EP1913065A1

EP1913065A1 - Solid organic salt preparation, the production thereof and its use

Info

Publication number: EP1913065A1
Application number: EP06762428A
Authority: EP
Inventors: Frank Reichwald; Stefan Fokken
Original assignee: Baerlocher GmbH
Current assignee: Baerlocher GmbH
Priority date: 2005-07-06
Filing date: 2006-07-05
Publication date: 2008-04-23
Also published as: WO2007003433A3; WO2007003433A2; DE102005031623A1

Abstract

The invention relates to a solid salt preparation with an improved usability, which contains a mixture consisting of an organic onium salt of a halogen-containing oxy acid and of a solvent. The invention also relates to a method for producing salt preparations of the aforementioned type and to their use, particularly in stabilizer compositions for halogen-containing polymers.

Description

Solid organic salt preparation, its preparation and use

The present invention relates to a solid salt preparation having improved handleability, which contains a mixture of an organic onium salt, a halogen-containing oxyacid and a solvent. Furthermore, the present invention relates to a process for preparing such salt preparations and their use, in particular in stabilizer compositions for halogen-containing polymers.

As is known, halogen-containing plastics tend to undergo undesired decomposition and degradation reactions during thermal stress during processing or in long-term use. The degradation of halogenated polymers, especially in PVC, produces hydrochloric acid, which is eliminated from the polymer strand, resulting in a discolored, unsaturated plastic with colored polyene sequences.

In particular, in the case of moldings which are exposed to light, changing temperatures or other external influences, the duration of use leads to changes in the color and the material properties, which can possibly progress to the unusability of the molded body.

Various stabilizer systems have been proposed to stabilize halogen-containing polymers with respect to long term damage by the action of light or heat. Thus, for example, systems are described in the prior art containing perchlorate salts for the stabilization of halogen-containing polymers.

A disadvantage of the described systems, however, is often that not in all applications, the desired stabilization effect in terms of stabilizing polymers can be achieved. Often the stabilizing effect lags behind the requirements.

Another problem with the use of perchlorate salts is that such sensitive oxidants usually have to be handled very carefully in order to damage the health of persons or damage to material, for example due to explosions, to avoid. For this reason, users often have reservations about the use of perchlorate salts in stabilizer compositions. Therefore, various solutions have been proposed as to how such perchlorate-containing stabilizer compositions can be improved in terms of their handleability.

For example, EP-B 0 457 471 describes a stabilizer composition containing perchlorate, calcium silicate and calcium carbonate. To prepare the stabilizer compositions described, an aqueous solution of sodium perchlorate is mixed with calcium silicate or a mixture of calcium silicate and calcium carbonate. The problem with the described stabilizer compositions is that they still contain crystallites of sodium perchlorate. These crystallites may, as described above, possibly cause problems in handling. Moreover, in some cases such stabilizer compositions can not be sufficiently homogeneously incorporated in a halogen-containing polymer to be stabilized. Furthermore, the presence of a carrier material often limits the stabilizer effect compared to other stabilizer compositions. In addition, the calcium silicate used in the described case has a high Mohs hardness, whereby processing plants can possibly be permanently damaged.

There was therefore a need to improve the performance of stabilizer compositions containing a salt of a halogenated oxyacid. In particular, there was a need to improve the performance of stabilizer compositions containing a salt of a halogen-containing oxyacid in view of the light and thermal stability of the halogen-containing polymers to be stabilized.

Due to the problems with regard to the handling of perchlorate salts or preparations based thereon, there has continued to be a need for those formulations which contain a salt of a halogen-containing oxyacid in a preparation which markedly reduces the risk of handling such perchlorate salts.

While preparations are known in the prior art, which include perchlorate salts in the form of a liquid solution in water or, for example, butyldiglycol, such liquid preparations are in many cases in terms of their applications, For example, in stabilizer compositions for halogen-containing polymers limited, in many cases it is the desire of the formulator of such stabilizer compositions that corresponding perchlorate salts of the stabilizer composition in solid form, so be added as solid salt preparations in order to have the greatest possible freedom from formulation in the adjustment of the consistency of the stabilizer composition , Liquid Perchloratzubereitungen often do not meet this desire.

It is therefore an object of the present invention to provide such solid salt preparations and stabilizer compositions and processes for their preparation based thereon.

The objects underlying the invention are achieved by salt preparations and stabilizer compositions containing such salt preparations, as well as processes for their preparation, as described in the context of the following text.

The present invention provides salt preparations that enable easy handling of perchlorate salts. In addition to the handling of perchlorate salts, however, the advantages according to the invention can in principle be achieved with all salts of halogen-containing oxyacids, for example also with chlorites, hypochlorites, chlorates, bromates, iodates, perbromates and the like.

The present invention therefore relates to a salt preparation containing at least one organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids and a solvent or a mixture of two or more solvents, wherein the organic onium salt of a halogen-containing oxyacid or the mixture from two or more organic onium salts of halogen-containing oxyacids in the solvent or the mixture of two or more solvents at 20 ⁰ C to at least 0.1 wt .-%, based on the solvent or the mixture of two or more solvents, is soluble and the Salt preparation at 5 ⁰ C is fixed. According to further embodiments, a salt preparation according to the invention at 80 ° C or at 70 ⁰ C or at 60 ° C or at 50 ° C or at 40 ° C or at 30 ⁰ C or at 20 ° C or at 10 ° C solid. A salt preparation according to the invention has at least two constituents. As a first component, a salt preparation according to the invention contains at least one organic onium salt of a halogen-containing oxyacid, in particular a perchlorate of the general formula M (C10 ₄ ) _k , where M is a suitable organic cation. The index k stands for the value of M for an integer, for example, the number 1, 2, 3 or 4.

Suitable organic cations M according to the invention are, for example, organic onium ions, the term "organic onium ion" being understood in the context of the present text to mean ammonium, sulfonium or phosphonium ions each carrying at least one organic radical. A corresponding onium ion according to the present invention may carry, depending on the nature of the onium group, 1, 2, 3 or 4 organic radicals The organic radicals may be, for example, via a CX linkage, where X is N, S or P, with However, it is likewise possible for the organic radicals to be bonded via another heteroatom, for example an O atom, to a positively charged N, S or P atom of an onium ion according to the invention. or P atom of an onium ion according to the invention are connected.

A suitable in the context of the present invention as part of a salt preparation according to the invention onium perchlorate, for example, a positively charged N, S or P atom or two or three or four or more such positively charged N, S or P atoms or mixtures two or more of said positive charged atom types.

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

Therefore, compounds according to the invention are therefore suitable as onium perchlorates which have a positive charge due to protonation reactions. It is the same, however it is possible to use onium perchlorates in the context of the salt preparations or stabilizer compositions according to the invention which have a positive charge due to an alkylation or 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 perchlorate perchlorate suitable according to the invention has an aryl, alkaryl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl radical. It is likewise possible and provided according to the invention for an onium salt which can be used in the context of a salt preparation according to the invention to have two or optionally more different substituent types, for example an alkyl and a cycloalkyl radical or an alkyl radical and an aryl radical.

It is likewise possible and provided in the context of the present invention for a onium salt which can be used in the context of a salt preparation according to the invention to have substituents which in turn are substituted by one or more functional groups. The term "functional groups" refers to groups which improve or at least do not or only insignificantly worsen the effects of the salt preparation or stabilizer composition. Corresponding functional groups may 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.

As phosphonium perchlorates are in the context of the present invention, in principle, all compounds can be used, which lead by appropriate reaction of suitable reactants to a Phosphoniumperchlorat. In this case, phosphonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of tetraalkyl, tetracycloalkyl or tetraarylphosphorus 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-pentylphosphonium bromide, tetra-n-hexylphosphonium bromide and the like Tetraalkylphosphorsalzen from.

In principle, phosphonium perchlorates which are suitable for use, for example, in the salt preparations according to the invention are also suitable Derive tetracycloalkylphosphorus salts or Tetraarylphosphorsalzen. Suitable phosphonium perchlorates are therefore based, for example, on tetracycloalkyl or tetraarylphosphonium salts, such as tetracyclohexylphosphonium bromide or tetraphenylphosphonium bromide, and the like tetracycloalkyl or tetraarylphosphorus salts. The compounds mentioned above may be unsubstituted in the context of the present invention, but they may also have one or more of the abovementioned substituents, provided that these substituents in the salt preparation or stabilizer composition have no adverse effects and do not adversely affect the intended use of the salt preparation.

Also usable in the context of the present invention are organic phosphonium perchlorates which carry on a phosphorus atom different types of organic substituents, which in turn may optionally be substituted differently.

In a preferred embodiment of the present invention, the phosphonium perchlorates used are tetra-n-butylphosphonium perchlorate or triphenylbenzylphosphonium perchlorate.

As sulfonium perchlorates in the context of the present invention, in principle, all compounds can be used which lead by appropriate reaction of suitable reactants to a Sulfoniumperchlorat. 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, allyl benzyl sulfide or alkyl disulfides such as hexane disulfide, heptane disulfide, octane disulfide and the like alkyl disulfides.

In principle, sulfonium perchlorates which are derived, for example, from tricycloalkylsulfonium salts or triarylsulfonium salts are also suitable for use in the context of the salt preparations 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. Also suitable are tri-alkyl, triaryl or Tricycloalkylsulfoxoniumsalze as Trimethylsulfoxoniumperchlorat. The The compounds mentioned above may be unsubstituted in the context of the present invention, but they may also have one or more of the abovementioned substituents, provided that these substituents in the salt preparation or stabilizer composition have no adverse effects and the purpose of the salt preparation of a stabilizer composition prepared from such salt preparation not adversely affect.

Also usable in the context of the present invention are organic sulfonium perchlorates which carry different types of organic substituents on a sulfur atom, which in turn may optionally be substituted differently.

In a preferred embodiment of the present invention, the sulfonium perchlorate used is trimethylsulfoxonium perchlorate.

As ammonium perchlorates are in the context of the present invention, in principle, all compounds can be used, which lead by appropriate reaction of suitable reactants to an ammonium perchlorate. In this case, 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. Suitable ammonium perchlorates are therefore derived, for example, from primary mono- or polyamino compounds having from 2 to about 40, for example from 6 to about 20, carbon atoms. For example, these are ethylamine, n-propylamine, i-propylamine, n-butylamine, substituted amines having 2 to about 20 carbon 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 of these are 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-Diaminocyclohexan, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or l, 8-diamino-4-aminomethyloctan or tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-ethyl, N-methyl, N-cyclohexylmor - pholine, 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, Pentamethyldiethylen- triamine, Tetramethyldiaminoethylether, bis- (dimethylaminopropyl) -urea, N ₅ N'-dimethylpiperazine, 1, 2-dimethylimidazole or di- (4- N, N-dimethylaminocyclohexyl) methane.

Also suitable are secondary aliphatic amino alcohols having 2 to about 40, preferably 2 to about 20 C atoms, for example diethanolamine, dipropanolamine, dibutanolamine, dipentanolamine, 2- (dimethylaminoethoxy) ethanol, aromatic-aliphatic or aromatic-cycloaliphatic secondary amino alcohols having 6 to about 20 carbon atoms.

Also suitable are aliphatic amino alcohols having 2 to about 40, preferably 2 to about 20 C-atoms, for example ethanolamine, diethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, tripentanolamine, l-amino-3,3-dimethyl-pentane-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-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentan-methanol, 2-amino-2-ethyl-1,3-propanediol, 2 - (dimethylaminoethoxy) - ethanol, aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols having 6 to about 20 C-atoms, wherein as aromatic structures heterocyclic or isocyclic ring systems such as naphthalene or especially benzene derivatives such as 2-aminobenzyl alcohol, 3- (hydroxymethyl) aniline, 2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propanediol and also Gem may be used from two or more such compounds.

According to a further embodiment of the present invention, the perchlorates of heterocyclic compounds which have a cyclic, amino-containing ring system are used as ammonium perchlorates.

In a preferred embodiment of the present invention, a salt preparation according to the invention contains, for example, triethanolammonium perchlorate.

A salt preparation according to the invention may contain, for example, only an organic onium salt of a halogen-containing oxyacid. However, it is within the scope of the present Invention also possible and provided that a salt preparation according to the invention contains a mixture of two or more organic onium salts of halogen-containing oxyacids.

The proportion of an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids in the salt preparation according to the invention is from about 0.01 to about 99.99% by weight, for example from about 0.1 to about 90% by weight. or from about 1 to about 85 weight percent, for example from about 5 to about 80 weight percent, or from about 10 to about 70 weight percent. Further suitable amounts are approximately in a range of about 15 to about 65 wt .-% or about 20 to about 60 wt .-%, each based on the total salt preparation.

As a second component, a salt preparation according to the invention contains at least one solvent. In the context of the present invention, a "solvent" is understood as meaning a compound which can dissolve an organic onium salt of a halogen-containing oxy acid or a mixture of two or more organic onium salts of halogen-containing oxyacids.

A salt preparation according to the invention may for example contain only one solvent. However, it is also possible and contemplated in the context of the present invention that a salt preparation according to the invention contains a mixture of two or more solvents.

The proportion of a solvent or a mixture of two or more solvents in the salt preparation according to the invention is for example about 0.01 to about 99.99 wt .-%, each based on the total salt preparation and substantially complements the organic onium salt of a halogen-containing oxyacid or the mixture of two or more such salts in the salt preparation at 100% by weight.

An organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids is "soluble" in the context of the present invention in a solvent or a mixture of two or more solvents, provided that it is present at 20 ° C. in an amount of at least 0.1 wt .-% or at least 0.5 wt .-% or at least 1.0 wt .-% or at least 3.0 wt .-% or at least 5.0 wt .-% or at least 10% by weight or at least 15% by weight or at least 20 wt .-%, each based on the solvent or the mixture of two or more solvents, dissolves. In particular cases, the solubility is for example at least about 40% by weight or at least about 60% by weight or at least 80% by weight or even higher, for example at least about 100% by weight or at least about 120% by weight .-%, in each case based on the solvent or the mixture of two or more solvents.

For example, a salt preparation according to the invention can be made exclusively from a solution, i. a mixture of organic onium salts of halogen-containing oxyacids and solvents which is essentially distributed in a molecularly dispersed manner. However, it is also possible for a salt preparation according to the invention to contain essentially any desired amount of undissolved salt constituents, for example up to about 90% by weight or less, for example up to about 80, 70, 60, 50, 40, 30, 20, 10 or 5% by weight or less, based in each case on the total salt preparation, of undissolved organic onium salts of a halogen-containing oxyacid. In a further embodiment of the present invention, a salt preparation according to the invention contains less than about 30, in particular less than about 10 or less than about 5 wt .-%, each based on the total salt preparation of undissolved organic onium salts of halogen-containing oxyacids.

The mixing ratio between an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or the mixture of two or more solvents in a mixture can be varied within wide limits, provided that the salt preparation is at a temperature of 80 ° C, for example at 70 ° C or at 60 ⁰ C or at 50 ° C or at 40 ° C or at 30 ° C or at 20 ⁰ C or at 10 ⁰ C or at 5 ° C is fixed.

"Solid" in the context of the present invention describes the presence of a substance, for example a salt preparation according to the invention, a stabilizer composition, an organic onium salt of a halogen-containing oxyacid or a solvent, in a state in which its shape is independent of the vessel in which it is located. For the purposes of the present invention, a solid substance has, for example, a viscosity of 10 ⁶ mPa s or more than 10 ⁶ mPa s or more than 10 ⁷ mPa s or more than 10 ⁸ mPa s or more than 10 ⁹ mPa s or more than 10 ¹⁰ mPa s or more than 10 ¹¹ mPa s on. A solid material in the sense of the present invention may for example be cut-resistant.

For example, the mixing ratio between an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or the mixture of two or more solvents in a mixture is between 1: 100 and 100: 1 or 1: 80 and 80 : 1 or 1: 60 and 60: 1 or 1:40 and 40: 1 or 1:20 and 20: 1 or 1:10 and 10: 1, said ratios relating to mass ratios.

In the context of the present invention, the mixing ratio between an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or the mixture of two or more solvents in a mixture can be adjusted so that the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids in the solvent or in the mixture of two or more solvents substantially completely dissolves and forms a solid solution at 5 ⁰ C.

The present invention also relates in particular to the provision of solid salt preparations comprising at least one low-melting organic onium salt of a halogen-containing oxyacid. Low-melting organic onium salts of halogen-containing oxyacids in the context of the present invention are for example those onium salts which at 80 ° C or at 70 ° C or at 60 ⁰ C or at 50 ⁰ C or at 40 ⁰ C or at 30 ° C or at 20 ⁰ C or at 10 ⁰ C or at 5 ° C are liquid.

The subject of a specific embodiment of the present invention is therefore for example a salt preparation, characterized in that the organic onium salt of a halogen-containing oxyacid or at least one organic onium salt of a halogen-containing oxyacid of a mixture of two or more organic onium salts of halogenated oxyacids at 80 ° C is liquid.

"Liquid" in the context of the present invention describes the presence of a substance, for example an organic onium salt of a halogen-containing oxyacid, a Solvent, a salt preparation according to the invention or a stabilizer composition according to the invention in a state in which its shape depends on the vessel in which it is located. For the purposes of the present invention, a liquid substance has, for example, a viscosity of at least 0.2 mPa s and less than 10 ⁶ mPa s or less than 10 ³ mPa s or less than 10 mPa s or less than 1 mPa s or of less than 0.5 mPa s.

A further advantage of the present invention is the possibility of providing low-melting organic onium salts of halogen-containing oxy acids already at temperatures in the form of a solid salt preparation in which the corresponding organic onium salts of halogen-containing oxyacids are still in liquid form in pure form.

The subject of the present invention therefore also forms salt preparation, characterized in that the salt preparation at the melting point of the organic onium salt of a halogen-containing oxyacid or at the melting point of the lowest-melting organic onium salt of a mixture of two or more organic onium salts of halogen-containing oxy acids is solid.

In addition, a further advantage of the present invention is the possibility of providing organic onium salts of halogen-containing oxyacids even at temperatures in the form of a solid salt preparation in which the solvents used to prepare the salt preparation are still in liquid form in pure form.

The present invention thus further relates to a salt preparation, characterized in that the salt preparation is solid at the melting point of the solvent or at the melting point of the lowest melting solvent of a mixture of two or more solvents.

In a particular embodiment of the present invention, a salt preparation according to the invention is at the melting point of the organic onium salt of a halogenated oxyacid or at the melting point of the lowest melting organic onium salt of a mixture of two or more organic onium salts of halogenated oxyacids and at the melting point of the solvent or at the melting point of the lowest melting solvent of a mixture of two or more solvents.

Suitable solvents in the context of a salt preparation according to the invention are both inorganic and organic solvents and mixtures thereof. In a preferred embodiment, organic solvents are used.

The subject of the present invention is therefore also a salt preparation, characterized in that the salt preparation contains at least one organic solvent.

Solvents which are suitable according to the invention are, in particular, polar organic solvents. As polar organic solvents, all solvents are suitable according to the invention whose molecules have an electric dipole moment. Particularly suitable are polar organic solvents with electronegative heteroatoms, for example O, S, N, P, F, Cl, Br.

A further embodiment of the present invention relates to a salt preparation, characterized in that the salt preparation contains at least one polar organic solvent.

For example, polyols which can be used as polar organic solvents are polyols. In the context of the present invention, the term "polyols" refers to organic compounds which have two or more OH groups per molecule. Examples of suitable polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimetalolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcycloheptanol , Glycerin, diglycerin, polyglycerol, thiodiglycerine or 1-0-α-D-glycopyranosyl-D-mannitol dihydrate. Further suitable polyols according to the invention are polyethylene glycols, for example with a molar mass in a range from 200 to 15,000 g / mol or from 300 to 12,000 g / mol or from 400 to 10,000 g / mol or from 400 to 8,000 g / mol or from 600 to 8,000 g / mol. Examples of polyethylene glycols which are suitable according to the invention are PEG 200, PEG 300, PEG 400, PEG 600, PEG 900, PEG 1000, PEG 1500, PEG 2000, PEG 3400, PEG 4600, PEG 8000 or PEG 10000. In a further embodiment of the present invention, therefore, a salt preparation contains at least one polyol as solvent.

Also suitable as polar organic solvents are aliphatic amino alcohols, for example amino monoalcohols or amino polyols having 2 to about 40, preferably 2 to about 20 C atoms, for example ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri-n-propanolamine, tributanolamine, tripentanolamine, Amino-3,3-dimethylpentan-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-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentan-methanol, 2- Amino-2-ethyl-1, 3-propanediol, 2- (dimethylaminoethoxy) - ethanol, aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols having 6 to about 20 C atoms, wherein as aromatic structures 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-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propanediol and mixtures of two or more such compounds.

The present invention therefore relates to a salt preparation, characterized in that the salt preparation contains at least one amino alcohol as solvent. In a specific embodiment, the salt preparation comprises triethanolamine as solvent.

Within the scope of a preferred embodiment of the present invention, at least one solvent which has a beneficial effect on the stabilization of halogen-containing polymers is used as constituent of the salt preparation according to the invention.

The mixing of an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids and a solvent or a mixture of two or more solvents is carried out according to the invention in such a way that the solvent or the mixture of two or more solvents during mixing is used in liquid form. It is also provided according to the invention that the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts contains halogen Oxysäuren is used in liquid form. In a further embodiment, the mixing is carried out in such a way that both the solvent or the mixture of two or more solvents, and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids are used in liquid form.

The preparation of a solid salt preparation according to the present invention succeeds in principle by any method known to those skilled in mixing different solid and liquid substances, for example by simply mixing the organic onium salt of a halogenated oxyacid or the mixture of two or more organic onium salts of halogenated oxyacids and the solvent or of the mixture of two or more solvents. For example, the solvent or the mixture of two or more solvents may be initially charged and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids added. However, it is also provided according to the invention that the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids are initially charged and then the solvent or the mixture of two or more solvents is added. In addition, instead of the organic onium salts of halogen-containing oxyacids or mixtures thereof, suitable amines or mercaptans or sulfides or phosphines or mixtures of two or more of these compounds may be used together with an acid or a mixture of at least two acids instead of the organic onium salts become.

The present invention therefore also provides a salt preparation preparable by mixing

a. a solvent or a mixture of two or more solvents and b. at least one organic onium salt or c. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and at least one acid and d. at least one inorganic salt of a halogen-containing oxyacid, wherein at least 0.1 wt .-% of an organic onium salt of a halogenated oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids, based on the solvent or the mixture of two or more solvents are dissolved in this and the salt preparation at 5 ° C is fixed.

Acids which are suitable according to the invention for the preparation of organic onium salts are in principle all compounds known to the skilled person which are capable of protonating suitable amines or mercaptans or sulfides or phosphines according to the invention and which do not have the properties of a salt preparation according to the invention and of products prepared therefrom, for example stabilizer compositions only negligibly adversely affect.

Inorganic acids suitable according to the invention include, for example, mineral acids such as HCl, HClO ₂ , HClO ₃ , HClO ₄ , HBr, HBrO ₃ , HBrO ₄ , HI, HIO ₃ , HIO ₄ , H ₂ SO ₄ , H ₂ N-SO ₂ -OH, HNO ₃ , H ₃ PO ₃ , H ₃ PO ₄ . Inorganic acids suitable in accordance with the invention include, in particular, acidic zeolites.

Organic acids suitable according to the invention include, for example, abietic acid, adipic acid, malic acid, formic acid, arachic acid, behenic acid, benzoic acid, succinic acid, butyric acid, capric acid, caproic acid, caprylic acid, acetic acid, erucic acid, fumaric acid, uric acid, icosenoic acid, lauric acid, lignoceric acid, margaric acid, maleic acid, malonic acid, Methanesulfonic, lactic, myristic, nervonic, nonadecanoic, oleic, ennomanic, oxalic, palmitic, palmitoleic, pelargonic, pentadecanoic, propionic, stearic, trichloroacetic, tridecanoic, undecanoic, valeric, tartaric, citric acids.

According to the invention suitable inorganic salts of halogen-containing oxy acids include for example ACLO, ACLO _2, ACLO _3, ACLO _4, Åbro, Åbro _2, Åbro _3, Åbro _4, AIO, AIO _3, AlO _4, E (ClO) _2, E (Cloz) _2, e (C1O ₃₎ _2, e (C1O ₄₎ _2, e (BrO) _2, e ₍₂ BrO) ,, e (BrO ₃₎ _2, e (BrO ₄₎ _2, e (IO) _2, e (IO ₃₎ _2, e (IO ₄₎ _2, G (ClO) _3, G (C1O ₂₎ _3, G (C1O ₃₎ _3, G (C1O ₄₎ _3, G (BrO) _3, G (BrO ₂₎ ₃ , G (BrO ₃ ) ₃ , G (BrO ₄ ) ₃ , G (IO) ₃ , G (IO ₃ ) ₃ , G (IO ₄ ) ₃ , where A is an NH ₄ , Li, Na or K -Ion, E is an Mg, Ca, Sr, Ba or Zn ion and G is an Al or La ion. Furthermore suitable are compounds of cerium such as Ce (ClO) ₂ , Ce (C10 ₂ ) ₂ , Ce (ClO ₃ ) ₄ , Ce (C10 ₄ ) ₄ , Ce (BrO) ₄ , Ce (BrO ₂ ) ₄ , Ce (BrO ₃ ) ₄ , Ce (BrO ₄ ) ₄ , Ce (IO) ₄ , Ce (IO ₂ ) ₄ , Ce (IO ₃ ) ₄ , Ce (IO ₄ ) ₄ .

The protonation according to the invention suitable amines or mercaptans or sulfides or phosphines also succeeds through the use of ion exchangers. Suitable in principle according to the invention are all ion exchangers which are capable of exchanging cations for protons of an ion exchanger. According to the invention, both solid and liquid ion exchangers can be used. For example, zeolites or hydrotalcites are particularly suitable.

If, for example, an amine or mercaptan or sulfide or phosphine is used together with an inorganic salt of a halogen-containing oxyacid to prepare a salt preparation according to the invention, the inorganic cation of the inorganic salt of a halogen-containing oxyacid can be exchanged for protons of an ion exchanger, whereby the amine or mercaptan suitable according to the invention or sulfide or phosphine protonated and the corresponding organic onium salt of a halogen-containing oxyacid is prepared.

The subject of a further embodiment of the present invention is therefore a salt preparation preparable by mixing

a. a solvent or a mixture of two or more solvents and b. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and c. at least one inorganic salt of a halogen-containing oxyacid and treatment of mixing with an ion exchanger for the exchange of cations,

wherein at least 0.1 wt .-% of an organic onium salt of a halogenated oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids, based on the solvent or the mixture of two or more solvents are dissolved in this and the salt preparation at 5 ° C is fixed. The present invention therefore also provides processes for preparing salt preparations according to the invention.

The present invention thus also relates to processes for preparing salt preparations according to the invention, characterized by the mixing of

a. a solvent or a mixture of two or more solvents and b. at least one organic onium salt or c. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and at least one acid and d. at least one inorganic salt of a halogen-containing oxyacid.

For the preparation of salt preparations according to the invention, the solvent or the mixture of two or more solvents is preferably used in liquid form. For the production of salt preparations according to the invention, however, not only solvents which are liquid at room temperature are suitable. It is also provided according to the invention to use solvents, for example, above 80 ° C or at 80 ⁰ C or at 70 ⁰ C or at 60 ⁰ C or at 50 ° C or at 40 ° C or at 30 ° C or at room temperature are firm.

To provide, for example, above 80 ° C or at 80 ° C or at 70 ⁰ C or at 60 ° C or at 50 ⁰ C or at 40 ⁰ C or at 30 ⁰ C or at room temperature solid solvents or mixtures of two or more such solvents in liquid form may be heated during mixing to a suitable temperature suitable for producing the salt preparation according to the invention and / or kept within a suitable temperature range. For example, a solvent or a mixture of two or more solvents can be initially charged and heated and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids subsequently added. However, it is also provided according to the invention to provide a solvent or a mixture of two or more solvents and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids and both to a for preparing a salt preparation according to the invention to heat suitable temperature. According to the invention, a suitable temperature is understood to mean a temperature at which the mixing of an organic onium salt of a halogen-containing oxy acid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or a mixture of two or more solvents ensures the preparation of a salt preparation according to the invention.

The mixing of an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids with a solvent or a mixture of two or more solvents can therefore be carried out at different temperatures with the proviso that the solvent or the mixture of two or more Solvents is in liquid form.

The mixing can therefore be carried out, for example, at room temperature, but it is also provided according to the invention that the mixing also takes place at temperatures below or above room temperature. In principle, the temperature during mixing should be selected so that the dissolution process during mixing takes place as quickly as possible, but no or at least no significant reaction between the organic onium salt of a halogenated oxyacid or the mixture of two or more organic onium salts of halogenated oxyacids with the solvent or the mixture can be made of two or more solvents. Thus, the mixing can in principle be carried out in a temperature range of -50 ° C to 200 ° C. Within the scope of further embodiments of the present invention, the mixing in a temperature range from -30 ° C to 180 ⁰ C, or from -10 ° C to 160 ° C or from 10 ° C to 140 ° C or from 20 ° C to 130 ° C or from 20 ° C to 110 ° C or from 20 ° C to 90 ° C or from 20 ° C to 70 ° C.

A further subject of the present invention are methods for preparing salt preparations according to the invention using ion exchangers. The use of suitable ion exchangers makes it possible, for example, to protonate suitable amines or mercaptans or sulfides or phosphenes according to the invention without the use of a further acid. If, for example, an amine or mercaptan or sulfide or phosphine is used together with an inorganic salt of a halogen-containing oxy acid to prepare a salt preparation according to the invention, the inorganic compound can be used Exchange the cation of the inorganic salt of a halogen-containing oxyacid with protons of an ion exchanger, whereby the amine or mercaptan or sulfide or phosphine suitable according to the invention is protonated and the corresponding organic onium salt of a halogen-containing oxyacid is prepared.

The subject matter of the present invention is therefore a process characterized by the mixing of

a. a solvent or a mixture of two or more solvents and b. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and c. at least one inorganic salt of a halogen-containing oxyacid and d. Treatment of the mixture with an ion exchanger for the exchange of cations.

The use of ion exchangers allows the direct preparation of salt preparations according to the invention which contain substantially no further compounds in addition to a solvent or a mixture of two or more solvents and an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids. Immediately in this context means that the use of ion exchangers, the preparation of inventive salt preparations, for example, without further, subsequent to the ion exchange process steps, which serve, for example, the removal of undesirable production-related impurities, succeeds.

The use of ion exchangers according to the invention makes it possible to formulate a salt preparation directly after the ion exchange. In this context, "direct" means that the salt preparation after the ion exchange and before the preparation is not subjected to any process steps known to the person skilled in the art and used for the preparation, in particular for the purification. A purification step of the present invention is any process step that is suitable for removing from a mixture of substances, for example a salt preparation according to the present invention, substances and / or compounds or separating a mixture of substances. The present invention therefore provides a process for preparing a salt preparation according to the invention, characterized in that the salt preparation is formulated directly after the ion exchange.

In the context of the present invention, "packaging" means providing, for example, a salt preparation in a form suitable, for example, for transport or storage. Such forms are, for example, granules, lozenges, flakes and other physical forms known to those skilled in the art.

A salt preparation according to the present invention can be used, for example, as a stabilizer composition or as a constituent of a stabilizer composition for stabilizing halogen-containing polymers.

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

A salt preparation according to the present invention may already be used alone, i. without the addition of further additives as a stabilizer composition for stabilizing halogen-containing polymers. Frequently, however, it is advantageous to mix a salt preparation according to the invention with further additives to form a stabilizer composition.

Also suitable as additives are, for example, amino alcohols, provided they are not already present as solvents in the salt preparation according to the invention. Suitable amino alcohols in the context of the present invention are in principle all compounds which have at least one OH group and one primary, secondary or tertiary amino group or a combination of two or more of the amino groups mentioned. In principle, both solid and liquid are within the scope of the present invention Amino alcohols are suitable as part of the Stabilisatorzusatnmensetzungen invention. In the context of the present invention, however, the proportion of liquid aminoalcohols is chosen, for example, such that the entire stabilizer composition is substantially in solid form.

Suitable examples are OH-bearing 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-containing derivatives of ethylamine, n-propylamine, i-propylamine, sec-propylamine, tert-butylamine, 1-aminoisobutane, substituted amines having two to about 20 C atoms such as 2- (N, N-dimethylamino) -l-aminoethane. Suitable OH-bearing derivatives of diamines are, for example, those which are based on diamines having a molecular weight of from 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 of these are 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 diethylenetriamine or 1,8-diamino-4-aminomethyloctane, triethylamine, tributylamine, dimethylbenzylamine, N-ethyl, N-methyl, N-cyclohexylmorpholine, dimethylcyclohexylamine, Dimoφholinodiethyl 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.

Particularly suitable are aliphatic amino alcohols having 2 to about 40, preferably 6 to about 20 C atoms, for example, 1-amino-3,3-dimethyl-pentane-5-ol, 2-aminohexane-2 ', 2 "- diethanolamine, l -Amino-2,5-dimethylcyclohexan-4-ol-2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-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 having 6 to about 20 carbon atoms, wherein as aromatic structures 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-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1, 3 propanediol as well as mixtures of two or more such compounds come into consideration.

Within the scope of a particularly preferred embodiment of the present invention, heterocyclic compounds which have a cyclic, amino-containing ring system are used as the amino alcohols, the OH groups being connected either directly to the ring or preferably via the spacer.

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

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

CHYOH

(CH ₂ L

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 or branched, saturated or unsaturated alkyl group having 1 to about 10 C atoms. Particularly preferred within the scope of the present invention is the use of tris (hydroxyethyl) isocyanurate (THEIC) as constituent of the stabilizer compositions according to the invention. For example, a stabilizer composition according to the invention may contain only one aminoalcohol. However, it is also provided in the context of the present invention that a stabilizer composition according to the invention comprises a mixture of two or more different aminoalcohols.

Also suitable as additives in the context of the present invention are compounds having a structural element of the general formula II

wherein n is a number from 1 to 100,000, the radicals R ⁴ , R ⁵ , R ¹ and R ^{2 are} each independently hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 carbon atoms, a 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 ^{1 is} an optionally substituted acyl radical with 2 to 44 carbon atoms or the radicals R ¹ and R ² are bonded to 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 amino noalkylenrest having 1 to 44 carbon atoms, an optionally substituted saturated or unsaturated cycloalkyl or cycloalkylene radical or Oxycycloalkyl- or Oxycycloalkylenrest or Mercaptocycloalkyl- or Mercaptocycloalkylenrest or Aminocycloalkyl- or Aminocycloalkylenrest having 6 to 44 carbon atoms or an optionally substituted aryl or arylene radical 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 which is O, S, NH, NR ⁴ or CH ₂ C (O ) is connected to the parenthetical structural element, or the radical R ^{3 is} connected to the radical R ^{1 in} such a way that a total of one optionally substituted, saturated or unsaturated heterocyclic Ring system having 4 to 24 carbon atoms is formed, or a mixture of two or more compounds of the general formula I, included.

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

If the radical R ³ together with X stands for an alcohol or mercaptan radical, such a radical can be selected, for example, from 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, glycerol, tris- (2-hydroxyethyl) -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, the compound of general formula II used is a compound in which R ^{1 is} a linear alkyl radical having 1 to 4 C atoms, R ^{2 is} hydrogen and R ^{3 is} a linear or branched, saturated , mono- to hexahydric 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 II include, for example, β-aminocrotonic acid stearyl ester, 1,4-butanediol-di (β-aminocrotonic acid) ester, thio-diethanol-β-aminocrotonic acid ester, trimethylolpropane tri-β-aminocrotonic acid ester, pentaerythritol tetra-n-butylester. β-aminocrotonic acid ester, dipentaerythritol hexa-β-aminocrotonic acid ester and the like. The compounds mentioned can each be contained in a stabilizer composition according to the invention alone or as a mixture of two or more thereof. Likewise suitable for the purposes of the present invention as compounds of the general formula II are aminouracil compounds of the general formula III

wherein the radicals R ⁶ and R ^{7 are} each independently hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 carbon atoms, an optionally substituted saturated or unsaturated cycloalkyl radical having 6 to 44 carbon atoms or a 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 ^{6 is} an optionally substituted acyl radical having 2 to 44 carbon atoms or the radicals R ⁶ and R ⁷ to an aromatic or heterocyclic system and the radical R ^{8 is} hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 44 carbon atoms, an optionally substituted saturated or unsaturated cycloaliphatic hydrocarbon radical having 6 to 44 carbon atoms or a optionally substituted aromatic hydrocarbon radical having 6 to 44 carbon atoms and X is S or O.

The compound of formula III thus falls under the compounds of formula I, wherein n in the general formula I for 1 and the radicals R ¹ and R ³ according to the general formula I to the structural element of the general formula IV

R ⁹ wherein X is S or O. R ¹ in the case of a compound of the general formula IV is therefore NR ⁹ , while R ^{3 is} -RN-C = X and both radicals are covalently linked to a heterocyclic ring via an N-C bond. In the context of the present invention, preference is given to using compounds of the general formula IV in which R ^{9 is} hydrogen.

In the context of a further preferred embodiment of the present invention, compounds of general formula III are used in the stabilizer compositions according to the invention in which R ⁶ and R ^{8 are} a linear or branched alkyl radical having 1 to 6 C atoms, for example methyl, ethyl, propyl, butyl , Pentyl or hexyl, a substituted with OH groups linear or branched alkyl radical having 1 to 6 carbon atoms, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl or hydroxyhexyl, an aralkyl radical having 7 to 9 carbon atoms, for example benzyl, phenylethyl , Phenylpropyl, dimethylbenzyl or phenylisopropyl, where the said aralkyl radicals may be substituted by, for example, halogen, hydroxy or methoxy or an alkenyl radical having 3 to 6 C atoms, for example vinyl, alkyl, methallyl, 1-butenyl or 1-hexenyl.

In a preferred embodiment of the present invention, compounds of general formula III are used in the stabilizer compositions of the invention wherein R and R are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec- or t-butyl ,

Also suitable as compounds of the general formula I are, for example, compounds in which the radicals R ¹ and R ² are bonded to form an aromatic or heteroaromatic system, for example aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and their suitable derivatives.

In a preferred embodiment of the present invention, a stabilizer composition according to the invention contains a compound of general formula I or a mixture of two or more compounds of general formula I, for example a compound of general formula III, in an amount of about 0.1 to about 99 , 5 wt .-%, in particular about 5 to about 50 wt .-% or about 5 to about 25 wt .-%.

Other suitable additives in the context of the present invention are, for example, compounds which have at least one mercapto-functional, sp ² -hybridized C atom exhibit. In the context of the present invention, compounds which have at least one mercapto-functional, sp ² -hybridized carbon atom are in principle understood as meaning all compounds which have a structural element Z ^{1 =} CZ ² -SH or a structural element (Z ¹ H, Z ² ) C = S, wherein both structural elements may be tautomeric forms of a single compound. Z ¹ and Z ² denote substituted or unsubstituted organic radicals which, in combination with the mercapto-functional, sp ² -hybridized C atoms, realize compounds according to the invention which have at least one mercapto-functional, sp ² -hybridised C atom. In this case, Z ¹ and Z ^{2 may} optionally be bonded together and be part of a ring system. The sp ² -hybridized carbon atom may be part of an optionally substituted aliphatic compound or a constituent 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. Suitable compounds having at least one mercapto-functional, sp ² -hybridized carbon atom are mentioned, for example, in German Patent Application No. 101 09 366.7.

In a preferred embodiment of the present invention, thiourea or a thiourea derivative is used as the compound having at least one mercapto-functional, sp ² -hybridized carbon atom.

Also suitable as additives for the stabilizer compositions according to the invention are, for example, carbazole or carbazole derivatives or mixtures of two or more thereof.

Also suitable as additives are, for example, 2,4-pyrrolidinedione or its derivatives, as they are mentioned, for example, in German Patent Application No. 101 09 366.7, which is not prepublished.

Other suitable additives are, for example, 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 bonded directly to a carbon, oxygen, nitrogen or sulfur atom. Glycidyl or methyl glycidyl esters are obtainable by reacting a compound having 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.

As compounds having at least one carboxyl group in the molecule, for example, aliphatic carboxylic acids can be used. Examples of these carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic acid, methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid or pelargonic acid, and the mono- or tri-acid mentioned in the further course of this text polycarboxylic acids. Likewise suitable are cycloaliphatic carboxylic acids such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid or 4-methylhexahydrophthalic acid. Also suitable are aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

Glycidyl ethers or methyl glycidyl ethers can be obtained by reacting a compound having 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. Ethers of this type are derived for example from acyclic alcohols such as ethylene glycol, diethylene glycol or higher poly (oxyethylene) glycols, propane-l, 2-diol or poly (oxypropylene) glycols, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane -1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bis-trimethylolpropane, pentaerythritol, sorbitol and of polyepichlorohydrins, butanol, amyl alcohol, Pentanol and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol or technical alcohol mixtures, such as technical fatty alcohol mixtures from.

Suitable ethers are also derived from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1-bis (hydroxymethyl ) cyclohexan-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline. Suitable epoxy compounds can also be derived from mononuclear phenols, for example from phenol, resorcinol or hydroquinone, or based on polynuclear phenols, such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 4,4'-Dihydroxydiphe- nylsulfonen or obtained under acidic conditions condensation products of phenol with formaldehyde, such as phenol novolacs.

Other terminal epoxides suitable as additives in the context of the present invention are, for example, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-diphenyl glycidyl ether, N- (2,3-epoxypropyl) phthalimide or 2,3-epoxypropyl-4-methoxyphenyl ether ,

Also suitable are N-glycidyl compounds as obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing 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.

Also suitable are S-glycidyl compounds, for example di-S-glycidyl ether derivatives which are derived from dithiols such as ethane-l, 2-dithiol or bis (4-mercaptomethylphenyl) ether.

Particularly suitable epoxy compounds are described, for example, in EP-A 1 046 668 on pages 3 to 5, wherein the disclosure contained therein is expressly incorporated by reference and 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. 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, which are particularly suitable with regard to the radicals R ', are suitable for the purposes of the present invention. R "and R ^'" , and the disclosure of which is considered to be part of the disclosure of the present text. Particularly suitable here are, for example, acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert- Nonylthioheptanedione-2,4, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-

Hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, benzoylformylmethane, benzoylacetylphenylmethane, 1-benzoyl-1-acetylnonane, Stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylphenylacetylmethane, bis (cyclohexanoyl) methane, dipivaloylmethane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, diacetacetic acid methyl, -ethyl, -butyl, 2-ethylhexyl, dodecyl or octadecyl esters and also propionyl or butyrylacetic acid esters having 1 to 18 C atoms and stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters or polynuclear β-ketoesters as described in EP-A 433 230 to which reference is expressly made, or dehydroacetic acid and its zinc, magnesium or alkali metal salts or the alkali, alkaline earth, or zinc chelates of said compounds, if any exist.

1, 3 -Diketo compounds may be present in a stabilizer composition according to the invention in an amount of up to about 20 wt .-%, for example up to about 10 wt .-%.

Also suitable as additives in the context of the stabilizer composition according to the invention are polyols. Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimetylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, tetramethylolcyclohexanol, tetramethylolcyclopentanole , Tetramethylolcycloheptanol, glycerin, diglycerin, polyglycerol, thiodiglycerin or 1-O-α-D-glycopyranosyl-D-mannitol dihydrate.

The polyols suitable as additives may be present 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, hindered amines as they are mentioned in EP-A 1 046 668 on pages 7 to 27. On the sterically revealed there hindered amines are referred to, the compounds mentioned there are considered part of the disclosure of the present text.

The sterically hindered amines suitable as additives may be present 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 in the stabilizer compositions according to the invention are hydrotalcites, zeolites and alkali metal aluminocarbonates. Suitable hydrotalcites, zeolites and alkali metal aluminocarbonates 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, of DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 described on pages 2 and 3. These references are hereby incorporated by reference and their disclosure in the specified places is considered to be part of the disclosure of the present text.

The hydrotalcites, zeolites and alkali metal aluminates suitable as additives may be present in a stabilizer composition according to the invention in an amount of up to about 50% by weight, for example up to about 30% by weight.

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

M ²⁺ ₍₂₊ χAl ³⁺ (i _{+ y)} (OH) _{(6 + z)} A ^j - _a [B _r ] ^rl _b * m H ₂ O (V)

wherein M is calcium, magnesium or zinc, or mixtures of two or more thereof, A is a j-valent inorganic or organic acid anion, j is 1, 2 or 3, B is an inorganic or organic acid anion other than A, r is a integer> 1 and, if r> 1, indicates the degree of polymerization of the acid anion and 1 is 1, 2, 3 or 4 and indicates the valence of the acid anion, wherein for r = 1 1 for 2, 3 or 4 and for r> 1 1 indicates the valency of the individual monomer units of the polyanion and stands for 1, 2, 3 or 4 and rl indicates the totality of the polyanion and the following rules for the parameters x, y, a, b, r, z, and j apply:

0 <x <0.6, 0 <y <0.4, where either x = 0 or y = 0,

0 <a <0.8 / r and z = l + 2x + 3y-jar / b.

In a preferred embodiment of the present invention are used as additives compounds of general formula V, wherein M is calcium, which may optionally be present in admixture with magnesium or zinc or magnesium and zinc.

In the general formula V, A is an R-valent inorganic or organic acid anion, where r is 1, 2 or 3. Examples of acid anions present within the scope of inventive hydrocalumites are halide ions, SO ₃ ^" , SO ₄ ^2" , S ₂ O ₃ ^{2 "} , S ₂ O ₄ ^2" , HPO ₃ ^{2 "} , PO ₄ ^3" , CO ₃ ^{2 "} , Alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates, wherein the alkyl groups may be identical or different, straight-chain, branched or cyclic and preferably have from 1 to about 20 C. Also suitable as acid anions A are the anions of optionally functionalized di-, tri or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate, pyromellitate, maleate, tartrate, citrate and anions of the isomeric forms of hydroxyphthalic acid or of hydroxymesinic acid Within the scope of a preferred embodiment of the present invention, A represents an inorganic acid anion, in particular a halide ion, for example F ^" , Cl ^" or Br ^" , preferably for Cl ^" .

In the general formula V, B represents an acid anion other than A. In the event that in the general formula V r is the number 1, letter B stands for a 1-, inorganic or organic acid anion, where 1 is the number 2, 3 or 4. Examples of acid anions B present in the context of compounds of general formula V that can be used according to the invention are, for example, O ^" , SO ₃ ^" , SO ₄ ^" , S ₂ O ₃ ^" , S ₂ O ₄ ^" , HPO ₃ ^2" , PO ₄ ^{3 "} , CO ₃ ^{2 "} , alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates in which the alkyl groups, identical or different, may be straight-chain or branched or cyclic and preferably have 1 to about 20 C atoms. Also suitable as acid anions A are the anions of optionally functionalized di-, tri- or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate, pyromellitate, maleate, tartrate, citrate and anions of the isomeric forms of hydroxyphthalic acid or of hydroxymesic acid. Preferably B is in the context of the present invention in formula V is a borate or an anion of an optionally functionalized di-, tri- or tetracarboxylic acid. Particular preference is given to carboxylic anions and anions of hydroxycarboxylic acids having at least two carboxyl groups, with citrates being very particularly preferred.

In the event that r in the general formula V stands for a number of more than 1, the term [B _r ] ^{rl "stands} for an inorganic or organic polyanion having the degree of polymerization r and the valency 1 of the individual monomer units of the polyanion with the total value wherein 1 is equal to or greater than 1. Examples of suitable polyanions [B _r ] ^{rl ~} are polyacrylates, polycarboxylates, polyborates, polysilicates, polyphosphates or polyphosphonates.

In all the cases mentioned above, the acid anions A and B may be present in any ratio a / b in the compounds of general formula V.

The compounds of general formula V are not layered compounds of the hydrotalcite or hydrocalumite type, but a physical mixture of M ²⁺ / alumina hydrates with salts of divalent metals. X-ray diffractograms of the compounds of the general formula V used in the stabilizer composition according to the invention clearly show that they are not discrete crystalline compounds of a known type but X-ray amorphous mixtures.

For the preparation of the compounds according to the general formula V, solutions or suspensions of oxidic forms of the desired cations (eg NaAlO ₂ , Ca (OH) ₂ , Zn (OH) ₂ , Al (OH) ₃ ) with solutions or solutions may be prepared according to known methods Suspension of salts or the corresponding acids of the desired anions are mixed and reacted at temperatures between 40 and 95 ° C. The reaction times can be varied between 15 and 300 minutes.

If a surface treatment of the reaction products is desired, the reaction products may be treated directly with the surface treatment agent, the product separated by filtration from the mother liquor and at suitable temperatures between 100 and 100 ° C 250 ° C are dried. The amount of surface treatment agent added is, for example, about 1 to about 20% by weight.

Compounds of general formula V can be used in the context of the stabilizer compositions according to the invention in an amount of up to about 50 wt .-%, for example up to about 30 or up to about 15 wt .-%.

In another embodiment of the present invention, a stabilizer composition according to the invention comprises at least one basic calcium salt. Suitable basic calcium salts are, for example, calcium oxide, calcium carbonate or, if it is not already a mandatory constituent of the stabilizer compositions according to the invention, calcium hydroxide. The basic calcium salts may optionally be surface-modified.

Also suitable as additives to the stabilizer composition 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 having preferably about 2 to about 22 carbon atoms.

As metal cations, the metal oxides, metal hydroxides or metal soaps which are suitable as additives preferably have a divalent cation, the cations of calcium or zinc or lead or mixtures of two or more thereof are particularly suitable, but in a preferred embodiment of the present invention the stabilizer compositions according to the invention are free from zinc.

Examples of suitable carboxylic acid anions include anions of monovalent carboxylic acids such as acetic, propionic, butyric, valeric, hexanoic, enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pelargonic, decanoic, undecanoic, dodecanoic, tridecanoic, myristic, palmitic, lauric, isostearic, stearic, 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, toluic 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, malic acid, glycolic acid, oxalic acid, salicylic acid, Polyglykoldicarbonsäuren with a degree of polymerization of 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 triesters as described in Hemirnellithsäure, trimellitic acid, pyromellitic acid or citric acid and also so-called overbased carboxylates as described for example in DE-A 41 06 404 or DE-A 40 02 988, the disclosure of the latter Documents as part of the disclosure of the present text is considered.

In a preferred embodiment of the present invention, metal soaps are used as additives whose anions are derived from saturated or unsaturated carboxylic acids or hydroxycarboxylic acids having about 8 to about 20 C atoms. Particular preference is given here to 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. Within the scope of a further preferred embodiment of the present invention, a stabilizer composition according to the invention comprises calcium stearate or zinc stearate or a mixture thereof.

A stabilizer composition according to the invention may contain said metal oxides, metal hydroxides or metal soaps 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 may furthermore furthermore contain, as thermostabilizer component, an organotin compound or a mixture of two or more organotin compounds. Examples of suitable organotin compounds are methyltin tris (isooctyl thioglycolate), methyltin tris (isooctyl) 3-mercaptopropionate, methyltin tris (isodecyl thioglycolate), dimethylzimi bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), monobutyltin tris (isooctyl thioglycolate), diocryltin bis (isooctyl thioglycolate), monooctyltin tris (isooctyl tioglycolate) or dimethyl tin bis (2-ethylhexyl -beta-mercaptopropionate). In addition, within the scope of the stabilizer compositions according to the invention, the organotin compounds mentioned in EP-A 0 742 259 on pages 18 to 29 and described in their preparation can be used. The above-mentioned disclosure is expressly incorporated by reference, 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 may contain the described organotin compounds in an amount of up to about 20% by weight, in particular up to about 10% by weight.

Within the scope of a further embodiment of the present invention, a stabilizer composition according to the invention may contain organic phosphite esters having 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 C atoms, optionally substituted alkyl radicals having 6 to 20 C atoms or optionally substituted aralkyl radicals having 7 to 20 C 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 may contain the described phosphite compounds 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 furthermore comprise, as additives, mercaptans blocked, as are mentioned in EP-A 0 742 259 on pages 4 to 18. The disclosure in the indicated specification is expressly incorporated, it is understood as part of the disclosure of the present text. A stabilizer composition according to the invention may contain the described blocked mercaptans 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 further comprise lubricants such as paraffin waxes, polyethylene waxes, polypropylene waxes, montan waxes, ester lubricants such as fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps. Useful lubricants are also in "plastic additives", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, p. 478-488. Also suitable as lubricants are, for example, fatty ketones as described in DE 4,204,887 and silicone-based lubricants, as mentioned, for example, in EP-A 0 259 783, or combinations thereof, as mentioned in EP-A 0 259 783. The documents cited are hereby incorporated by reference, the disclosure of which relates to lubricants being considered part of the disclosure of the present text. In the context of the present invention, lubricants of the product series Baerolub® from Baerlocher GmbH (Unterschleissheim, Germany) are particularly suitable.

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

Also useful as additives for stabilizer compositions according to the present invention are organic plasticizers.

Suitable plasticizers are, 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-, dimethyl glycol, dibutyl glycol, benzyl butyl or diphenyl phthalate and mixtures of phthalates, for example mixtures of alkyl phthalates having 7 to 9 or 9 to 11 C atoms in the ester alcohol or Mixtures of alkyl phthalates having 6 to 10 and 8 to 10 C 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 Benzylbutylphthalat and the said mixtures of alkyl phthalates. 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, diisooctyl adipate, diiso-nonyl adipate, diisodecyl adipate, benzyl butyl adipate, benzyloctyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate. Within the scope of a further embodiment of the present invention, preference is given to di-2-ethylhexyl acetate and diisoctyl adipate.

Likewise suitable as plasticizers are trimellitic esters, such as tri-2-ethylhexyl trimellitate, triiso-tridecyl trimellitate, triisoctyl trimellitate and trimellitic esters having 6 to 8, 6 to 10, 7 to 9 or 9 to 11 C atoms in the ester group or mixtures of two or more of said compounds.

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. Titov, 4th Edition, Elsevier Publishers, 1984, pp. 165-170. The most common starting materials for the preparation 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 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.

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 may 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 a preferred embodiment of the present invention, the lower limit for the described plasticizers as part of the stabilizer compositions according to the invention about 0.1 wt .-% or more, for example about 0.5 wt .-%, 1 wt .-%, 2 wt. -% or 5%, -%.

Also suitable as a constituent of the stabilizer compositions according to the invention are pigments. 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, perylene pigments, diketopyrrolopyrrole pigments or anthraquinone pigments.

A stabilizer composition according to the invention may further comprise fillers as described in the Handbook of PVC Forming, EJ Wickson, John Wiley & Sons, Inc., 1993, pages 393-449, or reinforcing agents as described in the "Plastic Adhesive Handbook". , 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 one preferred embodiment of the present invention, one contains Stabilizer composition according to the invention Cretaceous.

Within the scope of a further embodiment of the present invention, the stabilizer compositions according to the invention may contain antioxidants, UV absorbers and light stabilizers or blowing agents. Suitable antioxidants are described, for example, in EP-A 1 046 668 on pages 33 to 35. For the purposes of the present invention, the products of the Irganox® series (manufacturer: Ciba Specialty Chemicals), for example Irganox® 1010 or 1076 or products of the Lowinox series from Great Lakes, are preferably used as antioxidants. Suitable UV absorbers and light stabilizers are mentioned in EP-A 1 046 668 on pages 35 and 36. Both disclosures are hereby incorporated by reference, the disclosures being considered as part of this 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 also soda and sodium bicarbonate. Particularly suitable are, for example, ammonium citrate, azodicarbonamide or sodium bicarbonate or mixtures of two or more thereof.

In addition, a stabilizer composition according to the invention may also contain impact modifiers and processing aids, gelling agents, antistatics, biocides, metal deactivators, optical brighteners, flame retardants and

Contain 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", EJ. Wilson, J. Wiley & Sons, 1993.

The present invention therefore also provides a stabilizer composition at least comprising a salt preparation according to the present invention or a salt preparation prepared by a process according to the invention and at least one further additive.

In addition to the stabilizer composition according to the invention itself, the process for its preparation is also the subject of the present invention.

The present invention therefore also relates to a process for the preparation of a stabilizer composition, characterized in that a salt preparation according to the invention or a salt preparation prepared according to the invention and at least one further additive are mixed.

The stabilizer compositions according to the invention are suitable, for example, for stabilizing halogen-containing polymers. Examples of such halogen-containing polymers are polymers of vinyl chloride, vinyl resins containing vinyl chloride units in the polymer backbone, copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially 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 rumarate or maleic anhydride, postchlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and other compounds such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, Vinyl isobutyl ethers and the like, polymers and copolymers of vinylidene chloride with vinyl chloride and other polymerizable compounds as mentioned above , Vinylchloroacetate and dichlorodivinyl ether polymers, chlorinated vinylacetate polymers, chlorinated polymeric esters of acrylic acid and α-substituted acrylic acids, chlorinated polystyrenes, for example polydichlorostyrene, chlorinated polymers of ethylene, polymers and chlorinated butachlorated polymers of chlorobutadiene and their copolymers with vinyl chloride, and mixtures of two or more of said polymers or polymer blends containing one or more of the above polymers. In a preferred embodiment of the present invention, the stabilizer compositions according to the invention are used for the production of PVC-U shaped parts, such as window profiles, technical profiles, pipes and plates.

Also suitable for stabilization with the stabilizer compositions according to the invention are the graft polymers of PVC with EVA, ABS or MBS. Preferred substrates for such graft copolymers are also the abovementioned 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.

Also suitable for stabilization with the stabilizer compositions according to the invention are 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. Furthermore, it is also possible with the stabilizer compositions according to the invention to stabilize recyclates of chlorine-containing polymers, where in principle all recyclates of the abovementioned halogenated polymers are suitable for this purpose. Suitable in the context of the present invention, for example, P VC recyclate.

A further subject of the present invention is therefore a polymer composition containing at least one halogen-containing polymer and a salt preparation according to the invention or a salt preparation prepared according to the invention or a stabilizer composition according to the invention or a stabilizer composition prepared according to the invention.

In 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 about 0.5 to about 15 phr or about 1 to about 12 phr. The unit phr stands for "per hundred resin" and thus relates to parts by weight per 100 parts by weight of polymer.

Preferably, a polymer composition according to the invention as a halogenated polymer at least partially contains PVC, wherein the PVC content is in particular at least about 20, preferably at least about 50 wt .-%, for example at least about 80 or at least about 90 wt .-%.

The present invention also relates to a process 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 be carried out at any time before or during the processing of the polymer. For example, the stabilizer composition may be blended into the powdered or granulated polymer prior to processing. However, it is equally possible that Stabilisatorzusatnmensetzung the polymer or the polymers in softened or molten 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 melt to add.

The present invention therefore also provides a process 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 a salt preparation according to the invention or one according to the invention prepared salt preparation or a stabilizer composition according to the invention or a stabilizer composition according to the invention is mixed.

A polymer composition according to the invention can be brought into a desired form in a known manner. Suitable methods are, for example, calendering, extrusion, injection molding, sintering, extrusion blow molding 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, in particular for the production of PVC-U.

A polymer composition according to the invention can be processed into shaped bodies. The present invention thus also relates to shaped articles, at least comprising a salt preparation according to the invention or a salt preparation prepared according to the invention or a stabilizer composition according to the invention or a stabilizer composition prepared according to the invention or a polymer composition according to the invention.

In the context of the present invention, the term "shaped body" basically encompasses all three-dimensional structures that can be produced from a polymer composition according to the invention. The term "shaped body" in the context of the present invention, for example, wire sheaths, automotive components, such as automotive components such as those used in the interior of the car, in the engine compartment or on the outer surfaces, cable insulation, decorative films, agricultural films, hoses, sealing profiles, Office films, hollowware (bottles), packaging films (thermoformed films), blown films, tubes, foams, heavy profiles (window frames), lightwall profiles, building profiles, sidings, fittings, sheets, foam sheets, recycled core coextrudates or housings for electrical equipment or machines, such as computers or Domestic appliances.

Further examples of moldings which can be produced from a polymer composition according to the invention are artificial leather, floor coverings, textile coatings, wallpaper, coil coatings or underbody protection for motor vehicles.

The invention will be explained in more detail by examples.

Examples

Preparation of Inventive Examples EB 1-7:

45.0 g of PEG 200 and 14.9 g of triethanolamine were mixed with 12.2 g of sodium perchlorate and heated to 145 ° C, 20.0 g of zeolite were stirred in and the mixture was cooled. Zeolites were used according to Table 1.

Table 1: Zeolites of Examples EB 1-7 according to the invention

Preparation of Inventive Examples EB 8-9:

26.7 g of stearic acid and 14.5 g trialkanolamine were heated to 110 ⁰ C, it was slowly added 20.0 g of a 58% calcium perchlorate solution and admit cooling the mixture. Amino alcohols were used according to Table 2. Table 2: Amino alcohols of the inventive examples EB 8-9

Preparation of Comparative Examples VB 1-2:

In 45.0 g of PEG 200 and 14.9 g of triethanolamine were stirred at 145 ⁰ C 20.0 g of zeolite, the mixture was cooled. Zeolites were used according to Table 3.

Table 3: Zeolites of Comparative Examples

Test procedure:

In accordance with the below-mentioned test formulation and stabilizers according to Table 4, dry blends were rolled for 5 minutes at 190 ° C. on a mixing mill. The HCl data were determined by Congo red test.

Test recipe: S-PVC (K value 65) 100.00

(In phr) Chalk 2.00

Ca (OH) ₂ 0.20

Ceasit SW 0.60

Microwax (Baerolub LKT) 0.60

Ester wax (Baerolub 43 C) 0.50

Hardened castor oil (Baerolub LCD) 0.10

Hydrotalcite 0.60

TiO ₂ 0.10

Butylene glycol bis (aminocrotonate) 0.20

Stabilizer * 0.20 Table 4: Test results

As can be clearly seen, the thermal stability is improved by the stabilizers according to the invention.

Claims

claims

A salt preparation containing at least one organic onium salt of a halogen-containing oxy acid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or a mixture of two or more solvents, wherein the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts halogen-containing oxyacids in the solvent or the mixture of two or more solvents at 20 ⁰ C to at least 0.1 wt .-%, based on the solvent or the mixture of two or more solvents, is soluble and the salt preparation at 5 ⁰ C solid is.

2. Salt preparation according to claim 1, characterized in that the organic onium salt of a halogen-containing oxyacid or at least one organic onium salt of a halogen-containing oxyacid a mixture of two or more organic onium salts of halogenated oxyacids at 80 ° C is liquid.

3. Salt preparation according to claim 1 or 2, characterized in that the salt preparation at the melting point of the organic onium salt of a halogen-containing oxyacid or at the melting point of the lowest-melting organic onium salt of a mixture of two or more organic onium salts of halogen-containing oxyacids is fixed.

4. Salt preparation according to claim 1 to 3, characterized in that the salt preparation is solid at the melting point of the solvent or at the melting point of the lowest melting solvent of a mixture of two or more solvents.

5. salt preparation according to one of claims 1 to 4, characterized in that the salt preparation contains at least one polar organic solvent.

6. salt preparation according to one of claims 1 to 5, characterized in that the salt preparation contains at least one polyol as a solvent.

7. Salt preparation according to one of claims 1 to 6, characterized in that the salt preparation contains at least one amino alcohol as a solvent.

8. Salt preparation according to one of claims 1 to 7, characterized in that the salt preparation comprises triethanolamine as a solvent.

9. Salt preparation, producible by mixing

a. a solvent or a mixture of two or more solvents and b. at least one organic onium salt or c. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and at least one acid and d. at least one inorganic salt of a halogen-containing oxyacid,

wherein at least 0.1 wt .-% of an organic onium salt of a halogenated oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids, based on the solvent or the mixture of two or more solvents are dissolved in this and the salt preparation at 5 ° C is fixed.

10. salt preparation according to claim 9, prepared by mixing

a. a solvent or a mixture of two or more solvents and b. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and c. at least one inorganic salt of a halogen-containing oxyacid and

Treatment of the mixture with an ion exchanger for the exchange of cations, wherein at least 0.1 wt .-% of an organic onium salt of a halogenated oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids, based on the solvent or Mixture of two or more solvents are dissolved in this and the salt preparation at 5 ° C solidifies.

11. A process for preparing a salt preparation according to any one of claims 1 to 10, characterized by the mixing of

12. The method according to claim 11, characterized by the mixing of

a. a solvent or a mixture of two or more solvents and b. at least one amine or at least one mercaptan or at least one sulfide or at least one phosphine or a mixture of two or more of these compounds and c. at least one inorganic salt of a halogen-containing oxyacid and d. Treatment of mixing with an ion exchanger to exchange cations.

13. The method according to claim 12, characterized in that the salt preparation is formulated directly after the ion exchange.

14. A stabilizer composition at least comprising a salt preparation according to any one of claims 1 to 10 or a prepared according to a method of any one of claims 11 to 13 salt preparation and at least one further additive.

15. Stabilizer composition according to claim 14, characterized in that the salt preparation is substantially free of further inorganic additives.

16. A process for preparing a stabilizer composition, characterized in that a salt preparation according to one of claims 1 to 10 or a salt preparation prepared according to a method of any one of claims 11 to 13 and at least one further additive are mixed.

A polymer composition containing at least one halogen-containing polymer and a salt preparation according to any one of claims 1 to 10 or a salt preparation prepared according to a process of any one of claims 11 to 13 or a stabilizer composition according to any one of claims 14 or 15 or one according to the process of claim 16 prepared stabilizer composition.

18. A method for stabilizing halogen-containing polymers, wherein 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 a salt preparation according to one of claims 1 to 10 or with a prepared according to a method according to any one of claims 11 to 13 or with a stabilizer composition according to any one of claims 14 or 15 or with a stabilizer composition prepared according to the method of claim 16.

19. Shaped body, at least comprising a salt preparation according to one of claims 1 to 10 or a salt preparation prepared by a process according to any one of claims 11 to 13 or a stabilizer composition according to any one of claims 14 or 15 or one prepared by a process according to any one of claims 16 A stabilizer composition or a polymer composition according to claim 17.