n- droxyethyl) morpholinium perchlorate or trioctylammonium perchlorate or mixtures of two or more thereof.

In the context of the present invention, a stabilizer composition according to the invention can contain, for example, only one of the above-mentioned onium perchlorates. In the context of the present invention, it is also possible and also provided that a stabilizer composition according to the invention contains a mixture of two or more of the above-mentioned onium perchlorates. It can be a mixture of two or more different types of onium perchlorates, i. that is, for example, a mixture of ammonium perchlorates and sulfonium perchlorates or ammonium perchlorates and phosphonium perchlorates or sulfonium perchlorates and phosphonium perchlorates or ammonium perchlorates and sulfonium perchlorates and phosphonium perchlorates. It is also possible within the scope of the invention that a stabilizer composition according to the invention is a mixture of two or more onium perchlorates of one type, i.e. H. contains a mixture of two or more ammonium perchlorates and a mixture of two or more sulfonium perchlorates and a mixture of two or more phosphonium perchlorates.

If a stabilizer composition according to the invention contains a mixture of two or more onium perchlorates, these two or more onium perchlorates can in principle be present in any ratio in the stabilizer composition according to the invention. In the context of the present invention, a stabilizer composition according to the invention contains, based on the total composition, from 0.01 to about 30% by weight, for example about 0.1 to about 20% by weight of an organic onium salt of a perchlorate or a mixture of two or more organic onium salts of perchlorates.

In the context of the present invention, a stabilizer composition according to the invention preferably contains an ammonium or a sulfonium salt or a mixture of two or more thereof, in particular an ammonium salt, as the organic onium salt.

If a stabilizer composition according to the invention is in the liquid state, it can have, in addition to an onium perchlorate, for example one or more of the solvents listed below or one or more of the following additives.

In addition to an onium perchlorate or a mixture of two or more onium perchlorates, a stabilizer composition according to the invention also contains at least one organic solvent.

In the context of the present invention, a “solvent” is understood to mean a compound or a mixture of two or more compounds which is liquid within a certain temperature range and is capable of an onium perchlorate present in a composition according to the invention or a mixture of two or more to dissolve such onium perchlorates. A solvent which is suitable in the context of the present invention is at least within a temperature range from approximately 45 to approximately 100 ° C., preferably within a temperature range from approximately 30 to approximately 120 ° C., for example within a temperature range from approximately 15 to approximately 150 ° C. and in particular within a temperature range of about 0 to about 200 ° C liquid.

In a preferred embodiment of the present invention, compounds or mixtures of two or more compounds which are suitable as plasticizers for halogen-containing polymers are used as solvents.

Suitable solvents in the sense of the present text are therefore, for example, compounds from the group of phthalic acid esters such as dimethyl, diethyl, dibutyl, dihexyl, di- 2-ethylhexyl, di-n-octyl, di-iso-octyl , Di-iso-nonyl, di-iso-decyl, dicyclohexyl, di methylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl or diphenyl phthalate and mixtures of phthalates, for example mixtures of alkyl phthalates with 7 to 9 or 9 to 11 carbon atoms in the ester alcohol or mixtures of alkyl phthalates with 6 to 10 and 8 to 10 carbon atoms in ester alcohol. Particularly suitable for the purposes of the present invention are dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl, di-iso-decyl, Di-iso-tridecyl and benzyl butyl phthalate and the mixtures of alkyl phthalates mentioned.

Also suitable as solvents are the esters of aliphatic dicarboxylic acids, in particular the esters of adipic, azelaic or sebacic acid or mixtures of two or more thereof. Examples of such solvents are di-2-ethylhexyl adipate, di-isooctyl adipate, di-isononyl adipate, di-iso-decyl adipate, benzyl butyl adipate, benzyl octyl adipate, di-2-ethyl hexyl azelate, di-2-ethyl hexyl sebacate and di-iso-decylseb. In a further embodiment of the present invention, preference is given to di-2-ethylhexyl acetate and di-iso-octyl adipate.

Also suitable as solvents are trimellitic acid esters such as tri-2-ethylhexyl trimellithate, tri-iso-tridecyl trimellithate, tri-iso-octyl trimellithate and trimellitic acid esters with 6 to 8, 6 to 10, 7 to 9 or 9 to 11 carbon atoms in the ester group or mixtures of two or more of the compounds mentioned.

Other suitable solvents are, for example, polymer plasticizers, as described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, chapter 5.9.6, pages 342-489, or "PVC Technology", WV Titow, 4th edition, Elsevier Publishers, 1984, pages 165-170. Reference is hereby expressly made to the publications mentioned and the plasticizers listed in the context of the first-mentioned reference (R. Gächter / H. Müller) and suitable as solvents in the sense of the invention, in particular the ones in Tables 9a (pp. 388 - 392) , 10 (p. 396), 11 (p. 400), 12a (p. 402 - 404), 13a (p. 408 - 410), 13b (p. 412), 14 (p. 413), 16 (p . 418), 3 (pp. 479) and 4 (pp. 486 - 488) are considered to be part of the disclosure of the present text. The most common starting materials for the production of polyester plasticizers are, for example, dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid and diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol or diethylene glycol or mixtures of two or more thereof.

Also suitable as plasticizers are phosphoric acid esters, as can be found in the "Taschenbuch der Kunststoffadditive", chapter 5.9.5, pp. 408-412. Examples of suitable phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, triphenyl phosphate, tricresyl phosphate or trixylenyl phosphate, or mixtures of two or more thereof.

The compounds listed below are particularly suitable as solvents in the context of the present invention: methyl 2-hydroxy-5-methylbenzoate, 2-ethoxybenzyl alcohol, N-ethyl-2,3-dimethylaniline, methyl 2-hydroxy-3-methylbenzoate , Benzyl laurate, 3,4,5-trimethoxybenzyl alcohol, 3,5-dimethylbenzyl alcohol, 3-methylbenzophenone, 2-methoxyactetophenone, 3-cyclohexylpropionic acid, cyclopentanecarboxylic acid, 2,5-dimethylbenzonitrile, 4- (4-methoxyphenyl) butane-2 -on, cinnamic formate ester, triethyl citrate, dibutyl decanate, diethyl heptaethylene glycol, dibutyl adipate, dibutyl adipate, 1, 2-bis (2-acetoxy-ethoxy) ethane, diethyl azelaate, ethyl acetate, ethyl acetate, glutarate ester, ethyl glutarate ester, diethyl glutarate ester Decyl acetate, butyl cyanoacetate, pentyl hexanoate, nyl acetate, methyl decanoate, methyl nonanoate, Undecylene alcohol, N-methyldioctylamine, diethylene glycol dibutyl ether, dioctyl ether, decan-3-one, 4-oxa-heptane nitrile, nonannitrile, diethylene glycol monohexyl ether, diisobutyl ketone, formic acid butyl ester, ethylenedimethylamethylthioethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamidoethylamethylamethylamethylamethylthioamethylamethylamethane hexan-l, 3-diol, decan-4-ol, decan-1-thiol, hexamethylene dimercaptan, trimethylene iodide, dodecane-2-ol, N-butylformamide, diisopentyl sulfide, hexaethylene glycol, pentaethylene glycol, trioctylamine, dipropylenetriamine, trodecylene glycol, diethylene glycol, 2'-dithiodiglycol, diethyl carbonate, m-tolyl isothiocyanate, linolenic acid, triethylene tetramine, 5H-furan-2-one, 4-benzylpiperidine, 1-phenylpiperidine, isonicotinic acid ethyl ester, pyridine-2-carboxylic acid ethyl ester, 2,3,3-trimethyl-3H-indole , 3-methylsulfolane, propylene carbonate, 3- Piperidinopropionitrile, Sulfolan, tetrahydrothiophene-1-oxide, 4-Mo holinoethanol or 4-octylaniline.

In a stabilizer composition according to the invention, the abovementioned solvents can each be present alone or as a mixture of two or more thereof. If a stabilizer composition according to the invention is a liquid stabilizer composition which contains two or more of the abovementioned compounds as solvents, one or more of the compounds can lie outside the above definition of the term "liquid", provided that the entire solvent mixture is within this definition lies.

A stabilizer composition according to the invention contains solvents or solvent mixtures in an amount of about 99.99 to about 2 percent by weight, for example about 98 to about 3 or about 95 to about 5 percent by weight. The solvent content can vary within wide limits, depending on whether the stabilizer composition according to the invention is used as the sole stabilizer or together with one or more additives or is to be in a solid or liquid state. For example, a liquid stabilizer composition according to the present invention can contain about 20 to about 99.99% by weight or about 99 to about 30% by weight or about 95 to about 35% by weight or about 90 to about 40% by weight of solvent .-% or about 85 to about 50 wt .-%.

In addition to an onium perchlorate or a mixture of two or more onium perchlorates or an onium perchlorate or a mixture of two or more onium perchlorates and a solvent or a mixture of two or more solvents, a stabilizer composition according to the invention can contain one or more further additives in an amount of up to up to about 95% by weight, for example up to about 93% by weight or about 91% by weight or about 0 to about 90% by weight or about 1 to about 85% by weight. These are preferably additives which are distributed in a polymer to be stabilized, preferably dissolved in such a way that a stabilized polymer does not become opaque due to the additives. Solid stabilizer compositions according to the present invention can in principle be produced using any method known to those skilled in the art for mixing different solid or solid and liquid substances, for example by simply mixing an onium perchlorate with other additives.

The liquid stabilizer composition according to the invention can be produced in different ways. In principle, to produce a stabilizer composition according to the invention it is possible, for example, to dissolve an onium perchlorate in a suitable organic solvent.

The present invention therefore relates to a method for producing a stabilizer composition according to the invention, in which an onium perchlorate is dissolved in an organic solvent.

Since many of the onium perchlorates which can be used in the context of the present method and in a stabilizer composition according to the invention are not commercially available and therefore have to be prepared by the user himself, it makes sense to integrate the method for producing the onium perchlorates into the method according to the invention for producing the stabilizer composition according to the invention. Different approaches can be selected for this, a selection of which is described below as an example.

For example, it is basically possible, first of all, to produce an onium perchlorate from an organic compound capable of forming an onium salt or a salt of such a compound by reaction with perchloric acid or a suitable inorganic salt of perchloric acid. This onium perchlorate can then be separated off and dissolved in an appropriate organic solvent. The reaction is preferably carried out in aqueous solution, the perchloric acid or the corresponding suitable salt of perchloric acid usually being added dropwise as an aqueous solution with a concentration of about 50 to about 70% by weight. If it is insoluble in water, the onium perchlorate formed can be separated off as a precipitate by means of customary separation methods, for example filtration or centrifugation. The present invention therefore furthermore relates to a process for the preparation of a stabilizer composition according to the invention, in which an organic compound capable of forming an onium salt or a salt of such a compound is mixed with perchloric acid or an inorganic salt of perchloric acid, the onium salt formed in the process separated organic compound and dissolved in an organic solvent.

If the organic compound used to form an onium salt forms a water-insoluble organic perchlorate, an alkali perchlorate, for example sodium perchlorate or potassium perchlorate, is reacted with an onium chloride in aqueous solution as the inorganic salt of perchloric acid. This creates a water-soluble organic onium perchlorate and a water-soluble alkali chloride. The water-insoluble organic onium perchlorate can be separated off in the usual way and then dissolved in an organic solvent. If necessary, water can also be removed from the organic onium perchlorate in an intermediate step.

If the organic compound used to form an onium salt forms a water-soluble organic perchlorate, a compound which forms a water-soluble chloride is used as the inorganic salt of perchloric acid. The water-soluble chloride can be separated off in the usual way. The soluble onium perchlorate can then be freed of water in the usual way.

In the context of a further embodiment of the present invention, a water-soluble organic onium chloride is used as the organic compound capable of forming an onium salt, and silver perchlorate is preferably used as the inorganic salt of perchloric acid. When silver perchlorate is added to the water-soluble organic onium chloride in aqueous solution, an insoluble silver chloride forms a precipitate and an aqueous solution of an organic onium perchlorate is formed. The precipitate is then filtered off and the organic onium perchlorate in aqueous solution is isolated by customary separation methods, for example by distilling off the water. The present invention therefore also relates to a process for the preparation of a stabilizer combination according to the invention, in which an organic onium chloride is used as the organic compound capable of forming an onium salt and an alkali perchlorate is used as the inorganic salt of perchloric acid, the organic onium chloride being mixed with an aqueous solution of the alkali perchlorate is, whereby a water-soluble organic onium perchlorate and alkali chloride is formed and the water-soluble organic onium perchlorate is separated.

However, the production of an onium perchlorate and a stabilizer composition according to the invention is not only possible from an aqueous solution. It is also possible to produce an appropriate onium perchlorate in organic solution.

For this purpose, an aqueous solution of an organic compound capable of forming an onium salt or a salt of such a compound is mixed with aqueous perchloric acid or an aqueous solution of an inorganic salt of perchloric acid. An organic onium perchlorate is formed, which remains in the organic solution. It is possible to work both in organic solvents that are not miscible with water and in organic solvents that are miscible with water. The water is then removed from the mixture.

The present invention therefore also relates to a process for producing a stabilizer composition according to the invention, in which an organic solution of an organic compound capable of forming an onium salt or a salt of such a compound is admixed with aqueous perchloric acid or an aqueous solution of an inorganic salt of perchloric acid, where a solution of an organic onium perchlorate is formed.

A stabilizer composition according to the invention can, as is evident from the processes described by way of example, in principle contain any suitable compound as a solvent. As a special case, which should be mentioned here in particular, a stabilizer composition according to the invention can contain a compound as a solvent or as a component of the solvent, which compound serves as the basis for the production of an onium chlorate, in particular can serve as the basis for the production of an onium perchlorate contained in a stabilizer composition according to the invention.

A stabilizer composition according to the invention can contain, in addition to the obligatory compounds already described above (onium perchlorate or onium perchlorate and at least one organic solvent), one or more further additives in an amount mentioned above.

In the context of the present text, additives are listed below which are suitable in principle for use in a stabilizer composition according to the invention alone or as a mixture of two or more thereof.

The aminouracil compounds of the general formula II are suitable as additives in the context of the present invention

R ³

1 wherein the radicals R and R are each independently of one another hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 C atoms, an optionally substituted saturated or unsaturated cycloalkyl radical having 6 to 44 C atoms or an optionally substituted aryl radical having 6 to 44 carbon atoms or an optionally substituted aralkyl radical having 7 to 44 carbon atoms or the radical R ^{1 is} an optionally substituted acyl radical having 2 to 44 carbon atoms and the radical R ^{3 is} hydrogen , an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 44 C atoms, an optionally substituted saturated or unsaturated cycloa- lipatic hydrocarbon radical having 6 to 44 carbon atoms or an optionally substituted aromatic hydrocarbon radical having 6 to 44 carbon atoms.

Compounds with a structural element of the general formula III are also generally suitable as additives

wherein n for a number from 1 to 100,000, the radicals R ^a , R ^b , R ⁴ and R ⁵ each independently of one another for hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 C atoms, one optionally substituted saturated or unsaturated cycloalkyl radical having 6 to 44 carbon atoms or an optionally substituted aryl radical having 6 to 44 carbon atoms or an optionally substituted aralkyl radical having 7 to 44 carbon atoms or the radical R ^{4 is} an optionally substituted acyl radical with 2 up to 44 carbon atoms or the radicals R ⁴ and R ⁵ are linked to form an aromatic or heterocyclic system and in which the radical R ^{6 is} hydrogen, an optionally substituted, linear or branched, saturated or unsaturated aliphatic alkyl or alkylene radical or oxyalkyl radical or oxyalkylene or mercaptoalkyl or mercaptoalkylene or aminoalkyl or amine oalkylene 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 mercaptocycloalkylene radical or aminocycloalkyl or aminocycloalkylene radical with 6 to 44 C atoms or an optionally substituted aryl Arylene radical with 6 to 44 C atoms or an ether or thioether radical with 1 to 20 O or S atoms or O and S atoms or for a polymer which has O, S, NH, NR ^a or CH ₂ C (O) is connected to the structural element in parenthesis, or the radical R ^{6 is so} with the radical R ⁴ is connected that an optionally substituted, saturated or unsaturated heterocyclic ring system with 4 to 24 carbon atoms is formed.

In the context of a preferred embodiment of the present invention, a compound based on an α, β-unsaturated β-aminocarboxylic acid, in particular a compound based on β-aminocrotonic acid, is used as the compound of the general formula I. The esters or thioesters of the corresponding aminocarboxylic acids with monohydric or polyhydric alcohols or mercaptans are particularly suitable here, where X in the cases mentioned is in each case O or S.

If the radical R ⁶ together with X represents an alcohol or mercaptan radical, such a radical can be composed, for example, of methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, isooctanol, isononanol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol , Stearyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, thio-diethanol, trimethylolpropane, glycerin, tris (2-hydroxymethyl) isocyanurate , Triethanolamine, pentaerythritol, di-trimethylolpropane, diglycerol, sorbitol, mannitol, xylitol, di-pentaerythritol and the corresponding mercapto derivatives of the alcohols mentioned.

In a particularly preferred embodiment of the present invention, a compound of the general formula III is used in which R is a linear alkyl radical having 1 to 4 carbon atoms, R ^{5 is} hydrogen and R ^{6 is} a linear or branched, saturated, mono- to hexavalent alkyl or alkylene radical having 2 to 12 carbon atoms or a linear, branched or cyclic 2- to 6-valent ether alcohol radical or thioether alcohol radical.

Suitable compounds of the general formula III include, for example,

Aminocrotonic acid stearyl ester, 1,4-butanediol-di (ß-aminocrotonic acid) ester, thio-diethanol-ß-aminocrotonic acid ester, trimethylolpropane-tri-ß-aminocrotonic acid ester, pentaerythritol-tetra-ß-aminocrotonic acid ester, dipentaerythritol-aminocrotonate and the like-aminocrotonic acid. The Compounds mentioned can be contained in a stabilizer composition according to the invention either alone or as a mixture of two or more of them.

Also suitable as compounds of the general formula III are, for example, compounds in which the radicals R ⁴ and R ⁵ are linked to form an aromatic or heteroaromatic system, for example aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and their suitable derivatives.

Examples of suitable additives are compounds which have a mercapto-functional sp ² -hybridized carbon atom, carbazoles, carbazole derivatives or 2,4-pyrrolidinedione or 2,4-pyrrolidinedione derivatives.

In the context of the present invention, suitable compounds which have at least one mercapto-functional, sp-hybridized carbon atom are in principle all compounds which have a structural element Z = CZ-SH or a structural element Z ₂ C = S, both structural elements being tautomeric forms of one single connection can be. The sp - hybridized carbon atom can be part of an optionally substituted aliphatic compound or part of an aromatic system. Suitable types of compounds are, for example, thiocarbamic acid derivatives, thiocarbamates, thiocarboxylic acids, thiobenzoic acid derivatives, thioacetone derivatives or thiourea or thiourea derivatives.

In a further embodiment of the present invention, thiourea or a thiourea derivative is used as an additive with at least one mercapto-functional, sp ² -hybridized carbon atom.

Epoxy compounds are also suitable as additives. 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.

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 is taken and which is considered 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 R ^' C (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. Acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptanedione-2,4, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, steaanylylzoyloylmethane, 5-ylbenzylmethane

Hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, benzoyllacetylmethyl, phenyl 1 Stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylphenylacetylmethane, bis (cyclohexanoyl) methane, dipivaloylmethane, 2-

Acetylcyclopentanone, 2-benzoylcyclopentanone, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester as well as propionyl or butyrylacetic acid esters with 1 to 18 C-atoms as well as stearoyl acetic acid ethyl, -propyl, ethyl -, Hexyl- or octyl esters or polynuclear ß-keto esters as described in EP-A 433 230, to which express reference is made, or dehydroacetic acid and its zinc, magnesium or alkali salts or the alkali, alkaline earth or zinc chelates of the compounds mentioned, insofar as they exist and are soluble in the stabilizer compositions according to the invention or with them to achieve the abovementioned Results are miscible.

1,3-diketo compounds can be contained in an inventive stabilizer composition in an amount of up to about 20% by weight, for example up to about 10% by weight. Also suitable as additives in the stabilizer composition according to the invention are polyols. Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, Bistrimetylolethan, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxymethyl) isocyanurate, palatinite, tetramethylolcyclohexanol, Tetramethylolcyclopenta - nol, tetramethylolcycloheptanol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1- O-α-D-glycopyranosyl-D-mannitol dihydrate.

The polyols suitable as additives can be contained in a stabilizer composition according to the invention in an amount of up to about 30% by weight, for example up to about 10% by weight.

Also suitable as additives are, for example, sterically hindered amines as mentioned on pages 7 to 27 of EP-A 1 046 668. 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.

A stabilizer composition according to the invention can furthermore contain, as an additive, an organotin compound or a mixture of two or more organotin compounds. Suitable organotin compounds are, for example, methyltin tris (isooctyl thioglycolate), methyltin tris (isooctyl 3-mercaptopropionate), methyltin tris (isodecyl thioglycolate), dimethyltin bis (isooctyl thioglycolate), dibutyltin (isooctyl thioglycolate), monobutyltin tris (isooctyl thioglycolate), dioctyltin bis (isooctyl thioglycolate), monooctyltin tris (isooctyl thioglycolate) or dimethyltin bis- (2-ethylhexaptopylate). 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 40% by weight, in particular up to about 20% 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, butyl dikresyl -, octyl-di (octylphenyl) -, tris- (2-ethylhexyl) -, tritolyl-, tris- (2-cyclohexyl-phenyl) -, 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 can also contain blocked mercaptans as additives, as are 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 can furthermore 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 soaps, provided that these lubricants do not fall under the term “solvent” in the sense of the present text 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. Fat ketones such as these are also suitable as additives are described in DE 4,204,887, and silicone-based lubricants, as they are called, for example, EP-A 0 259 783, or combinations thereof, as they are mentioned in EP-A 0 259 783. The documents mentioned are hereby expressly referred to, their disclosure regarding lubricants is part of the disclosure 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.

Also suitable as additives for stabilizer compositions according to the present invention are organic plasticizers, provided that these plasticizers do not already fall under the term “solvent” in the sense of the present text.

Suitable plasticizers are, for example, the compounds mentioned above in the description of the solvents from the group of phthalic acid esters, such as dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di- iso-octyl, di-isononyl, di-iso-decyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl or diphenylphthalate as well as mixtures of phthalates, for example mixtures of alkyl phthalates with 7 up to 9 or 9 to 11 carbon atoms in the ester alcohol or mixtures of alkyl phthalates with 6 to 10 and 8 to 10 carbon atoms in the ester alcohol. Particularly suitable for the purposes of the present invention are dibutyl, dihexyl, di-2-ethylhexyl, di-n- octyl, di-iso-octyl, di-iso-nonyl, di-iso-decyl, di-iso-tridecyl and benzyl butyl phthalate and the mixtures of alkyl phthalates mentioned.

Also suitable as plasticizers are the esters of aliphatic dicarboxylic acids, in particular the esters of adipic, azelaic or sebacic acid or mixtures of two or more thereof. Examples of such plasticizers are di-2-ethylhexyl adipate, di-isooctyl adipate, di-iso-nonyl adipate, di-iso-decyl adipate, benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-iso-decylseb. Within the scope of a further embodiment of the present invention, preference is given to di-2-ethylhexyl acetate and di-iso-octyl adipate.

Trimellitic acid esters such as tri-2-ethylhexyl trimellithate, tri-iso-tridecyl trimellithate, tri-iso-octyl trimellithate and trimellitic acid esters with 6 to 8, 6 to 10, 7 to 9 or 9 to 11 carbon atoms in the ester group are also suitable as plasticizers or mixtures of two or more of the compounds mentioned.

Further 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", W.V. Titow, 4th edition, Elsevier Publishers, 1984, pages 165-170. The most common starting materials for the production of polyester plasticizers are, for example, dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid and diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or diethylene glycol or mixtures of two or more thereof.

Also suitable as plasticizers are phosphoric acid esters, as can be found in the "Taschenbuch der Kunststoffadditive", chapter 5.9.5, pp. 408-412. Examples of suitable phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-diphenyl phosphate, triphenyl phosphate, tricresyl phosphate or trixylenyl phosphate, or mixtures of two or more thereof. Also suitable as plasticizers are chlorinated hydrocarbons (paraffins) or hydrocarbons as described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, chapter 5.9.14.2, pp. 422-425 and chapter 5.9.14.1, p. 422.

A stabilizer composition according to the invention can contain the plasticizers described in an amount of up to about 99.5% by weight, in particular up to about 30% by weight, up to about 20% by weight or up to about 10% by weight , In the context of a preferred embodiment of the present invention, the lower limit for the plasticizers described as part of the stabilizer compositions according to the invention is about 0.1% by weight or more, for example about 0.5% by weight, 1% by weight, 2 % By weight or 5% by weight.

In the context of a further embodiment of the present invention, the stabilizer compositions according to the invention can contain antioxidants, UV absorbers or light stabilizers. 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, the disclosures being considered part of the present text.

A stabilizer composition according to the invention can contain, in addition to a polymer and a stabilizer composition according to the invention, further additives which are not soluble in the stabilizer compositions according to the invention. In principle, all additives are suitable, for example those which do not or not significantly affect the transparency of a polymer composition produced with the aid of such a stabilizer composition.

Also suitable as additives in the stabilizer compositions according to the invention are hydrotalcites, hydrocalumites, zeolites and alkali alumocarbonates. Suitable hydrotalcites, hydrocalumites, zeolites and alkali alumocarbonates are described, 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 page 2 and 3 or DE-C 41 06 404 on page 2 and 3 or DE-C 198 60 798. Reference is expressly made to these publications and their disclosure is regarded as part of the disclosure of the present text.

The hydrotalcites, hydrocalumites, zeolites and alkali alumocarbonates suitable as additives can be present in an inventive stabilizer composition in an amount of up to about 50% by weight, for example from 0 to about 30% by weight.

Also suitable as additives in the stabilizer compositions according to the invention are metal oxides, metal hydroxides and metal soaps of saturated, unsaturated, straight-chain or branched, aromatic, cycloaliphatic or aliphatic carboxylic acids or hydroxycarboxylic acids with preferably about 2 to about 22 carbon atoms.

As metal cations, the metal oxides, metal hydroxides or metal soaps suitable as additives preferably have a divalent cation; the cations of calcium or zinc or mixtures thereof are particularly suitable.

Examples of suitable carboxylic acid anions include anions of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, lauric acid, palmitic acid, palmitic acid, palmitic acid 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert- butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, sorbic acid, anions of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid, mandelic acid , Glycolic acid, oxalic acid, salicylic acid, polyglycol dicarboxylic acids with a polymer Degree of isation from about 10 to about 12, phthalic acid, isophthalic acid, terephthalic acid or hydroxyphthalic acid, anions of tri- or tetravalent carboxylic acids or their mono-, di- or triestemes such as those in hemimellitic acid, trimellitic acid, pyromellitic acid or citric acid and also so-called overbased carboxylates such as them for example in DE-A 41 06 404 or DE- A 40 02 988 can be described, the disclosure of the latter documents being considered part of the disclosure of the present text.

In the context of a preferred embodiment of the present invention, metal soaps are preferably used, the anions of which are derived from saturated or unsaturated carboxylic acids or hydroxycarboxylic acids having about 8 to about 20 C atoms. Stearates, oleates, laurates, palmitates, behenates, versatates, hydroxystearates, dihydroxystearates, p-tert-butylbenzoates or (iso) octanoates of calcium or zinc or mixtures of two or more thereof are particularly preferred. In the context of a further preferred embodiment of the present invention, a polymer composition according to the invention has calcium stearate or zinc stearate or a mixture thereof.

A stabilizer composition according to the invention can contain the metal oxides, metal hydroxides or metal soaps mentioned or a mixture of two or more thereof in an amount of up to about 50% by weight, for example in an amount of up to about 30% by weight.

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, or contain pigments.

A stabilizer composition according to the invention may also contain impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, flame retardants and antifogging 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.

In the context of the present invention, it has been shown that the onium salts of perchlorates are suitable for stabilizing halogen-containing organic polymers. The present invention therefore relates to a polymer composition containing at least one halogenated organic polymer and an onium salt of a perchlorate. The amounts of onium salts to be used correspond to the amounts described in the context of the further text for the stabilizer compositions according to the invention.

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, ketones and other compounds such as acrolein, cronones - nylmethyl 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 above n were mentioned, 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 their 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 homo- and copolymers mentioned above, 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 above-mentioned 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, with basically 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.

In the context of a preferred embodiment of the present invention, a polymer composition according to the invention contains the stabilizer composition according to the invention in an amount of 0.1 to 20 phr, in particular approximately 0.5 to approximately 15 phr or approximately 1 to approximately 12 phr. The unit phr stands for "per hundred resin" and thus relates to parts by weight per 100 parts by weight of polymer.

A polymer composition according to the invention preferably contains PVC as a halogenated polymer, the PVC content being in particular at least about 20, preferably at least about 50% by weight, for example at least about 80 or at least about 90% by weight.

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.

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 rigid or, in particular, 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 “molded body” basically encompasses 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 jackets, automotive components, for example automotive components such as are used in the interior of the automobile, in the engine compartment or on the outer surfaces, cable insulating rods, decorative foils, agricultural foils, hoses, sealing profiles, office foils, hollow bodies ( Bottles), packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (window frames), light wall profiles, building profiles, sidings, fittings, plates, foam plates., Coextradates with recycled core or housing 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 present invention also relates to the use of a stabilizer composition according to one of claims 1 to 4 or a stabilizer composition produced according to one of claims 5 to 8 or a polymer composition according to one of claims 9 or 10 in the production of polymeric moldings or surface coating compositions.

The invention is explained in more detail below by examples.

Preparation of the perchlorate onium salts:

Example 1 :

15.11 g of nicotinic acid ethyl ester (2-ethylcarboxypyridine) were suspended in 100 ml of water and 16.73 g of a 60% aqueous HClO solution were added dropwise. After stirring for 20 minutes, a clear solution had formed. After the water had been drawn off in vacuo, crystalline 2-ethylcarboxypyridinium perchlorate was obtained. For further experiments, the product was used as a 10% solution (based on perchlorate) in propylene carbonate.

Example 2:

16.73 g of a 60% aqueous HClO solution were added dropwise to a solution of 4.5 g of formamide in 100 ml of water with stirring. After a reaction time of 20 minutes, the water was removed under vacuum. Crystalline formamidinium perchlorate was obtained. For further experiments, this was used as a 10% solution (based on perchlorate) in formamide.

Example 3:

1.6 g of 60% by weight HClO ₄ were slowly added dropwise to a solution of 3.39 g of tetra-n-butylphosphonium bromide in 50 ml of water with vigorous stirring. After a few minutes the formation of a crystalline precipitate was observed. After filtering off, 3.55 g of tetra-n-butylphosphonium perchlorate were isolated. For further experiments, the product was used as a 10% solution (based on perchlorate) in dioctyl phthalate (DOP).

Example 4:

22 g of trimethylsulfoxonium iodide were dissolved in 300 ml of water at room temperature. 16.74 g of HC1O4 (60% strength) were slowly added dropwise to this solution with stirring. The trimethylsulfoxonium perchlorate was quantitatively isolated by careful evaporation in vacuo. Furthermore, a solution in DOP (10% based on perchlorate) was used.

Example 5:

16.66 g of a 60% aqueous HClO were added dropwise to a solution of 26.05 g of trishydroxyethyl isocyanurate in dibutyl oxalate with stirring. The 10% solution obtained was dewatered in vacuo and used as received in further experiments. Example 6:

16.73 g of 60% aqueous HClO were added dropwise to a suspension of 11.72 g of 2- (diethylamino) ethanol in water with stirring. The corresponding perchlorate salt was quantitatively isolated by evaporation in vacuo. The product obtained was used as a 10% solution based on perchlorate in epoxidized soybean oil.

Example 7a

16.73 g of aqueous 60% HClO _{4 were} added dropwise to a solution of 13.12 g of N- (2-hydroxyethyl) morpholine in 100 ml of water with stirring. The corresponding N- (2-hydroxyethyl) -moφholinium perchlorate was obtained quantitatively by removing the water in a vacuum. In addition, a 10% solution was obtained by dissolving 2.3 g of the product obtained in N- (2-hydroxyethyl) morpholine, obtained based on perchlorate. This was used in the further experiments. Example 7b

8.37 g of aqueous, 60% HC10 were added dropwise to 45 g of N- (2-hydroxyethyl) morpholine with stirring. By removing the water in vacuo, the corresponding N- (2-hydroxyethy) morpholinium perchlorate was quantitatively obtained in the form of a 10% solution in N- (2-hydroxyethy) morpholine and used further.

Example 8a

16.73 g of aqueous 60% HClO were added dropwise to a solution of 35.36 g of trioctylamine in 100 ml of water with stirring. The corresponding trioctylammonium perchlorate was quantitatively obtained by removing the water in vacuo. Furthermore, a 10% solution, based on perchlorate, was obtained by dissolving 4.5 g of the product obtained in DOP. This was used in the further experiments.

Example 8b

8.37 g of aqueous 60% HClO were added dropwise to a mixture of 17.68 g of trioctylamine and 27.5 g of DOP with stirring. By removing the water in vacuo, the corresponding trioctylammonium perchlorate was obtained quantitatively in the form of a 10% solution in DOP and used further. Table 1:

Claims

claims

1. stabilizer composition, characterized in that it contains at least 0.05% by weight of an organic onium salt of a perchlorate or a mixture of two or more organic onium salts of perchlorates and at least one organic solvent.

2. Stabilizer composition according spoke 1, characterized in that it contains, based on the total composition 0.1 to 20 wt .-% of an organic onium salt of a perchlorate or a mixture of two or more organic onium salts of perchlorates.

3. Stabilizer composition according spoke 1 or 2, characterized in that it is an ammonium or an organic onium salt

Contains sulfonium salt or a mixture of two or more thereof.

Stabilizer composition according to one of claims 1 to 3, characterized in that it contains an organic solvent.

5. A method for producing a stabilizer composition according to any one of claims 1 to 4, in which an onium perchlorate is dissolved in an organic solvent.

6. A process for producing a stabilizer composition according to any one of claims 1 to 4, in which an organic compound capable of forming an onium salt or a salt of such a compound is mixed with perchloric acid or an inorganic salt of perchloric acid. sets, the formed onium salt of the organic compound is separated and dissolved in an organic solvent.

7. The method according to claim 6, characterized in that a water-soluble organic onium chloride is used as the organic compound capable of forming an onium salt and silver perchlorate is used as the inorganic salt of perchloric acid, the water-soluble organic onium chloride being mixed with silver perchlorate in aqueous solution, causing a precipitate and an aqueous solution of an organic onium perchlorate is formed, the precipitate formed is filtered off and the organic onium perchlorate in aqueous solution is isolated.

8. The method according to claim 6, in which an organic onium chloride is used as the organic compound capable of forming an onium salt and an alkali perchlorate is used as the inorganic salt of perchloric acid, the organic onium chloride being mixed with an aqueous solution of the alkali perchlorate, whereby a water-soluble organic Onium perchlorate and alkali chloride are formed and the water-insoluble organic onium perchlorate is separated off.

9. A method for producing a stabilizer composition according to any one of claims 1 to 4, in which an organic solution of an organic compound capable of forming an onium salt or a salt of such a compound is mixed with aqueous perchloric acid or an aqueous solution of an inorganic salt of perchloric acid , forming a solution of an organic onium perchlorate.

10. Polymer composition, at least containing a halogen-containing organic polymer and an onium salt of a perchlorate.

11. A polymer composition containing at least one halogen-containing organic polymer and a stabilizer composition according to one of claims 1 to 4 or a stabilizer composition produced according to one of claims 5 to 9.

12. Polymer composition according spoke 11, characterized in that it contains the stabilizer composition in an amount of 0.1 to 10 wt .-%.

13. Use of a stabilizer composition according to one of claims 1 to 4 or a stabilizer composition produced according to one of claims 5 to 9 or a polymer composition according to one of claims 10 to 12 in the production of polymeric moldings or surface coating agents.

14. 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 with one

Onium salt of a perchlorate or a stabilizer composition according to one of claims 1 to 4 or a stabilizer composition prepared according to one of claims 5 to 9 is mixed.

15. Shaped article containing at least one stabilizer composition according to one of claims 1 to 4 or a stabilizer composition produced according to one of claims 5 to 9 or a polymer composition according to one of claims 10 to 12.