MXPA06011296A - Crosslinkabe elastomer compositions, process for preparation, and use thereof - Google Patents

Abstract

The present invention provided a novel crosslinkable composition based on elastomers, at least one of which has a carboxyl and/or carboxylate group, is provided. The crosslinkable composition contains a special unsaturated organic salt of a metal ion and a crosslinking system which acts as a free radical donor. A crosslinked elastomer which has excellent physical properties is obtainable from the crosslinkable composition. The novel crosslinkable composition have a wide range of uses.

Description

RETICULABLE COMPOSITIONS, PROCESSES FOR THE PREPARATION AND USE OF THE SAME DESCRIPTION OF THE INVENTION The invention relates to crosslinkable compositions which contain elastomers having carboxyl and / or carboxylate groups and special organic salts of metal ions and a crosslinking system based on free radical donors. The invention further relates to the preparation of such crosslinkable compositions and the use thereof. There is a demand for vulcanizable compositions which can be processed in liquid form, or as much as possible free of solvent or having a low content of solvents and, after curing or vulcanization, having the properties typical of vulcanized elastomers. There is a particular requirement for materials which can be processed in a low viscosity form and, after vulcanization, have high thermal stability and adjustable physical properties and therefore combine the properties of customary systems processable in liquid form, such as silicone rubbers or polyurethanes with the properties of high resolution elastomers, such as, for example rubbers ABR, EVM, ACM and AEM. There is a particular need also for materials which first have a very low viscosity at high Ref .: 176000 temperatures or under high shear stress but are also provided with sufficient stability under load at room temperature. This combination of properties can mean that on the other hand they can be molded by customary methods (extrusion, injection, calendering, pressure) to give bodies which are dimensionally stable for a short time at room temperature, such as, for example, leathers, lining strips or lining bodies, and can be used as such but acquire a low viscosity at higher temperatures and can then typically be processed "in liquid form". An object of the present invention is therefore to provide compositions which have low viscosities at the processing temperature while at the same time having stability over time under load at room temperature and additionally high thermal stability and a high level of physical properties after vulcanization. Surprisingly, it was found that by combining the elastomers containing carboxyl and / or carboxylate groups, in a defined viscosity range, with salts of special unsaturated carboxylic acids of metal ions and a free radical crosslinking system, the vulcanizable compositions are obtained which have the desired profile of properties, achieve the object according to the invention and, after the subsequent vulcanization of the elastomers or polymerization of the salts of unsaturated carboxylic acids, they lead to vulcanizates which fulfill the requirements mentioned above since they are simultaneously high strength and elastic products which have a high adhesive effect with respect to the usual polar metals and substrates, such as polyurethanes, polyamides, polyesters, polyethers, polyepoxides, polyalcohols, polyacids and derivatives and mixtures thereof. The present invention relates to crosslinkable compositions which contain (1) one or more elastomers, at least one of which has carboxyl and / or carboxylate groups, (2) one or more different salts of the general formula (I) (Ry-) x / yMx + (I) in which R? ~ Represents a carboxylate of C3-C? a, ß-unsaturated which contains and carboxylate groups, and can represent the values 1, 2, 3, or 4, x is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal and, (3) one or more crosslinking agents which act as free radical donors. Characterized because (a) the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together have a Mooney viscosity (ML 1 + 4 in 100 ° C), measured according to the ASTM D1646 standard, in a range of 1-35 and (b) the crosslinkable composition (i) has a complex viscosity? *, Measured in a Rubber Process Analyzer (RPA for short) in English at 60 ° C, 1Hz and an amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of? * ( in 1Hz and 10% amplitude) a? * (in 1Hz and 100% amplitude), more than 1.4, (iii) a temperature-dependent change in the complex viscosity, measured in the RPA as the proportion of T | * (at 60 ° C, 1Hz and 10% amplitude) at T | * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 and (iv) a change dependent on the viscosity amplitude complex, measured in the RPA at 130 ° C as the ratio of T | * (in 1Hz and 10% amplitude) to T | * (in 1 Hz and 100% amplitude), is less than 1.5, values established for the complex viscosity (? *) in all the above-mentioned cases iormente (i) - (iv) indicate in each case the mathematical magnitude of the complex viscosity. All the above-mentioned complex viscosities are measured in a Process Analyzer of Rubber (RPA 2000) of Alpha Technologies under the conditions established in each case. The Alpha Technologies Rubber Process Analyzer and the operation thereof are clearly known to the person skilled in the art. This is an oscillation rheometer to investigate the viscoelastic properties and the processing behavior of rubber mixtures. Preferred crosslinkable compositions are those which contain (1) 10-94% by weight of one or more elastomers, at least one of which has carboxyl and / or carboxylate groups, (2) 5-89% by weight of one or more salts of the general formula (I) (R? ") x / and Mx + (I) in which R? ~ represents an α, β-unsaturated C3-Cl4 carboxylate which contains the carboxylate groups, and may represent the values, 1, 2, 3, or 4, X is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal (3) 1-20% by weight of one or more crosslinking agents which act as free radical donors, the sum of the components (1), (2), and (3) is less than or equal to 100% by weight . Characterized because (a) the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together has a Mooney viscosity (ML 1 + 4 at 100 ° C), measured according to the ASTM D1646 standard, in a range of 1-35 and (b) the crosslinkable composition (i) has a complex viscosity? *, Measured in a Process Analyzer of Rubber (RPA) at 60 ° C, 1Hz and an amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured at the RPA at 60 ° C as the proportion of T | * (at 1Hz and 10% amplitude) a? * (at 1Hz and 100% amplitude), more than 1.4, (iii) a temperature-dependent change of the complex viscosity, measured at the RPA as the proportion of? * (at 60 ° C, 1Hz and 10% amplitude) ar | * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 (iv) a change dependent on the viscosity amplitude complex, measured in the RPA at 130 ° C as the proportion of? * (in 1Hz and 10% amplitude) to? * (in 1 Hz and 100% amplitude), of less than 1.5, the values established for the Complex viscosity (? *) in all the cases mentioned above (i) - (iv) i In each case, they indicate the mathematical magnitude of the complex viscosity. Particularly preferred crosslinkable compositions are those containing (1) 30-84% by weight of one or more elastomers, at least one of which having carboxyl and / or carboxylate groups, (2) 14-68% by weight of one or more salts of the general formula (I) (Ry)? / Y Mx + (I) in which R? ~ represents a C3-Cl4, β-unsaturated carboxylate which contains the carboxylate groups, and may represent the values , 1, 2, 3, or 4, X is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal and (3) 2-15% by weight of one or more crosslinking agents as radical donors,, the sum of the components (1), (2), and (3) is less than or equal to 100% by weight. characterized in that (a) the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together has a Mooney viscosity (ML 1 + 4 at 100 ° C), measured from according to the ASTM Di646 standard, in a range of 1-35 and (b) the crosslinkable composition has (i) has a complex viscosity? *, measured on a Rubber Process Analyzer (RPA) at 60 ° C, 1Hz and a amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of? * (at 1Hz and 10% amplitude) to? *. (in 1Hz and 100% amplitude), more than 1.4, (c) a change dependent on temperature of the complex viscosity, measured in the RPA as the proportion of? * (in 60 ° C, 1Hz and 10% of amplitude) a? * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 (c) a change dependent on the amplitude of the complex viscosity, measured at the RPA at 130 ° C as the proportion of? * (in 1Hz and 10% of amplitude) to? * (in 1 Hz and 100% of amplitude), of less than 1.5, and the values established for the complex viscosity (? *) in all the cases mentioned above indicate in each case the mathematical magnitude of the complex viscosity. In all the above mentioned embodiments, the crosslinkable compositions according to the invention can optionally contain, as component (4), up to 84% by weight, preferably 4-64% by weight and particularly and preferably 10-40% by weight of one or further auxiliary agents, such as, for example, fillers, fibers, polymers which are not converted by the definition according to the invention of the elastomer (I), oils, stabilizers, processing aids, plasticizers, additional polymerizable monomers dimers, trimers or oligomers, or vulcanization activators, the sum of the components (1), (2), (3) and (4) which is 100% by weight. The crosslinkable compositions according to the invention are distinguished in that they resemble the Neo-tonic fluids in their properties. This means that they do not show a significant change in the complex viscosity (in this application, the mathematical magnitude of the complex viscosity is always established for this) with high shear at the processing temperature (for example 130 ° C). At room temperature, however, the crosslinkable compositions show substantially higher viscosities than at the processing temperature and clear non-Newtonian behavior at high shear stress, i.e. a decrease in viscosity with high shear stress. The crosslinkable compositions according to the invention have (i) a complex viscosity T | *, measured in a Rubber Process Analyzer (RPA) at 60 ° C, 1Hz and an amplitude of 10%, of more than 30,000 Pas, preferably of more than 40,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of r | * (at 1Hz and 10% amplitude) to? * (at 1Hz and 100% amplitude), of more than 1.4, preferably of more than 1.6, (iii) a change dependent on temperature of the complex viscosity, measured in the RPA as the ratio of? * (at 60 ° C, 1Hz and 10% amplitude) to? * (at 130 ° C, 1 Hz and 10% amplitude) ), of more than 6, preferably more than 8, (iv) a change dependent on the amplitude of the complex viscosity, measured in the RPA at 130 ° C as the proportion of? * (in 1Hz and 10% amplitude) ) a? * (in 1 Hz and 100% amplitude), less than 1.5, preferably less than 1.4, and the values established for the complex viscosity (? *) in all the cases mentioned above (i) - (iv ) indicate in each case the mathematical magnitude Attic of complex viscosity. The value of more than 1.4, preferably more than 1.6, for the change in the complex viscosity dependent on amplitude (ii) (reduction in viscosity), measured in the RPA at 60 ° C as the ratio? * (In 1Hz and 10% amplitude) a? * (At 1Hz and 100% amplitude), means that a typical behavior of a filled rubber mixture having non-Newtonian behavior is present. The value of more than 6, preferably of more than 8, for the change of the complex viscosity dependent on temperature (iii) (reduction of viscosity), measured in the RPA as the ratio T | * (at 60 ° C, 1 Hz and 10% amplitude) a? * (At 130 ° C, 1 Hz and 10% amplitude), means that a transition from non-Newtonian to approximately Newtonian behavior takes place as the temperature increases. The value of less than 1.5, preferably is less than 1.4, for the change in the complex viscosity dependent on the amplitude (iv) (reduction in viscosity), measured in the RPA at 130 ° C since the ratio T | * ( at 1 Hz and 10% amplitude) a? * (at 1 Hz and 100% amplitude), means that there is approximately Newtonian behavior at the processing temperature. One or more typical elastomers can be used as elastomers (I). It is of decisive importance that at least one of the elastomers contains carboxyl and / or carboxylate groups attached to the polymer chains. Usually, the elastomer (1) or the mixture of the elastomers (1), if a plurality of elastomers (1) is used, contains 0.5-15% by weight, based on 100% by weight of the elastomer (1) or based on the total mixture of the elastomer (1), if a plurality of elastomers (1), carboxyl and / or carboxylate groups are used. The elastomer (1) or the elastomer mixture, if a plurality of elastomers (1) is used, preferably contains 0.5-10% by weight, particularly preferably 1-7% by weight and in particular 1.5-6% by weight, on the basis of 100% by weight of the elastomer (1) or on the basis of the total mixture of the elastomer (1), if a plurality of elastomers (1), carboxyl and / or carboxylate linked groups are used. These carboxyl or carboxylate groups may be randomly distributed along the polymer chains of the elastomers and may also be present at the ends of the chains. Suitable elastomers (1) containing carboxyl and / or carboxylate groups are, for example, the following: 1. carboxylated nitrile rubber (also abbreviated as XNBR), hydrogenated nitrile carboxylated rubber (also abbreviated as HXNBR), 3. maleic anhydride grafted rubber ("MAH") based on EPM, EPDM, ABR, EVA, EVM, SBR, NR OR BR, 4. carboxylated styrene-butadiene rubber (also abbreviated as XSBR). 5. AEM which has free carboxyl groups, 6. ACM which has free carboxyl groups and any mixtures of the polymers mentioned above. The Mooney viscosity (ML 1 + 4, measured at 100 ° C) of the elastomer (1) used or, if a plurality of elastomers is used, the total mixture of all the elastomers (1) is in the range of 1-35, preferably in the range of 2 to 25, particularly and preferably in the range of 5 to 20. The Mooney viscosity is determined according to ASTM D 1645 standard. Some of the elastomers are commercially available but additionally they are obtainable in all cases by preparation processes accessible to the person skilled in the art by means of the literature. Under the carboxylated nitrile rubber (also referred to as XNBR) is understood to mean rubbers which are terpolymers or at least one unsaturated nitrile, at least one conjugated diene and at least one additional thermonomer which contains carboxyl and / or carboxylate groups . The β-unsaturated nitrile used can be any known as α, β-unsaturated nitrile, and α, β-unsaturated nitriles of C 3 -C 5, such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof, are preferred. Acrylonitrile is particularly preferred. The conjugated diene can be of any type. The conjugated dienes (C4-C6) are preferably used. 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof are very particularly preferred. The monomers containing carboxyl and / or carboxylate groups which can be used are, for example, α, β-unsaturated carboxylic acids or esters thereof. Preferred are fumaric acid, maleic acid, acrylic acid and methacrylic acid as acids and esters thereof are preferred. Suitable esters are, for example, the methyl, ethyl propyl, isopropyl, n-butyl, isobutyl, n-hexyl and 2-ethylhexyl monoamines of fumaric acid and / or maleic acid and / or the methyl, ethyl esters; propyl, isopropyl, n-butyl, isobutyl, n-hexyl and 2-ethylhexyl of acrylic acid and / or methacrylic acid. Other monomers containing carboxyl and / or carboxylate groups which may be used are unsaturated dicarboxylic acids or derivatives thereof, such as esters, amides or anhydrides, such as, for example, maleic anhydride. The carboxylated nitrile rubbers can be polymers which have either one or more monomers which contain carboxyl groups or one or more monomers which contain carboxylate groups. However, there may also be polymers which simultaneously have one or more monomers which contain carboxyl groups and one or more monomers containing carboxylate groups. For example, the polymers of butadiene and acrylonitrile and acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid and / or the monoesters of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl and 2-ethylhexyl of fumaric acid and / or maleic acid and / or the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl and 2-ethylhexyl esters of acrylic acid and / or methacrylic acid are suitable. For example, polymers of butadiene and acrylonitrile and a monomer which contains carboxyl groups, in particular fumaric acid, maleic acid, acrylic acid or methacrylic acid, are preferred. Additionally, the polymers of butadiene and acrylonitrile and a monomer which contains carboxyl groups, in particular fumaric acid, maleic acid, acrylic acid or methacrylic acid, and a monomer which contains carboxylate groups, in particular the monoesters of methyl, ethyl, propyl , isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl of fumaric acid or maleic acid or the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl esters of acrylic acid or methacrylic acid; they are also preferred. The proportions of the conjugated diene and α, β-unsaturated nitrile in the XNBR polymers can vary within wide ranges. The proportion of the conjugated diene or the sum of the conjugated dienes is usually in the range of 40 to 90% by weight and preferably in the range of 55 to 75% by weight, based on the total polymer. The proportion of the nitrile a, β-unsaturated or of the sum of the nitriles, β-unsaturated is usually 9.9 to 60% by weight, preferably 15 to 50% by weight, based on the total polymer. Additional monomers are present in amounts of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total polymer. The proportions of all monomers in each case amount to 100% by weight. The preparation of XNBR by polymerization of the monomers mentioned above is sufficiently well known to the person skilled in the art and is described extensively in the literature (for example EP-A-0 933 381 and US-A-5,157,083; Nippon Zero). In order to obtain particularly low viscosity XNBR types, it has been proven useful to subject a starting XNBR to a reduction in molecular weight by a metathesis reaction known from the literature. The hydrogenated nitrile carboxylated rubbers (also abbreviated as HXNBR) are obtainable by several routes: It is possible, for example, to graft an HNBR with compounds which contain carboxyl groups. They can additionally be obtained by hydrogenation of the XNBR carboxylated nitrile rubbers described above. Such hydrogenated carboxylated nitrile rubbers are described, for example, in O-A-01/77185. In the context of this application, "hydrogenation" or "hydrogenated" is understood as meaning at least 50%, preferably 75%, particularly and preferably 85%, of conversion of the double bonds originally present in the carboxylated nitrile rubber. The hydrogenated carboxylated nitrile rubbers HXNBR are therefore a nitrile carboxylated rubber XNBR based on at least one unsaturated nitrile, at least one conjugated diene and at least one additional thermonomer which contains carboxyl and / or carboxylate groups, at least 50% of the double bonds originally present in the XNBR that are saturated. Suitable HXNBRs are, for example, hydrogenated carboxylated nitrile rubbers based on an XNBR obtained from butadiene and acrylonitrile, and acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid and / or methyl monoesters, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl and / or 2-ethylhexyl of fumaric acid and / or maleic acid and / or the esters of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n -hexyl, and / or 2-ethylhexyl of acrylic and / or methacrylic acid. Suitable HXNBRs are additionally, for example, hydrogenated carboxylated nitrile rubbers based on XNBR obtained from butadiene and acrylonitrile and a monomer which contains carboxyl groups, in particular fumaric acid, maleic acid, acrylic acid or methacrylic acid. Suitable HXNBRs are additionally, for example, hydrogenated carboxylated nitrile rubbers based on XNBR obtained from butadiene and acrylonitrile and a monomer which contains carboxyl groups, in particular fumaric acid, maleic acid, acrylic acid or methacrylic acid, and a monomer which contains carboxylate groups, in particular the monoesters of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl of fumaric acid and maleic acid or the n-butyl, isobutyl, n-esters hexyl or 2-ethylhexyl of fumaric acid and maleic acid or the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl esters of acrylic acid or methacrylic acid. It is possible in principle to carry out the hydrogenation of XNBR using homogeneous or heterogeneous hydrogenation catalysts. As described in the application WO-A-01/77185, it is possible, for example, to carry out the reaction with hydrogen using homogeneous catalysts, such as, for example, the catalyst known as a "ilkinson" catalyst.

((PPh3) 3RhCI), or others. The processes for the hydrogenation of nitrile rubber are known. Rhodium or titanium are usually used as catalysts, but it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt, or copper, either as a metal, or, preferably, in the form of metal compounds (with reference, for example, to U.S. Patent 3,700,637, U.S. Patent 2 539 132, U.S. Patent A-134 023, DE-A 35 41 689, DE-A-35 40 918, EP-A- 298 386, DE-A-35 29 252, DE-A-34 33 392, US-A-4, 464, 515 and US-A-4, 503, 196). Catalysts and solvents suitable for hydrogenation in the homogeneous phase are described below and are described in DE-A-25 39 132 and EP-A-0 471 250. Selective hydrogenation can be achieved, for example, in the presence of a catalyst which contains rhodium. For example, a catalyst of the general formula (R ^ B)! RhXn in which R1 are identical or different and represent an alkyl group of Ci-Cs, a cycloalkyl group of C4-C8, a aryl group of Cß-Cis or an aralkyl group of C7-C5 can be used. B is phosphorus, arsenic, sulfur or a sulfoxide group S = 0, X is hydrogen or an anion, preferably halogen and particularly preferably chlorine or bromine, 1- is 2, 3 or 4, m is 2 or 3 and n is 1, 2 or 3, preferably 1 or 3.

Preferred catalysts are tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride, and tris (dimethylsulfoxide) rhodium (III) chloride and tetrakis (triphenylphosphine) rhodium hydride of the formula (C5H5) ) 3P) 4RhH and the corresponding compounds in which the triphenylphosphine is completely or partially replaced by tricyclohexylphosphine. The catalyst can be used in small amounts. An amount in the range of 0.01-1% by weight, preferably in the range of 0.03-0.5% by weight and particularly and preferably in the range of 0.1-0.3% by weight, based on the weight of the polymer, is suitable. It is usually expedient to use the catalyst together with a co-catalyst which is a ligand of the formula R'SnB, Ri, m and B which has the meanings mentioned above. These are preferably co-catalysts which comprise trialkyl, tricycloalkyl, triaryl, triaralkyl, diaryl monoalkyl, diaryl monocycloalkyl, dialkyl monoaryl, dialkyl monocycloalkyl or dicycloalkyl monoaryl radicals. Example of cocatalysts are found, for example in US-A-4, 631, 315. A preferred co-catalyst is triphenylphosphine. The co-catalyst is preferably used in amounts in a range of 0.3-5% by weight, and more preferably in the range of 0.5-4% by weight, based on the weight of the nitrile rubber to be hydrogenated. Additionally, the weight ratio of the radiolabelled catalyst to the cocatalyst is preferably in the range of 1: 3 to 1:55, and more preferably in the range of 1: 5 to 1:45. Based on 100 parts by weight of the nitrile rubber to be suitably hydrogenated 0.1 to 33 parts by weight of the co-catalyst, preferably 0.5 to 20 and very particularly and preferably 1 to 5 parts by weight, in particular more than 2 but less of 5 parts by weight co-catalyst based on 100 parts by weight of the nitrile rubber to be hydrogenated are used. The practical procedure for this hydrogenation is sufficiently well known to the person skilled in the art from US-A-6,683,136. It is usually effected by treating the nitrile rubber to be hydrogenated, in a solvent, such as toluene or monochlorobenzene, at 100-150 ° C and a pressure of 50-150 bar for 2-10 hours with hydrogen. The use of heterogeneous catalysts for the preparation of hydrogenated carboxylated nitrile rubbers by hydrogenation of the corresponding nitrile carboxylated rubbers usually involves catalysts based on palladium. In addition to one or more elastomers (1) which have carboxyl and / or carboxylate groups, in addition elastomers (1) which do not have carboxyl or carboxylate groups may also be present, with the proviso that the mixture of all the elastomers (1) in the composition according to the invention complies with the important characteristic of the Mooney viscosity (ML 1 + 4 at 100 ° C) in the range of 1-35. For example NBR and HNBR can be used as elastomers (1) which do not have carboxyl or carboxylate groups. NBR are understood as meaning rubbers which are copolymers of at least one n-a, n-unsaturated nitrile and at least one conjugated diene. A nitrile, ß-unsaturated which can be used is any known ß-unsaturated nitrile, and α, β-unsaturated nitriles of (C-Cs), such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof, are preferred. Acrylonitrile is particularly preferred. The conjugated diene can be of any type. Conjugated dienes are preferably used (C4-C6). Butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof are particularly preferred. In particular, mixtures of 1,3-butadiene and isoprene or mixtures thereof are preferred. 1,3-Butadiene is very particularly preferred. The hydrogenated nitrile rubbers, HNBR, can be obtained from the NBR types in an analogous manner, as described above for the preparation of HXNBR from XNBR. Component (2) Component (2) comprises one or more salts of the general formula (I) (R?) X / Y Mx + (I) in which R? ~ Represents a C3-Cl4 a, b-unsaturated carboxylate which contains the carboxylate groups, and can represent the values, 1, 2, 3, or 4, x is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal. M in the general formula (I) preferably represents Mg, Ca, Zn, Fe, Al, Ti, Pb, B, Sc, Yt, Sn or Hf, particularly and preferably Mg, Ca, Zn, Fe, Al, Ti or Pb . The radical Ry ~ in the general formula (I) is preferably a C3-Cs, β-unsaturated carboxylate which contains the carboxylate groups and, being possible to and assume the value 1, 2, 3, or 4. Particularly and preferably , Ry ~ represents acrylate, methacrylate, crotonate, isocrotonate, sorbent, fumarate or maleate or mixtures thereof. Component (3) As component (3), one or more free radical donors are used as crosslinking agents. Peroxide compounds, azides, photoinitiators, redox initiators or combinations of those mentioned above can be used as free radical donors. Suitable free radical donors (3) are, for example, the following peroxide compounds: Bis (2,4-dichlorobenzoyl) peroxide, dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butyl perbenzoate, 2,2-bis (tert-butylperoxy) butene, 4,4-di-tert-butylperoxynonyl valerate, dicumyl peroxide, 2,5 -dimethyl- 2, 5-di (tert-butylperoxy) exano, tert-butylcumyl peroxide, 2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) enene , di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin, tert-butyl hydroperoxide, hydrogen peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, decanoyl peroxide, peroxide 3, 5, 5-trimethylhexanoyl, di (2-ethylhexyl) peroxydicarbonate, poly (tert-butyl peroxycarbonate), 3, 3-di (ethyl tert-butylperoxybutyl), 3, 3-di (tert-amylperoxy) butyrate d and ethyl, n-butyl 4,4-di (tert-butylperoxy) valerate, 2,2-di (tert-butylperoxy) butane, 1,1-di (tert-butylperoxy) cyclohexane, 3,3,5-trimethylcyclohexane , 1, 1-di (tert-a-ylperoxy) cyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-3,5,5,5-trimethylhexanoate, tert-butyl peroxyisobutyrate, peroxy-2- ethylhexanoate tert-butyl peroxypivalate tert-butyl peroxypivalate tert-a yl, peroxyneodecanoate tert-butyl peroxyneodecanoate, cumyl peroxineodecanoto 3-hydroxy-1, 1-dimethylbutyl peroxybenzoate tert-butyl peroxide, tert -butyl, tert-amyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, cumyl peroxydecanoate, 3-hydroxy-l, 1-dimethylbutyl peroxineodecanoate, peroxide of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne (3-di-tert-amyl), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, hydroperoxide of tert- amyl, hydroperoxide cumol, 2,5-dimethyl-2, 5-di (hydroperoxy) exano, diisopropylbenzene monohydroperoxide and potassium peroxodisulfate. A suitable free radical donor (3) is, for example, 2, 2-azobismetylethylacetonitrile as an azide: suitable additional azides are, for example, commercially suitable azo initiators and free radical initiators, which can be obtained under the words " Vazo® free radical initiators "from DuPont and as" azo free radical initiators "from Wako Specialty Chemicals. The following photoinitiators can also be mentioned by the example form as donors of suitable free radicals (3): benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoylphenylcarbonyl, methylphenyl glyoxylate, 4,4'-diazidobiphenyl, 4,4'-diazidobenzophenone, 4,4'-diazidobiphenyl oxide, 4''-diazido-disulfonylbiphenyl, azidobenzene, 4-azidobenzoic acid, 1,2-bis (4-azidophenyl) ethylene, 4-aminophenyl-4'-azidophenylmethane, 2,6-di (4'-azidobenzal) cyclohexanone, 4, '-diazidostilbene-2, 2'- sodium disulfonate, benzophenone, benzophenone oxime, acetophenone, bromoacetophenone, cyclohexanone, diphenyl monosulfide, dibenzothiazolyl disulfide, s-acyl dithiocarbamate, m, m'-azoxistirene, benzyldimethyl ketal, 4-methylbenzophenone, 4-phenylbenzophenone, 4- Ethyl dimethylaminobenzoate (EPD), 2-hydroxy-2-methylphenylpropan-1-one, isopropylthioxanthone (ITX) and 2-methyl-1- (4-methylthiophenyl) -2-morfo1inopropanol- 1-ona. The following redox initiators can also be mentioned by the exemplary form as suitable free radical donor (3): FE (II) / hydroperoxide, peroxide / tertiary amine, peroxydisulfate / thiosulfate, hydroperoxide / thiosulfate. Component (4) The crosslinkable composition according to the invention can additionally contain contain constituents as the component (4): • customary fillers in the rubber industry, such as carbon black, silica, talcum, calcium carbonate or dioxide of titanium, kaolins, bentonites, nanotubular carbon, aluminum hydroxide, magnesium hydroxide or Teflon (the latter preferably in the form of powder), • polymers which are not covered by the definition according to the invention of the elastomer (1), • oils, • plasticizers, • processing aids, • stabilizers and antioxy ates, • dyes, • fibers which comprise organic and inorganic fibers and fiber pulps, • vulcanization activators, • additional polymerizable monomers, dimers, trimers or oligomers The use of an antioxidant in the compositions according to the invention may be desired. Examples of customary antioxidants include p-dicumildiphenylamine (Naugard® 445), Vulkanox® DDA (diphenylamine with styrene), Vulkanox® ZMB2 (zinc salt of methylmercaptobenzimidazole), Vulkanox® HS (1, 2-dihydro-2, 2, -4-trimethylquinoline polymerized) and Irganox® 1035 (bis (3,5-di-tert-butyl-4-) hydroxy) thioethylene hydrocinnamate or thiodiethylene bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) The present invention also relates to a process for the preparation of crosslinkable compositions according to the invention by mixing all the components (1) - (3) and optionally the components (4) The sequence in which the components are mixed with one another is not of fundamental importance but is adapted in each case to the available mixing units The mixing of the components (1), (2), (3) and optionally (4) can, depending on the temperature, be effected with the use of typical mixing systems customary in the rubber industry, a) continuous mixing units in the form of mixing or mixing mixing rollers and b) mixing mixing Units, such as mixing extruders, can be used. This is appropriate in the temperature range in non-Newtonian behavior of the crosslinkable mixtures according to the invention but can also be carried out at temperatures higher in the range of the behavior Newtonian of mixtures. However, the use of custom units in the adhesives industry is also possible. It has proven particularly useful to carry out the mixing of the components (1), (2) and (3) and optionally as (4) at the predetermined mixer temperature in the range of about 30-40 ° C, since Sufficiently high cutting forces can be applied in the present by means of the aforementioned traditional mixing units in the rubber processing industry in order to achieve total mixing. Alternatively, the mixing can also be effected in suitable units at higher temperatures. In the individual case, it may be necessary to first mix the components (1) and (2) and optionally (4) and mix the free radical donor (3) only at the end. This can take place, for example, in the mixing unit in the final section of a nozzle immediately before the mixture emerges in the substrate / in the mold. Such reagent mixing of customary two component systems based on PU or silicone rubbers has not been described to date for conventional high resolution rubbers since these are not present in the low viscosity form required for this purpose. There is thus also a particular advantage of the compositions according to the invention on PU and silicone rubbers since the emerging molding materials quickly acquire high stability under load during cooling and therefore do not directly hamper the subsequent processing processes, such as, for example, by subsequent adhesion. In practice, the crosslinkable compositions are obtained, for example in the form of the so-called "ground sheets", endless strips or endless bodies, also as pellets or granules, after mixing with the components according to the invention. These can subsequently be pressed or molded by injection into molds and are crosslinked under suitable conditions according to the free radical donor used. The invention additionally relates to the preparation of crosslinked elastomers, at least one which has carboxyl and / or carboxylate groups, by subjecting the crosslinkable composition according to the invention, of the type mentioned above to the energy input. The energy input can be effected in the form of thermal energy or radiation energy, depending on the type of crosslinking agent (3) chosen in the crosslinkable composition. During the crosslinking of the crosslinkable composition according to the invention, the crosslinking agents (3) first lead to the polymerization of the unsaturated acid in the component (2) and additionally effect the crosslinking of free radicals between and with the elastomers (1) used. The invention additionally relates to the crosslinked elastomers, at least one of which has carboxyl and / or carboxylate groups, which are obtainable by crosslinking the mixtures according to the invention.

The crosslinked elastomers have a strength, measured in the tensile test according to DIN 53504, of more than 10 MPa and additionally have a hardness, measured in accordance with DIN 53505, of more than 60 Shore A. These elastomers crosslinked irreversibly by the agents of free radical donor donors are distinguished because, despite a low viscosity, they have surprising properties and excellent dynamic mechanical resistance, as can be obtained to date only from mixtures of high viscosity based on high resolution rubbers, such as HNBR, EVM, ACM, AEM, after vulcanization. As a result of this combination of properties, completely novel groups of components and application forms and uses are conceivable. These are high modulus vulcanizates based on the low viscosity mixtures according to the invention. The products that have this profile of properties in processing and vulcanization properties are not known in the market and have not been technically described. The crosslinkable compositions according to the invention can be used for the production of a multiplicity of different products, some of which are listed below: 1. Elastic adhesive materials The invention relates to the use of crosslinkable compositions as elastic adhesive materials. Elastic adhesive materials are usually based on systems of compounds which comprise epoxides, isocyanate diols, and carboxylic acids. The elastification typically takes place by means of low molecular weight amorphous diols or by the use of low molecular weight elastomeric additives. The customary systems have high resistances up to approximately 100 ° C. Depending on the melting point of the constituents, the resistances decrease substantially at higher temperatures. All these adhesives are sensitive to hydrolysis and only moderately oil resistant and therefore limited in their field of use. The crosslinkable compositions according to the invention are suitable in particular for the preparation of high strength adhesive materials having important elastic properties, which are applied in liquid form but are also present in a dimensionally stable form in the cold component. After pressure and crosslinking with energy input, an important adhesion layer between metals and metal, between metal and polar high temperature thermoplastics, between metal and fabrics / rope and rubber, between fabric / rope and fabric / rope and thermoplastics, between fabric / rope and rubber, between fabric / rope and fabric / rope you can start from these elastic adhesive materials. Adhesive materials based on the crosslinkable compositions according to the invention are distinguished above all by excellent oil resistance and thermal stabilities. 2 . IMPREGNATING MATERIALS The invention also relates to the use of the crosslinkable compositions according to the invention as impregnating materials. For this purpose, the crosslinkable composition according to the invention is applied to the substrate to be impregnated and then crosslinked by energy input. The application of the crosslinkable composition according to the invention to the substrate can be carried out, for example in the case of fabric impregnation, a) by direct application (impregnation) with the crosslinkable composition according to the invention or b) friction coating of fabric in the reticulable composition according to the invention. To carry out this process, expensive latex coating systems of difficult quality and environmentally problematic and complicated solution processes can be replaced or solutions of very high concentration can be prepared, in such a way that in turn the amounts of solvent can be saved and Production capacities which are often limited by the ability to recycle the solvent can be expanded. Compared with the latex application, the substantial advantage of the reticulable composition according to the invention is that the preheating of materials, as required to activate the latex, is necessary with the. Fields of use for such impregnated fabric are, for example, bellows of all types, membranes, bellows, pneumatic springs, rubber muscles and also hoses. 3. Tapes, for example in the form of toothed belts or drive belts The invention relates to the use of the crosslinkable compositions according to the invention for the production of belts, preferably toothed belts or drive belts. The typical production, known to the person skilled in the art, of tapes, for example in the form of toothed bands, takes place according to the following process: a drum which has a negative tooth is covered with a still flexible fabric (typically based on polyamide yarns). A rope (typically based on steel, brass, polyaram, glass or carbon fibers) is used to wrap tightly (rope filament spacings of approximately 0.05 to 1 mm) in this drum. Layers / milled sheets of rubber mixes are placed on this rope with which it is wrapped. Depending on the requirements, an additional fabric can be compressed on rubber mixtures. The finally covered drum is transferred to a vulcanization autoclave with semi-elastic membranes. The rubber layers are pressed through the rope layer into the cavities of the teeth, the fabric that forms the outer edge of the tooth. The thickness of the rubber layers is such that the cavities. teeth are filled and a desired layer thickness above the cord layer is obtained. After the pressure, the vulcanization / crosslinking process starts. After crosslinking, it is ready and can be cut to the desired width, since the drum for web production is typically 0.5-2.5 m wide while a band typically has a width of 1-30 cm. The back of the band (the part of the band which is above the rope layer) can subsequently also be ground or treated further. Bands commercially available according to the described process are typically produced on the basis of a simple mixture. A disadvantage of this is that the teeth and backside have to meet different requirements. In this way, the teeth often have to have a very high modulus and high resistances (which applies, for example, to toothed belts which are used as drive belts for motor control in traditional automobile models), while the Rear part has to be more flexible in order to avoid breaking, for example, during the revolution around small deflection rollers. These partially contrary requirements. limit the choice of suitable mixtures. It is possible in principle to choose the composition of the mixture of the ground sheet layers before vulcanization in such a way that the lower layer produces a high modulus vulcanizate and the back layer a low modulus vulcanizate. The difficulty is that these layers should not be mixed during pressure. In fact, high modulus vulcanizates are typically based on mixtures of relatively high viscosity (for example, they have a high filler content of reinforcing fillers, otherwise the dynamic properties required and the modulus of the product are not achieved), while the low modulus vulcanizates are based on comparatively low viscosity mixtures (which have a low filler content of reinforcing fillers). During the pressing of such ground sheets stacked one on top of the other through the rope layer on the teeth, mixing, which is critical to the operation of the band in this obtained manner, inevitably occurs. For this reason, such bands comprising at least two mixtures of quite different viscosity according to a one-stage production process are not on the market.

Additionally known to the person skilled in the art is a two-stage process which allows the advantages of the product described above of a band, which allows different mixes in the properties for the tooth as well as the back, where the bottom toothed which is partially constructed manually with mixing strips / extrudates and the ground sheet for the back which is applied only afterwards in a separate second step and then which is further processed as described above. This process has the main disadvantage that a two-stage process is necessary and special components are required for this process. Above all, this process is substantially more expensive in the process described first. The use, according to the invention, of the special crosslinkable compositions now makes it possible to combine the process of a more economical stage described with the advantages of the more complicated two-stage process. This is achieved by the possibility of providing mixtures of extremely low viscosity according to the invention which give high modulus vulcanizates, dynamically stable after crosslinking. The subsequent mixture can be based on a conventional blend composition, the viscosity which is substantially above the crosslinkable composition according to the invention for the teeth. The large differences in the viscosity of the mixture of the two layers (at high temperatures / high shear) makes possible a layer of high viscosity provided to the back to push the layer provided to fill the teeth in the front of it without main rear mixing in the notched cavities. It is particularly advantageous in this use of the crosslinkable composition according to the invention that the low viscosity composition according to the invention still has sufficient strength (green resistance) at room temperature that the toothed band can be constructed according to a traditional process using the traditional apparatuses, since the stable milled sheets which are necessary to manufacture the strip can still be produced from the composition according to the invention at room temperature. 4. Roller covers The invention additionally relates to the use of the compositions according to the invention for the production of roller covers. High modulus roller covers, as used, for example, in the transport, paper or steel industry, are usually produced, as is known to the person skilled in the art, in the rubber vulcanizing base. In order to achieve the required properties of extreme hardness and modules, mixtures of very high viscosity are typically required. These mixtures are placed in layers in the roller body as ground or extruded sheets directly. The viscosity and therefore the degree of filling which will be produced by the high modulus and hardness are subject to limits. Very high viscosity grinding sheets which comprise the mixture often can not run together during vulcanization, and therefore fractures and stresses preformed in the products are formed and lead to premature failure. Another process known to the skilled person for producing covers of a high modulus roll starts from the polyurethane blends which are applied in liquid form and, "after curing in situ" (by reacting crosslinking, crystallization, conversion into a polyurethane) thermoplastic (TPU)), has extreme hardness and very high dynamic stability, however, these products have the difficulty that the dynamic mechanical properties decrease quite significantly in temperatures> 100 ° C and additionally there is only poor stability, inter alia due to the hydrolysis, at a very wide range of media.The cause of this is thermoplasticity (TPU belonging to the class of material which consists of the TPE; after softening the crystalline fractions, the properties are substantially lost) and the chemical instability to acids and bases, as well as esters, aromatic oils and fats. In order to use the crosslinkable composition according to the invention for the production of such roller covers, on the other hand, it is possible to apply the compositions according to the invention to the roll body at temperatures > 100 ° C and / with high shear stress. The very low viscosity, in some cases the "liquid" starting material, ie the crosslinkable composition according to the invention, which however has sufficient stability under the load, is applied to the roll in order to be vulcanized and, After vulcanization, it leads to products that have important physical properties, high modulus and strength. In a "non-liquid" form of still processable application, it is possible in the present to achieve fill grades which are substantially superior to conventional systems without the processability that is damaged and the mentioned stress cracks occurring in the roll covers. 5. Vulcanized thermoplastics The invention additionally relates to the use of crosslinkable compositions for the preparation of thermoplastic vulcanizates. In addition to the crosslinkable composition based on the elastomer, one or more thermoplastic polymers are additionally used herein. In the preparation of thermoplastic vulcanizates by means of dynamic crosslinking, the kinetic process of the inversion phase, in which thermoplastic particles dispersed in the elastomer matrix are initially present, to give the phase structure where the elastomer particles are present in Vulcanized form and dispersed in a thermoplastic matrix, is of decisive importance. To ensure that a particle structure is achieved as homogeneous as possible by having a particle size as small as possible (as a basic precondition for good dynamic mechanical properties of the products) the viscosity of the thermoplastic melt and the viscosity of the Rubber phase should be as comparable in an order of magnitude as possible. If the viscosity differences are very large, only particle sizes of the rubber phase of > 1-50 um, which leads to only poor properties of the desired product. In order to adapt these viscosities, large amounts of plasticizers are frequently used, which of course leads to a deterioration in the properties of the elastomeric phase. For oil stable vulcanizates, the use of large amounts of plasticizers (partially compatible oils which are used to reduce the viscosity of a mixture) are undesirable due to the often poor compatibility of plasticizers and elastomer, because, in the case of Excessively large doses of plasticizers can exude from the component, which leads to a reduction in the optical quality of the components. By using the crosslinkable compositions according to the invention, it is now possible to provide highly polar, oil-stable elastomer phases of very low viscosity, although they have important physical properties, which overcome the disadvantages described, ie excellent processing properties and phase distribution are achieved while at the same time retaining the optical and mechanical properties. The polyamides which can be used in the composition according to the invention are homo or copolymers which contain, in the main chain of the polymer, monomer building blocks which are linked by means of amide bonds (-C (= 0) -NH-). Examples of polyamides which can be used are polycaprolactam (nyon 6), polylaurolactam (nylon 12), polyhexamethylene adipate (nylon 6.6), polyhexamethylenebenazelamide (nylon 6,9), polyhexamethylene sebacamide (nylon 6,10), polyhexamethylene phosphthalamine (nylon 6, IP), polyaminoundecanoic acid (nylon 11), polytetramethylene adipamide (nylon 4,6) and copolymers of caprolactam, hexamethylenediamine and adipic acid (nylon 6,66) and aramides, such as polyparaphenyleneterephlamide. Most polyamides have softening points and melting points in the range of 120 to 260 ° C. The polyamides preferably have a high molecular weight and are crystalline. The polyesters which can be used in the composition according to the invention are homo- or copolymers which have, in the main chain of the polymer, monomer building blocks which are linked by means of ester groups (-C (= 0) -0-). For example, the types of hydroxycarboxylic acids or types of dihydroxycarboxylic acids can be used as homopolyesters. The former can be prepared by polycondensation of a 5-hydroxycarboxylic acid or by ring-opened polymerization of cyclic esters (lactones), and the latter by polycondensation with two complementary monomers, for example a diol and a saturated or unsaturated dicarboxylic acid. Poly (ethylene terephthalate), poly (oxy-1,2-ethanediyloxycarbonyl-1, -phenylenecarbonyl), poly (1,4-dimethylenecyclohexane terephthalate), poly (butylene terephthalate), poly (tetramethylene terephthalate), poly (oxy-1, 4- butanedyloxycarbonyl-1,4-phenylenecarbonyl) can be used (with reference also to Ullmann's Encyclopedia of Industrial Chemistry Copyright © 2002 DOI: 10. 1002/14356007. a21_227 Article Online Posting Date: June 15, 2000).

The polyimides which can be used in the composition according to the invention are homo- or copolymers which contain, in the main chain of the polymer, monomer building blocks which are linked by means of imide groups. The imida groups can be presented as linear or cyclic units. The melting points of the suitable polyimides are in the range 150-260 ° C (also with reference to Ullmann's Encyclopedia of Industrial Chemistry Copyright © 2002 by wiley-VCH Verlag GmbH &Co. GaA.DOI: 10.1002 / 14356007. a21: 253). The polypropylenes which can be used in the composition according to the invention are all polypropylenes which have a melting point of > 150 ° C and a high degree of crystallinity. The polyethers which can be used in the composition according to the invention are homo- or copolymers which contain, in the polymer backbone, monomer building blocks which are linked by means of ether groups (CO) and are distinguished by a melting point greater than about 150 ° C and less than about 260 ° C. 6. Shaped articles The invention additionally relates to the use of the crosslinkable compositions according to the invention for the production of shaped articles.

The shaped articles are typically produced in the injection molding or compression process. The finer the desired structures are, the greater the requirements which have to comply with the flow properties of the materials used. Therefore, fine structures combined with high resistances and high modulus are a known challenge for the person skilled in the art. The flow properties can often be improved by means of process aids. The process assistant comes into contact with the surface of the mixtures during the processing processes and moistens the contact surfaces with the molds. In this way, the adhesion to the wall is reduced and the flow behavior is improved. This advantage is however also frequently accompanied by increasing the staining of the surfaces of the parts, and the latter therefore it has to be subjected to additional cleaning processes and therefore the times of use of the reduction of the molding and reduction times of the molding are increased. The composition according to the invention offers a solution to this problem since high fluidity is combined here with excellent properties after vulcanization. The following may be mentioned by the example form herein as a process for the production of shaped articles: A Junction at the site The so-called "site jointing" is a process in which usually very low viscosity, in some cases liquid starting materials, generally based on polyurethane or silicone rubbers, are processed in liquid form, emptied into molds and then reactively crosslinked. Both systems show only poor physical properties and low stability to swell in polar media at high usage temperatures of over 100 ° C compared to other high performance elastomers, such as HNBR, EVM, AEM and ACM, and it is for this reason that the potential uses are limited to the area of systems free of mechanical load with only little oil stability. With the composition according to the invention, the complex systems can now be filled by jointing at the site due to the low viscosity at relatively low temperature and / or with high shear stress and stability under load allows a downstream crosslinking process without critical loss of the dimension of the sealed parts. After vulcanization, these products show high thermal stability and oil stability and excellent dynamic mechanical properties. In this way, they combine the advantages of liquid systems with those based on the mixture of high-resolution high-viscosity elastomers. B co-injection molding of rubber plastic Co-injection molding of rubber plastic is a process in which first a plastic / thermoplastic component is injection molded into a thermoplastic mold. This is transported in a rotatable molding within the same machine to a rubber injection unit, the rubber is then injected and vulcanized on one side in contact with the thermoplastic molding and on the other side in contact with the metal mold. This process is advantageous since the complex thermoplastic rubber forming articles can be injected and linked in a single step. The critical for the production of complex components, for example shaped thermoplastic articles having complicated rubber vulcanizing sealing elements, is the fluidity of the rubber mixture and the property profile of the vulcanized rubber as well as the adhesion between the two components . Extremely flowable rubber blends on base, for example, silicone rubber shows good mold filling but very limited adhesion and vulcanization properties. Due to their high viscosity, conventional rubber blends can often fill cavities only with difficulty. An additional difficulty of conventional systems is the achievement of cycle times such as those possible in the case of reactive crosslinking systems of, for example, silicone rubber or polyurethane, since the crosslinking times with the use of suitable peroxides or with the use of amine crosslinking systems, such as, for example, in the case of AEM rubber, which are necessary for high temperature applications, are relatively large. The coupling of precuration and full healing is always difficult here. A large pre-cure time is possible in order to allow mold filling particularly in the case of high viscosity materials, and a short complete cure time is necessary in order to maintain cycle times in the process of co-injection molding of plastic-rubber short, since the rubber vulcanization process is the determining factor in time in this process. In this process according to the invention, the use of the compositions according to the invention allows both excellent mold filling and excellent vulcanization properties, comparatively short cycle times and high adhesion. In addition to the aforementioned broader possibilities of use, the crosslinkable compositions according to the invention can also be used for the following special applications, for example for the production of foamed shaped articles., shaped articles for sealing adhesive materials, flat packings (also referred to as soft material seals), joint packings (solid or foamed), fraction and brake linings, clutch linings, as additives for the elastification of phenol resin materials formaldehyde resin materials and epoxy resin materials, for impact modification of thermoplastics and thermosetting plastics, for the production of cylinder head gaskets, cylinder head cover gaskets, hoses, membranes, seals, bellows, rubber muscles , sheet metal coatings, adhesion systems which are solvent free or have a low solvent content, for bonding fabric adhesives without a separate adhesion layer, such as upper fabric layers, rubber metal bonding systems that they have a high module, for surface adhesion, for solvent-free flexibilization of circuit boards in place r of ground rubber, such as coated metal seals, repair mixes for conveyor belts or belts, as adhesion mixtures for the bonding of endless belts and belts and for the products produced by the screen printing process. The inventive object of the present invention originates not only from the subject matter of the individual patent claims but also from the combination of the individual patent claims with one another. The same applies to all the parameters described in the description and any combinations thereof. Examples The primary mixing unit used is a mixing roller which has a roller unit cooled to ° C, type WNU3 of Troester, with rollers which have a diameter of 200 mm. The elastomer is introduced initially and all the additional components are added in the sequence (2), then (4), then (3) (see the list of components shown later). The speed and friction of the roller is controlled in such a way that the stable milled sheets are obtained. After a mixing time of about 5 minutes the mixing is finished and the product is taken as a ground sheet from the roll. The vulcanization of these ground sheets is then carried out at 180 ° C for 15 minutes in plate presses. Components used: 1. Therban® AT-XT VP KA 8889 Hydrogenated nitrile carboxylated rubber, ACN content: 33% by weight, Mooney viscosity ML 1 + 4 @ 100 ° C: type a) 10 Me or type b) 25 ME , residual double bond content: 3.5%.

The elastomer used herein is prepared by metathesis of Therban® XT VP KA 8889 (XNBR) from Lanxess Deutschland GMBH and subsequent hydrogenation. 2. Therban® XT VP KA 8889 The carboxylated hydrogenated nitrile rubber from Lanxess Deutschland GMBH ACN content: 33%, viscosity Mooney ML 1 + 4 @ 100 ° C: 78 ME, residual double bond content: 3.5%. This elastomer is commercially available from Lanxess Deutschland GMBH. 3. Sartomer® SR 633 Zinc diacrylate from Sartomer 4. Statex N330 Carbon black from Columbian Chemical Company 5. Carbon black IRB7 black carbon industrial reference 7 6. Xinc oxide IRM 91 industrial reference ZnO 7. Rhenofit® OCD Diphenylamine octilatable (anti-aging agent) from Rheinchemie 8. Rhenofit® TAC / S triallyl cyanurate (vulcanization activator) Rheinchemie 9. Perkadox® 14-40 B-GR Bis (tert-butyl peroxyisopropyl) benzene from Akzo Nobel Chemicals B.V. lO.Vulcanox® ZMB2 / 5 The mercaptobenzimidazole zinc stabilizer from Lanxes Deutschland GMBH All the stated "phr" amounts in the tables denote parts per hundred parts of rubber. The elastomer component corresponds to 100 phr. The determination of the complex viscosity? * And the change of the complex viscosity as a function of temperature or amplitude is carried out in a rubber process analyzer (RPA 2000) from Alpha Technologies. The vulcanization measurement is carried out in a Monsanto MDR 2000 reometro at a test temperature of 180 ° C over a test time of 15 minutes. Example 1-9: All the comparative examples are characterized by a * next to the respective example number in the following tables.

Table 1: Crosslinkable compositions Table 2: Rheological properties of vulcanizable compositions (RPA test method) Table 3. Vulcanization measurement Table 4: Physical properties of the vulcanizates obtained by sheet pressure Only the compositions 4 and 5 according to the invention show "liquid" processability and high temperatures (130 ° C) and processability as normal rubber at low temperatures (60 ° C), as described above.

Only the compositions according to the invention in combination with liquid processability below the crosslinking temperature of 180 ° C. Only the compositions according to the invention show very low d values after crosslinking - as can be observed from the MDR measurement - despite extremely high crosslink densities and extremely low processing viscosities. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (26)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as prop: 1: Crosslinkable compositions which contain: (1) one or more elastomers, at least one of which has carboxyl and / or carboxylate groups ( 2) one or more different salts of the general formula (I) (Ry-) x / yMx + (I) in which R? "Represents a C3-C? 4 a, β-unsaturated carboxylate which contains carboxylate groups and , and may represent values 1, 2, 3, or 4, x is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal and, (3) one or more crosslinking agents which act as donors of free radicals, characterized in that a.the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together have a Mooney viscosity (ML 1 + 4 in 100 ° C), measured according to the ASTM Di6 6 standard, in a range of 1-35 and b. the crosslinkable composition (i) has a complex viscosity? *, measured on a Rubber Process Analyzer (RPA) at 60 ° C, 1Hz and an amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of? * (at 1Hz and 10% amplitude) to? * (at 1Hz and 100% amplitude), over 1.4, (iii) a temperature dependent change of the complex viscosity, measured in the RPA as the ratio of? * (At 60 ° C, 1Hz and 10% amplitude) to T | * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 and (iv) a change dependent on the amplitude of the complex viscosity, measured in the RPA at 130 ° C as the ratio of? * (at 1Hz and 10% amplitude) to T | * (in 1 Hz and 10% of amplitude), of less than 1.5, the values established for the complex viscosity (? *) In all the cases mentioned above (i) - (iv) indicate in each case the mathematical magnitude of the complex viscosity.
2. 2. The crosslinkable compositions according to claim 1, which contain (1) 10-94% by weight of one or more elastomers, at least one of which has carboxyl and / or carboxylate groups, (2) -89% by weight of one or more salts of the general formula (I) (Ry-) x / and Mx + (I) in which Ry ~ represents a C3-C4 α, β-unsaturated carboxylate which contains the groups carboxylate, Y can represent the values, 1, 2, 3, or 4, X is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal And (3) 1-20% by weight of one or more crosslinking agents which act as free radical donors, the sum of the components (1), (2), and (3) is less than or equal to 100% in weight. Characterized by (a) the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together has a Mooney viscosity (ML 1 + 4 at 100 ° C), as measured by according to the ASTM Di6 6 standard, in a range of 1-35 and (b) the crosslinkable composition (i) has a complex viscosity r *, measured on a Rubber Process Analyzer (RPA) at 60 ° C, 1Hz and a amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of? * (at 1Hz and 10% amplitude) to? * (in 1Hz and 100% amplitude), more than 1.4, (iii) a temperature-dependent change in the complex viscosity, measured in the RPA as the proportion of? * (in 60 ° C, 1Hz and 10% of amplitude) a? * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 (iv) a change dependent on the amplitude of the complex viscosity, measured at the RPA at 130 ° C as the proportion from? * (in 1Hz and 10% amplitude) to? * (in 1 Hz and 100% amplitude), less than 1.5, the values established for the complex viscosity (? *) in all the cases mentioned above (i) - (iv) indicate in each case the mathematical magnitude of the complex viscosity.
3. 3. The crosslinkable compositions according to claim 1, which contain (1) 30-84% by weight of one or more elastomers., at least one of them having carboxyl and / or carboxylate groups, (2) 14-68% by weight of one or more salts of the general formula (I) '(pRYyM' xX // yY (I. which Ry ~ represents a C3-C1, ß-unsaturated carboxylate which contains the carboxylate groups, Y may represent the values, 1, 2, 3, or 4, X is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal and (3) 2-15% by weight of one or more crosslinking agents which act as free radical donors, the sum of the components (1), (2), and (3) is lower or equal to 100% by weight, characterized in that (a) the elastomer (1) or, if a plurality of elastomers (1) is used, the mixture of all the elastomers (1) together has a Mooney viscosity (ML 1 + 4). at 100 ° C), measured according to ASTM D1646 standard, in a range of 1-35 and (b) the crosslinkable composition has (i) has a complex viscosity? *, measured in a Rubber Process Analyzer (RPA) at 60 ° C, 1Hz and an amplitude of 10%, of more than 30,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured at the RPA at 60 ° C as the ratio of? * (in 1Hz and 10% of amplitude) to? * (in 1Hz and 100% of amplitude), of more than 1.4, (iii) a temperature-dependent change of the complex viscosity, measured in the RPA in as the ratio of? * (at 60 ° C, 1Hz and 10% amplitude) to? * (at 130 ° C, 1 Hz and 10% amplitude), more than 6 (iv) a change dependent on amplitude of the complex viscosity, measured at the RPA at 130 ° C as the ratio of? * (at 1Hz and 10% amplitude) to? * (at 1 Hz and 100% amplitude), of less than 1.5, the values established for the complex viscosity (? *) in all the cases mentioned above (i) - (iv) indicate in each case the mathematical magnitude of the complex viscosity.
4. 4. The crosslinkable compositions according to one or more of claims 1-3, characterized in that the compositions contain, as the component (4), up to 84% by weight, preferably 4 to 64% by weight and particularly and preferably 10- 40% by weight of one or more additional auxiliaries, preferably containing fillers, fibers, polymers which are not converted by the definition of the elastomers (1) in claim 1, oils, stabilizers, processing aids, plasticizers, additional monomers, dimers, trimers or polymerizable oligomers, or vulcanization activators, the sum of the components (1), (2), (3) and (4) which is 100% by weight.
5. 5. The crosslinkable compositions according to one or more of claims 1 to 4, characterized in that they have (i) a complex viscosity? *, Measured on a Rubber Process Analyzer (RPA) at 60 ° C, 1 Hz and an amplitude of 10%, of more than 30,000 Pas, preferably of more than 40,000 Pas, (ii) a change in the complex viscosity dependent on the amplitude, measured in the RPA at 60 ° C as the ratio of? * (in 1Hz and 10% of amplitude) a? * (In 1Hz and 100% of amplitude), of more than 1.4, preferably of more than 1.6, (iii) a change dependent on temperature of the complex viscosity, measured in the RPA as the proportion of? * (at 60 ° C, 1Hz and 10% amplitude) a? * (at 130 ° C, 1 Hz and 10% amplitude), of more than 6, preferably of more than 8, and (iv) a change dependent on the amplitude of the complex viscosity, measured at the RPA at 130 ° C as the ratio of? * (at 1Hz and 10% amplitude) to? * (at 1 Hz and 100% amplitude), less of 1.5, preferably less than 1.4, the values established for the complex viscosity (? *) in all the cases mentioned above (i) - (iv) indicate in each case the mathematical magnitude of the complex viscosity.
6. 6. The crosslinkable composition according to one or more of claims 1 to 5, characterized in that the elastomer (1) or the total mixture of the elastomers (1), if a plurality of elastomers (1) is used, having 0.5- 15% by weight, preferably 0.5-10% by weight, particularly and preferably 1-7% by weight and in particular 1.5-6% by weight, based on 100% by weight of the elastomers (1) or based on the total mixture of the elastomers (1), if a plurality of elastomers (1) is used, of linked carboxyl and / or carboxylate groups. The reticulable composition according to one or more of claims 1 to 6, characterized in that it contains: 1. carboxylated nitrile rubber (also abbreviated as XNBR), 2. hydrogenated, carboxylated nitrile rubber (also abbreviated as HXNBR) 3 rubbers grafted with maleic anhydride ("MAH") on the basis of EPM, EPDM, HNBR, EVA, EVM, SBR, Nr or BR, 4. carboxylated styrene-butadiene rubber (also abbreviated as XSBR), 5. AEM which has free carboxyl groups, or 6. ACM having free carboxyl groups and any desired mixtures of the polymers mentioned above which are used as elastomers (1) containing carboxyl and / or carboxylate groups. 8. The crosslinkable compositions according to one or more of the claims 1-7, the Mooney viscosity (ML 1 + 4, measured at 100 ° C), characterized in that it is measured according to the ASTM D 1645 standard of the elastomer (1) used or if a plurality of elastomers (1) is used of the mixture of all elastomers, (1) which are in a range of 2 to 25, preferably 5 to 20. The crosslinkable composition according to one or more of claims 1-8, characterized in that it contains a carboxylated nitrile rubber (XNBR ) which is a terpolymer of at least one α, β-unsaturated nitrile, at least one conjugated diene and at least one additional thermonomer which contains carboxyl and / or carboxylate groups which are used as component (1). The crosslinkable composition according to one or more of claims 1-9, characterized in that the carboxylated nitrile rubber (XNBR) which comprises polymers of butadiene and acrylonitrile and acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid and / or monoesters of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl of fumaric acid and / or maleic acid and / or methyl, ethyl, propyl esters, isopropyl, n-butyl, isobutyl, n-hexyl, or 2-ethylhexyl of acrylic acid and / or methacrylic acid which is used as component (1). The crosslinkable composition according to one or more of claims 1-10, characterized in that it has a carboxylated nitrile rubber (XNBR) which comprises polymers of butadiene and acrylonitrile and a monomer which contains the carboxyl groups, in particular acid fumaric acid, maleic acid, acrylic acid or methacrylic acid, and a monomer which contains carboxylate groups, in particular the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl monoamide of fumaric acid or maleic acid or methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl or 2-ethylhexyl ester of acrylic acid or methacrylic acid which is used as component (1). 12. The crosslinkable composition according to one or more of claims 1-11, characterized in that the hydrogenated carboxylated nitrile rubber (also abbreviated as HXNBR) is used as the component (1). The crosslinkable composition according to one or more of claims 1-12, characterized in that the hydrogenated carboxylated nitrile rubber which is obtainable by hydrogenation of the carboxylated nitrile rubbers according to one or more of the claims 9-11 is used as component (1). 14. The crosslinkable composition according to one or more of claims 1-13, characterized in that in addition the elastomers (1), which do not have the carboxyl and / or carboxylate groups are used as the component (1), in addition to one or more elastomers (1) which has the carboxyl and / or carboxylate groups. 15. The crosslinkable composition according to claim 14, characterized in that NBR and HNBR are used as component (1). 16. The crosslinkable composition according to one or more of claims 1-15, one or more salts of the general formula (I) (RY ") x / y MX + characterized in that Ry ~ represents a C3-C carboxylate a, ß-unsaturated which contains the carboxylate groups y, Y can represent the values 1, 2, 3, or 4, X is 2, 3, or 4 and M is a divalent, trivalent or tetravalent metal and represents Mg, Ca, Zn , Faith, Al, Ti, Pb, B, Sc, Yt, Sn or Haf Being used as the component. 17. The crosslinkable composition according to one or more of claims 1-16, characterized in that in the component (2) the radical Ry ~ in the general formula (I) is representing a C3-Cs, unsaturated carboxylate. which contains the carboxylate groups, it being possible to and assume the value 1, 2, 3 or 4 and Ry ~ in the general formula (I) which preferably represents acrylate, methacrylate, crotonate, isocrotonate, sorbate, fumarate or maleate or mixtures of the same . 18. The crosslinkable composition according to one or more of claims 1-17, characterized in that one or more crosslinking agents in the form of peroxide compounds, azides, photoinitiators, redox initiators or mixtures of the aforementioned are used as the component (3). The crosslinkable composition according to one or more of claims 1-18, peroxide compounds from the following group characterized in that it is used as component (3): bis (2,4-dichlorobenzoyl) peroxide, dibenzoyl peroxide , bis (4-chlorobenzoyl) peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butyl perbenzoate, 2,2-bis (tert-butylperoxy) butene, 4-valerate , 4-di-tert-butylperoxinonyl, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, peroxide of di-tert-butyl, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin, tert-butyl hydroperoxide, hydrogen peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, decanoyl peroxide, peroxide 3 , 5, 5-trimethylhexanoyl, di (2-ethylhexyl) peroxydicarbonate, poly (tert-butylperoxycarbonate), 3, 3-di (tert-butylperoxy) ethyl butyrate, 3, 3-di (tert-amylper oxy) ethyl butyrate, 4,4-di (tert-butylperoxy) n-butyl valerate, 2,2-di (tert-butylperoxy) butane, 1,1-di (tert-butylperoxy) cyclohexane, 3,3, 5-trimethylcyclohexane, 1,1-di (tert-amylperoxy) cyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyisobutyrate, peroxy- 2- tert-butyl ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxine-3-oxalate, cumyl peroxine-decanate, 3-hydroxy-1, 1-dimethylbutyl peoxine-3-oxalate, tert-butyl peroxybenzoate, peroxyacetate tert-butyl, tert-amyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, cumyl peroxineodecanoate, 3-hydroxy-1, -dimethylbutyl peroxyne-3-oxalate , 2,5-dimethyl-2, 5-di (tert-butylperoxy) hexyne peroxide (3-di-tert-amyl), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, hydroperoxide tert-am ilo, cumol hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) exano, diisopropylbenzene monohydroperoxide and potassium peroxodisulfate. 20. The crosslinkable composition according to one or more of claims 1-18, characterized in that the, 2-azobismetylethylacetonitrile as an azide which is used as the component (3). The crosslinkable composition characterized in that it is in accordance with one or more of claims 1-18, a photoinitiator from the following group which is chosen as component (3): benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoylphenylcarbinol, methylphenyl glyoxylate, 4, '-diazidobiphenyl, 4,' -diazidobenzophenone, 4,4'-diazidobiphenyl, 4, '-diazido-disulfonylbiphenyl oxide, azidobenzene, acid 4-azidobenzoic acid, 1,2-bis- (4-azidophenyl) ethylene, 4-aminophenyl-4'-azidophenylmethanol, 2,5-di (4'-azidobenzal) cyclohexanone, 4,4'-diazidoestilbene-2, 2 ' sodium disulfonate, benzophenone, benzophenone oxime, bromoacetophenone, cyclohexanone, diphenyl monosulfide, dibenzothiazolyl disulfide, s-acyl dithiocarbamate, m, m'-azoxystyrene, benzimdimethyl ketal, 4-methylbenzophenone, 4-phenylbenzophenone, 4-dimethylaminobenzoate of ethyl (EPD), 2-hydroxy-2-methylphenylpropan-l-one, isopr opylthioxanthone (ITX), and 2-methyl-1- (4-methylthiophenyl) -2-morpholinoproppan-1-one. The crosslinkable composition according to one or more of claims 1-18, characterized in that a redox initiator is chosen from the following group as component (3): Fe (II) / hydroperoxide, peroxide / tertiary amine, peroxodisulfate / thiosulfate, hydroperoxide / thiosulfate. 23. Process for the preparation of the crosslinkable elastomers according to one or more of the crosslinks 1-22, characterized in that all the components (l) - (3) and optionally (4) are mixed. 24. The process for the preparation of crosslinked elastomers, at least one of which has carboxyl and / or carboxylate groups, characterized in that the crosslinkable composition according to one or more of claims 1-22 is subjected to the energy input , preferably in the form of thermal energy or radiation energy. 25. The crosslinked elastomers characterized in that they are obtained by the process according to claim 24. 26. The use of the crosslinkable compositions according to one or more of claims 1-22 as elastic adhesive materials, as impregnating materials, for the production of belts, preferably of toothed belts or drive belts, or for the production of roller covers, of thermoplastic vulcanizates or shaped articles.