EP3090019A1

EP3090019A1 - Phenol-containing hydrogenated nitrile rubber

Info

Publication number: EP3090019A1
Application number: EP14828164.5A
Authority: EP
Inventors: Werner Obrecht
Original assignee: Arlanxeo Deutschland GmbH
Current assignee: Arlanxeo Deutschland GmbH
Priority date: 2013-12-30
Filing date: 2014-12-29
Publication date: 2016-11-09
Also published as: WO2015101599A1; TWI649335B; CN105992797A; JP6457538B2; KR20160105833A; KR102240055B1; CN105992797B; JP2018145434A; TW201546096A; US20160376421A1; JP2017504696A

Abstract

The invention relates to novel hydrogenated nitrile rubber which has a specific phenol content, to a method for the production thereof, vulcanisable mixtures based thereon and vulcanisates obtained therefrom. Said vulcanisates are characterized in that they have a particularly good module level and compression set value in addition to very good storage stability.

Description

Phenol-containing hydrogenated nitrile rubbers

The invention relates to novel hydrogenated nitrile rubbers which have a specific phenol content, a process for their preparation, vulcanizable mixtures based on the hydrogenated nitrile rubbers and vulcanizates obtained therefrom.

Nitrile rubbers are copolymers and terpolymers of at least one unsaturated nitrile monomer, at least one conjugated diene and optionally one or more copolymerizable monomers. Processes for the production of nitrile rubber (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, pp. 255-261) and processes for the hydrogenation of nitrile rubber in suitable organic solvents are known (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993 , Pp. 320-324).

Hydrogenated nitrile rubber, also abbreviated "HNBR", is understood to mean rubbers which are obtained by hydrogenation using nitrile rubbers, also abbreviated to "NBR". Accordingly, in HNBR the C =C double bonds of the copolymerized diene units are completely or partially hydrogenated. The degree of hydrogenation of the copolymerized diene units is usually in a range of 50 to 100%. However, so-called "fully hydrogenated types" have already been mentioned in the art if the residual double bond content is at most about 0.9% The commercially available HNBR types usually have a Mooney viscosity (ML 1 + 4 at 100 ° C.) ranging from 10 to 120 Mooney units.

HNBR is a special rubber that has very good heat resistance, excellent resistance to ozone and chemicals, and excellent oil resistance. The aforementioned physical and chemical properties of the HNBR go along with very good mechanical properties, in particular a high abrasion resistance.

Because of this property profile, HNBR has found wide use in a wide variety of applications. HNBR is e.g. used for seals, hoses, belts, cable sheaths, roller coverings and damping elements in the automotive sector, as well as for stators, borehole seals and valve seals in the field of oil production as well as for numerous parts of the aerospace industry, the electrical industry, mechanical engineering and shipbuilding.

Vulcanizates of HNBR with a high modulus level and a low compression set play a special role, especially after long storage times at high temperatures. This combination of properties is important for applications where the rubber product is required to function both under static and dynamic load high restoring forces are required especially after long periods and possibly high temperatures. This applies in particular to different seals such as O-rings, flange seals, shaft seals, stators in rotor / stator pumps, valve stem seals, gaskets such as axle boots, hose seals, engine mounts, bridge bearings and blow-out preventer. Furthermore, high modulus vulcanizates are important for dynamically loaded articles, especially for belts such as drive and timing belts, in particular timing belts and for roller coverings.

The level of mechanical properties of HNBR-based vulcanizates achieved so far, in particular with regard to the module level and the compression set, is still unsatisfactory.

DE-A-3 921 264 describes the preparation of HNBR which, after peroxidic crosslinking, provides low compression set vulcanizates. In the hydrogenation ruthenium catalysts of various chemical constitution are used using a solvent mixture of a C3-C6 ketone and a secondary or tertiary C3-C6 alcohol. The proportion of the secondary or tertiary alcohol in the solvent mixture should be 2 to 60 wt.%. It is described that during the hydrogenation or during the cooling of the solution after hydrogenation it may lead to the formation of two phases. As a result, the desired degrees of hydrogenation are not achieved and / or the hydrogenated nitrile rubber gels during hydrogenation. The process described in DE-A-3 921 264 is not widely applicable because the hydrogenation phase separation and gelling unpredictably depends on a number of parameters. These include the acrylonitrile content and the molecular weight of the nitrile rubber feedstock, the composition of the solvent mixture, the solids content of the polymer solution in the hydrogenation, the degree of hydrogenation and the temperature in the hydrogenation. Even when the polymer solution is cooled following the hydrogenation or during the storage of the polymer solution, an unforeseen phase separation and contamination of the corresponding system parts or containers may occur. DE-A-3 921 264 does not teach how to improve the modulus level and compression set by the anti-aging agent used in the preparation of the nitrile rubber feedstock and its amount.

According to the teachings of EP-A-0 319 320, vulcanizates are obtained on the basis of HNBR which, while having good processability (low mixing viscosity), have both high modulus values and low compression set values and are suitable for the production of toothed belts. This combination of properties is achieved by adding metal salts of unsaturated methacrylic acids to the mixture preparation. EP-A-319 320 gives no teaching for the improvement of Module levels and the compression set by the used in the manufacture of the nitrile rubber feedstock aging inhibitor and its amount.

US 2,281,613 describes the portionwise or continuous addition of aliphatic mercaptans having a carbon number> 6, preferably 6-12 in the copolymerization of butadiene with other monomers such as acrylonitrile in emulsion for molecular weight control. The formation of gel in the polymerization can thus be avoided. The use of anti-aging agents is not mentioned. Measures to improve the module level and the compression set of vulcanizates of HNBR are not disclosed.

Also according to US Pat. No. 2,434,536, mercaptans with 8 to 16 C atoms are added in portions or continuously in the course of the copolymerization of butadiene and acrylonitrile, at the beginning of the polymerization mercaptans having a high molecular weight and with increasing monomer conversion mercaptans having a lower molecular weight being metered in , In this way, the "plasticity" and the "mastizability" and thus the processability on the roll and in the Banbury mixer of rubbers obtained at high polymerization conversions are improved. In US 2,434,536 the use of anti-aging agents is not mentioned. From GB 888040 a process is known for the coagulation of nitrile rubber and polychloroprene latices prepared with oleate-based emulsifiers. For coagulation, an aqueous solution of an ammonium salt is added to the alkaline latex and then heated. As a result of the reduction of the pH, coagulation of the latex occurs. It is apparent from the example section that 1.5 parts of 2,2'-dihydroxy-3,3'-dicyclohexyl-5,5'-dimethyldiphenylmethane are added to the nitrile rubber latex prior to coagulation. On the basis of GB 888040, no further conclusions can be drawn on the influence of anti-aging agents on the properties, in particular the module level and the compression sets of NBR or HNBR-based vulcanizates. From DD 154 702 a process for the radical copolymerization of butadiene and acrylonitrile in emulsion is known, which is controlled by a special metering program for the monomers and the molecular weight regulator, such as tert-dodecyl mercaptan, and in which the latices obtained by coagulation in an acidic medium be worked up to the solid rubber. As a significant advantage of the method is stated that the resin and / or fatty acid soaps used as emulsifiers remain by the use of acids during coagulation in the rubber, so not washed out as in other methods. For this purpose, in addition to the advantage of good properties of NBR especially the improvement of the economy of the process and the avoidance of wastewater pollution by leached emulsifier reclaimed. The resulting butadiene-acrylonitrile copolymers having 10-30 wt.% Of acrylonitrile are said to have good elasticity and low temperature properties combined with increased swelling resistance and advantageous processability. Information on the use of anti-aging agents and on the storage stability of the nitrile rubbers and on the influence of these anti-aging agents on the properties of hydrogenated nitrile rubber and its vulcanizates prepared therefrom are not found.

From DE-OS 23 32 096 it is known that rubbers can be precipitated from their aqueous dispersions with the aid of methyl cellulose and a water-soluble alkali metal, alkaline earth metal, aluminum or zinc salt. As an advantage of this method is described that a coagulum is obtained which is almost completely free of impurities such as emulsifiers, catalyst residues and the like, since these foreign substances removed together with the water in the separation of the coagulum and any remaining residues completely washed with more water become. In the DE-OS 24 25 441 are in the electrolytic coagulation of rubber latexes as adjuvant instead of methylcellulose 0.1-10 wt.% (Based on the rubber) of water-soluble C2-C4 alkylcelluloses or hydroxyalkylcelluloses in combination with 0.02 to 10 wt. %> (based on the rubber) of a water-soluble alkali, alkaline earth, aluminum or zinc salt, preferably sodium chloride. The coagulum is mechanically separated, optionally washed with water and the remaining water removed. Again, it is stated that the foreign substances are virtually completely removed along with the water when separating the coagulum and about any remaining residues are completely washed out by washing with more water. No information is given on the residual amounts of impurities in these nitrile rubbers. Furthermore, neither in DE-OS 23 32 096 nor in DE-OS 24 25 441 information on the type and amount of anti-aging agents that are added to the Nitrilkautschuklatex before work-up and on their influence on the properties of hydrogenated nitrile rubber produced therefrom and its vulcanizates.

In DE-OS 27 51 786 it is found that the precipitation and isolation of rubbers from their aqueous dispersions with a smaller amount of (hydroxy) alkyl cellulose can be carried out when 0.02 to 0.25 wt.%> A water-soluble calcium salt used become. It is again described as an advantage that an extremely pure coagulum is obtained according to this method, which is virtually completely free of foreign components such as emulsifiers, catalyst residues and the like. These foreign substances are removed together with the water when separating the coagulum and any remaining residues can be washed out with water. It is further stated that the properties of the isolated rubbers are not adversely affected by coagulation with a calcium salt. Rather, get one Rubber in which the vulcanizate properties are not impaired and fully satisfactory. This is surprising because degradation of rubber properties is often observed when polymers were precipitated from dispersions using polyvalent metal ions such as calcium or aluminum ions. The rubbers of DE-OS 27 51 786 showed no delay or deterioration, for example, during scorching and / or vulcanization. Information on the type and amount of anti-aging agents added to the nitrile rubber latex prior to working up and their influence on the properties of hydrogenated nitrile rubber produced therefrom and its vulcanizates are not found. As with the patents described above, it is also the goal of DE-OS 30 43 688 to reduce the amount of electrolyte necessary for the latex coagulation as much as possible. For this purpose, in the electrolytic coagulation of latices in addition to the inorganic coagulant as an aid used either on plants returning proteinaceous materials or polysaccharides such as starch and optionally water-soluble polyamine compounds. As inorganic coagulants, alkali or alkaline earth metal salts are preferably described. Due to the special additives, it is possible to reduce the quantities of salt necessary for quantitative latex coagulation. Information on the type and amount of anti-aging agents added to the nitrile rubber latex prior to working up and the influence of these anti-aging agents on the properties of hydrogenated nitrile rubber and its vulcanizates prepared therefrom are not provided.

According to US-A-2,487,263, the latex coagulation of styrene / butadiene rubbers is not carried out using metal salts, but with the aid of a combination of sulfuric acid with gelatin ("glue".) Quantity and concentration of the sulfuric acid are to be chosen such that the pH of the aqueous medium is adjusted to a value <6. In latex coagulation, discrete non-contiguous rubber crumbs are formed, which are well ablatable and washable.The resulting styrene / butadiene rubber has lower water absorbency, lower ash content, and higher electrical Resistance as rubbers which are coagulated with the aid of salts without added gelatin Whether and what effects coagulation with sulfuric acid under gelatin addition has on storage stability, vulcanization rate and vulcanizate properties and in particular on the modulus level of rubbers is not disclosed Anti-aging agents are also not included.

US Pat. No. 4,383,108 describes the preparation of a nitrile rubber by emulsion polymerization using sodium lauryl sulfate as emulsifier. The resulting latex is coagulated by an aqueous solution of magnesium and aluminum sulfate in the molar ratio of magnesium / aluminum 0.3 / 1 to 2/1. Here, the nitrile rubber is obtained as a powder with particle diameters in the range 0.3 to 4 mm, which may be with zinc soaps before drying Antiagglomerating agent is added. The examples of US Pat. No. 4,383,108 show that the latex is stabilized before coagulation by addition of 1.5 parts by weight of a "phosphite of polyalkylphenol." Information on the storage stability of nitrile rubber and on the amounts required for this purpose Phosphity-based anti-aging agents are not found.

US Pat. No. 5,708,132 describes the preparation of storage-stable and rapidly vulcanizing nitrile rubbers, wherein the nitrile rubber latex is mixed before coagulation with a mixture of a hydrolysis-susceptible and a hydrolysis-resistant aging inhibitor. The former is alkylated aryl phosphites, especially tris (nonylphenyl) phosphite. As hydrolysis-resistant aging inhibitors sterically hindered phenols, in particular octadecyl 3- (3,5-di-t.butyl-4-hydroxyphenyl) propionate (Ultranox® 276) and a chemical compounds with an incomprehensible structure "Thiodiethylene bis (3,5 The combination of two anti-aging agents reduces the rate of hydrolysis of the phosphite-based anti-aging agent, the sum of the anti-aging agents being from 0.25 to 3 parts by weight, based on 100 parts by weight It remains unclear in what proportion the two aging inhibitors are to be used and whether a good storage stability of the NBR can also be achieved by the sole use of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Furthermore, it is not disclosed whether it is possible to prepare nitrile rubbers with good storage stability which provide HNBR alone with sterically hindered phenols (without phosphite additives), its vulcanizates have high modulus values and a low compression set.

In US-A-4,920,176 it is disclosed that when coagulating a nitrile rubber latex according to the prior art using inorganic salts such as NaCl or CaC, very high sodium and calcium contents and also significant amounts of emulsifier remain in the nitrile rubber. In order to obtain as pure a nitrile rubber as possible, US Pat. No. 4,920,176 uses water-soluble cationic polymers instead of the inorganic salts in the coagulation of nitrile rubber latexes. These are, for example, those based on epichlorohydrin and dimethylamine. The resulting vulcanizates have a lower swelling in water storage and a higher electrical resistance. These property improvements are purely qualitatively attributed to the minimum cation levels remaining in the product. US-A-4,920,176 further describes the addition of anti-aging agents to the latex prior to coagulation. Various types of anti-aging agents such as phenolic anti-aging agents as well as explicitly 2,6-di-tert-butyl-p-cresol are explicitly mentioned. However, information on the dependence of the storage stability of the nitrile rubber on the type and amount of anti-aging agents is missing. Furthermore, US Pat. No. 4,920,176 contains no disclosure of the influence of the anti-aging agents used for stabilizing nitrile rubbers on the properties of vulcanizates of the hydrogenated nitrile rubbers obtained after the hydrogenation. The aim of EP-A-1 369 436 was to provide nitrile rubbers of high purity. The emulsion polymerization is carried out in the presence of fatty acid and / or resin acid salts as emulsifiers and then the latex coagulation by addition of mineral or organic acids at pH values equal to or less than 6, optionally with the addition of precipitants. As additional precipitating agents, alkali metal salts of inorganic acids can be used. Also precipitation aids such as gelatin, polyvinyl alcohol, cellulose, carboxylated cellulose and cationic and anionic polyelectrolytes or mixtures thereof can be added. The resulting fatty and resin acids are then washed out with aqueous alkali metal hydroxide solutions and the polymer is subjected to shearing until a residual moisture of less than or equal to 20% is established. Nitrile rubbers with low residual emulsifier contents and cation contents are obtained. There are no indications for the targeted production of nitrile rubbers with certain technological properties. The influence of anti-aging agents on product properties such as storage stability is not investigated. In US-A-4,965,323, the compression set of HNBR-based vulcanizates obtained by peroxidic or sulfur vulcanization is improved by contacting the nitrile rubber with an aqueous alkali solution or the aqueous solution of an amine after polymerization or after hydrogenation becomes. In example 1, rubber crumbs obtained after removal of the solvent are washed in a separate process step with aqueous soda solutions of different concentration. As a measure of the alkali content of the pH of an aqueous THF solution is used, which is obtained by dissolving 3 g of the rubber in 100 ml of THF and added with stirring 1 ml of water. The pH is determined by means of a glass electrode at 20 ° C. For the preparation of vulcanizates of the hydrogenated nitrile rubber with a low compression set, the pH of the aqueous THF solution should be> 5, preferably> 5.5, more preferably> 6. US-A-4,965,323 gives no indication as to whether the modulus level and compression set can be improved by the NBR feedstock's anti-aging agents.

EP-A-0 692 496, EP-A-0 779 301 and EP-A-0 779 300 each describe nitrile rubbers based on an unsaturated nitrile and a conjugated diene which have 10-60% by weight of unsaturated nitrile and also Mooney viscosity (ML 1 + 4 @ 100 ° C) in the range of 15-150 or according to EP-A-0 692 496 of 15-65 Mooney units and all at least 0.03 mol of a C 12 -C 16 -alkylthio Having group per 100 mol of monomer units, said alkylthio group includes at least three tertiary carbon atoms and a sulfur atom which is bonded directly to at least one of the tertiary carbon atoms. The preparation of the nitrile rubbers is carried out in the presence of a correspondingly structured Ci2-Ci6-alkylthiol as a molecular weight regulator, which acts as a "chain transfer agent" and is thus incorporated as an end group in the polymer chains. With regard to latex coagulation, it is stated in each case that any coagulants can be used. As inorganic coagulants, calcium chloride and aluminum chloride are mentioned and used. According to EP-A-0 779 301 and EP-A-0 779 300, a preferred embodiment is a nitrile rubber which is substantially halogen-free and is obtained by latex coagulation in the presence of a nonionic surfactant and using halogen-free metal salts such as aluminum sulfate, magnesium sulfate and sodium sulfate is performed. Coagulation using aluminum sulfate or magnesium sulfate is preferred to obtain the substantially halogen-free nitrile rubber. The nitrile rubber produced in the examples in this way has a halogen content of at most 3 ppm. For the preparation of the nitrile rubbers, it is essential that alkylthiols in the form of the compounds 2,2,4,6,6-pentmethylheptane-4-thiol and 2,2,4,6,6,8,8-heptamethylnonane-4 as molecular weight regulator -thiol can be used. It should be noted that when using conventional tert. Dodecylmercaptan can be obtained as a regulator nitrile rubbers with worse properties.

For the nitrile rubbers produced in EP-A-0 692 496, EP-A-0 779 300 and EP-A-0 779 301, an advantageous property profile is claimed which enables good processability of the rubber mixtures and low mold contamination during processing. The resulting vulcanizates should have a good combination of low temperature and oil resistance and have good mechanical properties. It is further claimed that the nitrile rubbers have a short scorching time, a high crosslinking density and a high vulcanization rate can be achieved, in particular with NBR types for injection molding. With respect to the use of anti-aging agents, nothing is said in the specifications of EP-A-0 692 496, EP-A-0 779 301 and EP-A-0 779 300. The examples show that the aging inhibitor used is an alkylated phenol which is not further defined in the chemical structure. Further, it can be seen from the examples that 2 parts of the alkylated phenol are used. It can be assumed that these are weight parts. The reference value remains open (based on monomer or polymer). No conclusions can be drawn from the influence of the alkylated phenol on the properties of nitrile rubber and of hydrogenated nitrile rubber from EP-A-0 692 496, EP-A-0 779 301 and EP-A-0 779 300.

DE 102007024011 A describes a rapidly vulcanizing nitrile rubber with good mechanical properties, in particular a high modulus 300 level, which has an ion index ("ICZ") of the general formula (I) in the range from 7 to 26 ppm x mol / g has.

3 c (Ca ²⁺ ) c (Na ⁺ ) c (K ⁺ )

Ion characteristic = + (I)

40 g / mol 23 g / mol 39 g / mol where c (Ca ²⁺ ), c (Na ⁺ ) and c (K ⁺ ) indicate the concentration of calcium, sodium and potassium ions in nitrile rubber in ppm. To obtain such a rapidly vulcanizing nitrile rubber, coagulation is carried out in the presence of a salt of a 1-valent metal and optionally a maximum of 5% by weight of a salt of a divalent metal and the temperature at coagulation and subsequent scrubbing is at least 50 ° C. The general part of DE 102007024011 enumerates some anti-aging agents which are added to the nitrile rubber latex before coagulation, quantities being missing. From the example section it is apparent that the investigations were carried out with a constant amount of di-tert-butyl-p-cresol of 1.25% by weight, based on solid rubber. On the influence of di-tert-butyl-p-cresol on the properties of NBR or HNBR no conclusions can be drawn from DE 102007024011.

DE 102007024008 A describes a particularly storage-stable nitrile rubber which contains specific isomeric C 16 -thiol groups and has a calcium ion content of at least 150 ppm and a chlorine content of at least 40 ppm, in each case based on the nitrile rubber. The Ca ion contents of the nitrile rubbers produced in the examples according to the invention are 171 -1930 ppm, the Mg contents are 2- 265 ppm. The Ca-ion contents of the comparative examples not according to the invention are 2-25 ppm, the Mg-ion contents 225-350 ppm. Such storage stable nitrile rubber is obtained by performing latex coagulation in the presence of at least one of aluminum, calcium, magnesium, potassium, sodium or lithium based salts and either coagulating or washing in the presence of a Ca salt or Ca Ion-containing wash water and in the presence of a Cl-containing salt. The chlorine contents of the examples according to the invention are in the range from 49 to 970 ppm and those of the comparative examples not according to the invention in the range from 25 to 39 ppm. However, the lower chlorine contents of 25 to 30 ppm are only obtained when coagulated with chloride-free precipitants such as magnesium sulfate, aluminum sulfate or potassium aluminum sulfate and then washed with deionized water. The general part of DE 102007024008 A enumerates a number of anti-aging agents which are added to the nitrile rubber latex prior to coagulation, the general part of which is devoid of quantities. The examples of DE 102007024008 show that the NBR latexes used in the investigations were each stabilized with 1.25% by weight of 2,6-di-tert-butyl-p-cresol, based on solid rubber, and did not vary in the investigations were. From DE 102007024008 A therefore no other conclusions about the influence of 2,6-di-tert-butyl-p-cresol on the properties of nitrile rubber or hydrogenated nitrile rubber can be drawn. DE 102007024010 A describes another rapidly vulcanizing nitrile rubber which has an ion index ("IKZ") of the general formula (I) in the range from 0-60, preferably 10-25 ppm × mol / g. c (Ca ²⁺ ) c (Mg ²⁺ ) c (Na ⁺ ) c ( ⁺ )

ICZ = 3 + +

(I)

40 g / mol 24 g / mol 23 g / mol 39 g / mol where c (Ca), c (Mg), c (Na) and c (K) represent the concentration of calcium, magnesium, sodium and potassium Indicated in ppm in nitrile rubber, and the Mg-ion content is 50-250 ppm based on the nitrile rubber. In the examples of the nitrile rubbers prepared according to the invention, the Ca ion content c (Ca ²⁺ ) is in the range of 163-575 ppm and the Mg ion content c (Mg ²⁺ ) is in the range of 57-64 ppm. In the examples of non-inventive nitrile rubbers, the Ca ion content c (Ca ²⁺ ) is in the range of 345-1290 ppm and the Mg ion content c (Mg ²⁺ ) is in the range of 2-440 ppm. These nitrile rubbers are obtained when the latex coagulation is carried out in compliance with special measures and the latex is adjusted to a temperature of less than 45 ° C. before coagulation with a magnesium salt. In the general part of DE 102007024010 a number of anti-aging agents are listed, which are added to the Nitrilkautschukuatex before coagulation, wherein quantities are missing. The examples show that the investigations were carried out with a constant amount of di-tert-butyl-p-cresol (1.25% by weight, based on solid rubber). About the influence of di-tert-butyl-p-cresol on the properties of nitrile rubber and hydrogenated nitrile rubber from DE 102007024010 no further conclusions can be drawn.

EP 2 238 177 describes the preparation of nitrile rubber with high storage stability by carrying out the latex coagulation with alkaline earth salts in combination with gelatin. The nitrile rubbers have a specific ion characteristic with respect to the contents of sodium, potassium, magnesium and calcium ions contained in the nitrile rubber. In the general part of EP 2 238 177 A, some anti-aging agents are listed, which are added to the nitrile rubber latex before coagulation, quantities are missing. From the examples, it is apparent that 2,2-methylene-bis (4-methyl-6-tert-butylphenol) was used, the amount of which varied in a range of 0.1 to 0.8% by weight based on solid rubber. It is shown that the storage stability of the nitrile rubber does not depend on the amount of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) and even when using the lowest amount (0.1% by weight) of 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) sufficient storage stabilities can be achieved. It can be concluded that the amount of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) has only a minor (if any) effect on the properties of nitrile rubber. Further conclusions regarding the influence of 2,2-methylenebis (4-methyl-6-tert.butylphenol) on the properties of hydrogenated nitrile rubber are not possible. EP 2 238 175 A describes nitrile rubbers having high storage stability, which are obtained by latex coagulation with alkali metal salts in combination with gelatin and by special conditions obtained in the latex coagulation and the subsequent crumb washing. The nitrile rubbers have particular ion characteristics with respect to the amounts of sodium, potassium, magnesium and calcium ions remaining in the nitrile rubber. The general part enumerates some anti-aging agents which are added to the nitrile rubber latex prior to coagulation, with detailed amounts being absent. In the examples, a constant amount of 2,6-di-tert-butyl-p-cresol (1.0% by weight, based on solid rubber) is used. From its influence on the properties of nitrile rubber and hydrogenated nitrile rubbers and its vulcanizates produced therefrom, it is thus not possible to draw any further conclusions from EP 2 238 175 A. EP 2 238 176 A describes further nitrile rubbers with high storage stability, which are obtained by latex coagulation with alkaline earth salts in combination with polyvinyl alcohol. The nitrile rubbers also have particular contents with respect to the sodium, potassium, magnesium and calcium ions remaining in the nitrile rubber. The general part enumerates some anti-aging agents added to the nitrile rubber latex prior to coagulation, with amounts lacking. From the example section, it is apparent that the investigations were carried out with a constant amount of 2,6-di-tert-butyl-p-cresol (1.0% by weight, based on solid rubber). On the influence of 2,6-di-tert-butyl-p-cresol on the properties of nitrile rubber and hydrogenated nitrile rubbers and its vulcanizates prepared therefrom, no further conclusions can be drawn from EP 2 238 176 A.

DE 40 32 598 A describes a process for the dry isolation of polymers from organic solutions using two-roll dryers with a vacuum housing, with the aid of which solvents from polymer solutions are removed by evaporation even under reduced pressure. The polymers or rubbers are also not specified in the examples. In the examples chlorobenzene and acetone are mentioned as solvents. Measures to improve the modulus and compression set levels of vulcanizates of hydrogenated nitrile rubbers can not be derived from this.

EP 1 331 074 A describes the preparation of mixtures based on nitrile-containing rubbers with a reduced tendency to mold contamination by injection molding. The object is achieved by nitrile rubber or hydrogenated nitrile rubber having a fatty acid acid content in the range of 0.1-0.5 wt.%. The influence of various constituents of the mixture on the shape contamination behavior, among others of di-tert-butyl-p-cresol, which is varied in amounts of 0.1-0.5 parts by weight, is investigated. There is no information on the contents of di-tert-butyl-p-cresol present in the nitrile rubber or in the hydrogenated nitrile rubber or on its influence on the vulcanizate properties of HNBR. Therefore, no further measures to improve the module level and the compression set of vulcanizates of HNBR can be derived. In summary, despite extensive literature on nitrile rubber, to date no hydrogenated nitrile rubber has become known which, on account of the anti-aging agent used in the preparation of the nitrile rubber feedstock and its amount after hydrogenation and workup, gives a hydrogenated nitrile rubber which, when vulcanized, has an improved modulo and Compression Set level possesses.

Object of the present invention:

The object of the present invention was thus to provide a hydrogenated nitrile rubber whose vulcanizates have very good moduli and low compression set values, in particular after storage at high temperatures. At the same time, the hydrogenated nitrile rubber should have excellent storage stability even after prolonged storage at high temperatures. The object was accordingly also to provide a process for producing such hydrogenated nitrile rubbers by suitable hydrogenation of nitrile rubber and subsequent isolation from the solution.

Solution:

It has surprisingly been found that hydrogenated nitrile rubber with improved vulcanizate properties, in particular with improved modulus and compression set values, is obtained when this hydrogenated nitrile rubber has a content of a defined substituted phenol in a range from 0.01% by weight to less than 0.45% by weight.

This applies in particular to hydrogenated nitrile rubbers according to the invention which have a high degree of hydrogenation, usually greater than 94.5 to 100%, preferably 95 to 100%, particularly preferably 96 to 100%, very particularly preferably 97 to 100% and in particular 98 to 100% ,

It has further been found, surprisingly, that this hydrogenated nitrile rubber according to the invention is obtainable by hydrogenating a nitrile rubber containing the corresponding substituted phenol, preferably in amounts of from 0.5 to 1% by weight, in solution, then removing the solvent and passing through the hydrogenated nitrile rubber according to the invention further methods familiar to the person skilled in the art are isolated and dewatered and the content of the substituted phenol is adjusted to the amount in the range from 0.01% by weight to less than 0.45% by weight.

The present invention thus provides a hydrogenated nitrile rubber containing at least one substituted phenol of the general formula (I) in an amount in the range of 0.01% by weight) to less than 0.45% by weight, preferably in the range of 0.05 % By weight> to 0.43% by weight>, especially preferably in the range from 0.1% by weight to 0.41% by weight and in particular in the range from 0.15% by weight to 0.4% by weight, in each case based on the hydrogenated nitrile rubber,

wherein

R, 1, π R2, - Rn.3, R and R are the same or different and are hydrogen, hydroxy, a linear, branched, cyclic or aromatic hydrocarbon radical having 1 to 8 carbon atoms and additionally one, two or three heteroatoms , which are preferably oxygen, wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ^{5 is} not hydrogen.

In an alternative embodiment, the content of the at least one substituted phenol of the general formula (I) in the hydrogenated nitrile rubber according to the invention may be in an amount in the range from 0.01% by weight to less than 0.3% by weight, preferably from 0.01 % By weight to 0.25% by weight, more preferably 0.1% by weight to 0.25% by weight, in each case based on the hydrogenated nitrile rubber.

The present invention furthermore relates to vulcanizable mixtures of these hydrogenated nitrile rubbers and to processes for the preparation of vulcanizates based thereon and to the vulcanizates obtainable thereby, in particular as moldings.

The present invention further provides a process for the preparation of these hydrogenated nitrile rubbers according to the invention containing at least one substituted phenol of the general formula (I) in an amount in the range from 0.01% by weight to less than 0.45% by weight, preferably from 0.05% by weight to 0.43% by weight, more preferably from 0.1% by weight to 0.41% by weight, and in particular from 0.15% by weight to 0.4% by weight. %>, characterized in that nitrile rubbers containing at least one substituted phenol of the general formula (I) is subjected to hydrogenation in solution, then the solvent is removed and the hydrogenated nitrile rubber is isolated and dewatered, thereby reducing the content of substituted phenol of the general formula (I) to a value in the range from 0.01% by weight to less than 0.45% by weight, preferably from 0.05% by weight 0 to 0.43% by weight, more preferably from 0.1% by weight > to 0.41% by weight> and from 0.15% by weight> to 0.4% by weight), in each case based on the hydrogenated nitrile bismuth chuk, stops. In an alternative embodiment, hydrogenated nitrile rubbers containing at least one substituted phenol of the general formula (I) in an amount in the range from 0.01% by weight to less than 0.3% by weight, preferably from 0.01% by weight, are used in the process according to the invention. %> to 0.25 wt.%), particularly preferably 0.1 wt.%> to 0.25 wt.%>, in each case based on the hydrogenated nitrile rubber produced.

The term dewatering in the sense of the present application also includes a thermal drying. Applicable are all methods by which said reduction of the content of the substituted phenol to the o.g. Quantity is possible.

Hydrogenated nitrile rubbers according to the invention:

The hydrogenated nitrile rubber according to the invention contains at least one substituted phenol of the general formula (I),

wherein

R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} identical or different and are hydrogen, hydroxy, a linear, branched, cyclic or aromatic hydrocarbon radical having 1 to 8 C atoms and additionally one, two or three heteroatoms, which are preferably oxygen, where at least one of the radicals R ¹ , R ² , R ³ , R ⁴ and R ^{5 is} other than hydrogen,

in an amount in the range from 0.01% by weight to less than 0.45% by weight, preferably in the range from 0.05% by weight 0 to 0.43% by weight, more preferably in the range from 0, 1 wt.%> To 0.41 wt.%> And in particular in the range of 0.15 wt.%> To 0.4 wt.%>, In each case based on the hydrogenated nitrile rubber,

In an alternative embodiment, the content of the at least one substituted phenol of the general formula (I) in the hydrogenated nitrile rubber according to the invention may be in an amount in the range from 0.01% by weight to less than 0.3% by weight, preferably from 0.01 % By weight to 0.25% by weight, more preferably 0.1% by weight to 0.25% by weight, in each case based on the hydrogenated nitrile rubber. The hydrogenated nitrile rubbers according to the invention, as defined above, have a degree of hydrogenation which is preferably in the range from greater than 94.5 to 100%, particularly preferably in the range from 95 to 100%, very particularly preferably in the range from 96 to 100%, in particular in the range from 97 to 100 % and more preferably in the range 98 to 100%.

For the stabilization of the nitrile rubber according to the invention, it is preferable to use substituted phenols of the general formula (I) in which

R ¹ , R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are hydrogen, hydroxy, a linear or branched CpCg alkyl radical, particularly preferably methyl, ethyl, propyl, n-butyl or t-butyl, a linear or branched CpCg alkoxy, more preferably methoxy, ethoxy or propoxy, a C3-C8 cycloalkyl, more preferably cyclopentyl or cyclohexyl, or represent a phenyl radical, wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ^{5 is} not hydrogen ,

For the stabilization of the hydrogenated nitrile rubber according to the invention, particular preference is given to using substituted phenols of the general formula (I) in which two or three of the

1 2 3 4 5 1 2 3

Radicals R, R, R, R and R are hydrogen and the remaining three or two of the radicals R, R, R, R ⁴ and R ^{5 are} identical or different and hydroxy, a linear or branched CpCg alkyl radical, more preferably methyl, Ethyl, propyl, n-butyl or t-butyl, a linear or branched CpCg alkoxy, more preferably methoxy, ethoxy or propoxy, a C3-C8 cycloalkyl, particularly preferably cyclopentyl or cyclohexyl, or a phenyl radical.

Very particular preference is given to using substituted phenols of the general formula (I) selected from the group consisting of the compounds mentioned below:

The substituted phenols present in the hydrogenated nitrile rubbers according to the invention are known, for example, from DE-OS 2150639 and DE 3337567 A1 and are either commercially available or preparable by the methods familiar to the person skilled in the art.

The compounds of the general formula (I) have in common that they are volatile in the context of a suitably carried out drying, preferably via a fluidized bed drying, and therefore their content to the value in the range of 0.01 wt.% To less than 0.45 % By weight, preferably from 0.05% by weight to 0.43% by weight, particularly preferably from 0.1% by weight to 0.41% by weight, and in particular from 0.15% by weight, to 0, 4% by weight> in the hydrogenated nitrile rubber. This adjustment is possible for the skilled person by known measures. The same applies to the alternative embodiment in which the hydrogenated nitrile rubbers according to the invention contain at least one substituted phenol of the general formula (I) in an amount in the range from 0.01% by weight to less than 0.3% by weight, preferably from 0, 01 wt.%> To 0.25 wt.%> And particularly preferably from 0.1 wt.% O to 0.25 wt.%> Contain. In addition to the phenols of the general formula (I) which are steam-volatile, it is also possible to use one or more further anti-theft agents, especially those which are not steam-volatile. Repeating units of the hydrogenated nitrile rubber:

The hydrogenated nitrile rubbers according to the invention have repeating units of at least one α, β-unsaturated nitrile monomer and at least one conjugated diene monomer. They may also have repeating units of one or more other copolymerizable monomers.

The hydrogenated nitrile rubbers according to the invention comprise completely or partially hydrogenated nitrile rubbers. The degree of hydrogenation may be in the range from 50 to 100% or from 80 to 100%). Often, hydrogenated nitrile rubbers having a degree of hydrogenation ranging from 90 to 100% are used. Hydrogenated nitrile rubbers having a degree of hydrogenation in the range from greater than 94.5 to 100%, particularly preferably in the range from 95 to 100%, very particularly preferably in the range from 96 to 100%, in particular in the range from 97 to 100%, are particularly preferred preferably in the range of 98 to 100%.

Of so-called "fully hydrogenated types" is already spoken in the art, when the residual double bond content (also abbreviated as "RDB") at a maximum of about 0.9%>, ie the degree of hydrogenation is greater than or equal to 99.1%. In a preferred embodiment, the hydrogenated nitrile rubbers according to the invention are thus fully hydrogenated nitrile rubbers which have a degree of hydrogenation greater than or equal to 99.1%. The repeat units of the at least one conjugated diene are preferably based on (C 4 -C 6) conjugated dienes or mixtures thereof. Particular preference is given to 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene and mixtures thereof. Particularly preferred are 1,3-butadiene, isoprene and mixtures thereof. Very particular preference is given to 1,3-butadiene. As α, β-unsaturated nitrile, any known α, β-unsaturated nitrile can be used for preparing the nitrile rubbers of the invention, preference is given to (C ₃ -C ₅ ) -α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particularly preferred is acrylonitrile.

If one or more further copolymerizable monomers are used, these may be, for example, aromatic vinyl monomers, preferably styrene, α-methylstyrene and vinylpyridine, fluorine-containing vinyl monomers, preferably fluoroethyl vinyl ether, fluoropropylvinyl ether, o-fluoromethylstyrene, Vinyl pentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or copolymerizable anti-aging monomers, preferably N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamide, N- (4-anilinophenyl) crotonamide, N phenyl-4- (3-vinylbenzyloxy) aniline and N-phenyl-4- (4-vinylbenzyloxy) aniline, as well as non-conjugated dienes, such as 4-cyanocyclohexene and 4-vinylcyclohexene, or also alkynes, such as 1 or 2 -Butin.

Furthermore, hydroxyl-containing monomers may be used as copolymerizable termonomers, preferably hydroxyalkyl (meth) acrylates. However, it is also possible to use appropriately substituted (meth) acrylamines.

Examples of suitable hydroxyalkyl acrylate monomers are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl ( meth) acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl ( meth) acrylate, 3-hydroxypropyl (meth) acrylamide, di- (ethylene glycol) itaconate, di (propylene glycol) itaconate, bis (2-hydroxypropyl) itaconate, bis (2-hydroxyethyl) itaconate, bis (2-hydroxyethyl) fumarate, Bis (2-hydroxyethyl) maleate and hydroxy methyl vinyl ketone. Furthermore, it is possible to use epoxy group-containing monomers as copolymerizable termonomers, preferably glycidyl (meth) acrylates.

Examples of epoxy group-containing monomers are diglycidyl itaconate, glycidyl p-styrene carboxylate, 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2 (n-butyl) glycidyl methacrylate, glycidylmethyl acrylate, glycidylmethyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethyl acrylate, (3', 4'-epoxyheptyl) -2-ethyl-methacrylate, (6 ', 7'-epoxyheptyl) acrylate, (6 ', 7'-epoxyheptyl) methacrylate, allyl glycidyl ether, allyl-3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether and 3-vinylcyclohexene oxide.

Alternatively, carboxy-containing, copolymerizable termonomers can be used as further copolymerizable monomers, for example α, β-unsaturated monocarboxylic acids, their esters, α, β-unsaturated dicarboxylic acids, their mono- or diesters or their corresponding anhydrides or amides.

Acrylic acid and methacrylic acid may preferably be used as α, β-unsaturated monocarboxylic acids. It is also possible to use esters of α, β-unsaturated monocarboxylic acids, preferably their alkyl esters and alkoxyalkyl esters. The alkyl esters, in particular CpCig alkyl esters of the α, β-unsaturated monocarboxylic acids, are particularly preferred. Alkyl esters, in particular CpCig alkyl esters of acrylic acid or of methacrylic acid, in particular methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. Also preferred are alkoxyalkyl esters of α, β-unsaturated monocarboxylic acids, more preferably alkoxyalkyl esters of acrylic acid or of methacrylic acid, in particular C 2 -C 12 -alkoxyalkyl esters of acrylic acid or of methacrylic acid, very particularly preferably methoxymethyl acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate. It is also possible to use mixtures of alkyl esters, such as those mentioned above, with alkoxyalkyl esters, for example in the form of the abovementioned. It is also possible to use cyanoalkyl acrylate and cyanoalkyl methacrylate in which the C atom number of the cyanoalkyl group is 2-12, preferably α-cyanoethyl acrylate, β-cyanoethyl acrylate and cyanobutyl methacrylate. It is also possible to use hydroxyalkyl acrylates and hydroxyalkyl methacrylates in which the C atom number of the hydroxyalkyl groups is 1-12, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl acrylate; It is also possible to use fluorine-substituted benzyl-containing acrylates or methacrylates, preferably fluorobenzyl acrylate, and fluorobenzyl methacrylate. It is also possible to use fluoroalkyl-group-containing acrylates and methacrylates, preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate. It is also possible to use amino-containing α, β-unsaturated carboxylic acid esters, such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.

Other monomers which can be used are .alpha.,. Beta.-unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.

It is also possible to use α, β-unsaturated dicarboxylic acid anhydrides, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.

Can also be used mono- or diesters of α, β-unsaturated dicarboxylic acids. These α, β-unsaturated dicarboxylic acid mono- or diesters may, for example, be alkyl, preferably C 1 -C 10 -alkyl, in particular ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or n-hexyl, alkoxyalkyl, preferably C 2 -C 12 -alkoxyalkyl, particularly preferably C 3 -C 5 -alkoxyalkyl, hydroxyalkyl, preferably C 1 -C 20 -hydroxyalkyl, particularly preferably C 2 -C 8 -hydroxyalkyl, cycloalkyl- preferably C ₅ -C 12 -cycloalkyl, particularly preferably C ₆ -C 12 -cycloalkyl, alkylcycloalkyl, preferably C ₆ -C 12 -alkylcycloalkyl, particularly preferably C ₇ -C 10 -alkylcycloalkyl, aryl, preferably C ₆ -C 14 -aryl-mono- or diesters, which may also be mixed esters in the case of the diesters. Particularly preferred alkyl esters of α, β-unsaturated monocarboxylic acids are

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-

Butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-propylheptyl acrylate and lauryl (meth) acrylate. In particular, n-butyl acrylate is used.

Particularly preferred alkoxyalkyl esters of the α, β-unsaturated monocarboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate. In particular, methoxyethyl acrylate is used.

As other esters of α, β-unsaturated monocarboxylic acids, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxymethyl) acrylamide and urethane (meth) acrylate are used.

Examples of α, β-unsaturated dicarboxylic acid monoesters include

Maleic monoalkyl esters, preferably monomethyl maleate, monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;

Malemic monocycloalkyl ester, preferably monocyclopentyl maleate, monocyclohexyl maleate and monocycloheptyl maleate;

Maleic acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl maleate and monoethylcyclohexyl maleate;

Maleic monoaryl ester, preferably monophenylmaleate;

Maleic acid monobenzyl ester, preferably monobenzyl maleate;

Fumaric acid monoalkyl esters, preferably monomethyliumarate, monoethyliumarate, monopropyl fumarate and mono-n-butyl fumarate;

Fumaric monocycloalkyl ester, preferably monocyclopentylium tartrate, monocyclohexyl fumarate and monocycloheptyl fumarate;

Fumaric acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl fumarate and monoethylcyclohexyl fumarate;

Fumaric monoaryl ester, preferably monophenyl fumarate;

Fumaric acid monobenzyl ester, preferably monobenzyl fumarate;

Citraconsäuremonoalkylester, preferably Monomethylcitraconat, Monoethylcitraconat, Monopropylcitraconat and mono-n-butyl citraconate;

Citraconic monocycloalkyl esters, preferably monocyclopentylcitraconate, monocyclohexyl citraconate and monocycloheptylcitraconate;

Citraconsäuremonoalkylcycloalkylester, preferably Monomethylcyclopentylcitraconat and Monoethylcyclohexylcitraconat;

Citraconsäuremonoarylester, preferably Monophenylcitraconat; Citraconic acid monobenzyl ester, preferably monobenzyl citraconate;

Itaconic acid monoalkyl ester, preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;

Itaconic acid monocycloalkyl ester, preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate;

Itaconic acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl itaconate and monoethylcyclohexyl itaconate;

Itaconic acid monoaryl ester, preferably monophenyl itaconate;

Itaconic acid monobenzyl ester, preferably monobenzyl itaconate;

Mesaconsäuremonoalkylester, preferably Mesaconsäuremonoethylester.

As α, β-unsaturated dicarboxylic acid diesters, the analog diesters can be used based on the aforementioned monoester groups, wherein the ester groups may also be chemically different.

Radical polymerizable compounds which contain at least two olefinic double bonds per molecule are also suitable as further copolymerizable monomers. Examples of polyunsaturated compounds are acrylates, methacrylates or itaconates of polyols, e.g. Ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, butanediol-1,4-diacrylate, propanediol 1,2-diacrylate, butanediol-1,3-dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, glycerol di- and triacrylate, pentaerythritol di-, tri- and tetraacrylate or methacrylate, dipentaerythritol tetra, penta- and hexaacrylate or -methacrylate or -itaconate, sorbitol tetraacrylate, sorbitol hexamethacrylate, diacrylates or dimethacrylates of 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2, 2-bis (4-hydroxyphenyl) propane, of polyethylene glycols or of oligoesters or oligourethanes with terminal hydroxyl groups. As polyunsaturated monomers it is also possible to use acrylamides, e.g. Methylenebisacrylamide, hexamethylene-1, 6-bisacrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane or 2-acrylamido-ethyl acrylate. Examples of polyunsaturated vinyl and allyl compounds are divinylbenzene, ethylene glycol divinyl ether, diallyl phthalate, allyl methacrylate, diallyl maleate, triallyl isocyanurate or triallyl phosphate.

The proportions of conjugated diene and α, β-unsaturated nitrile in the nitrile rubbers to be used in the process according to the invention or the hydrogenated nitrile rubbers according to the invention can vary within wide ranges. The proportion of or the sum of the conjugated dienes is usually in the range from 20 to 95% by weight, preferably in the range from 45 to 90% by weight, more preferably in the range from 50 to 85% by weight, based on the Total polymer. The proportion of or the sum of the α, β-unsaturated nitriles is usually from 5 to 80% by weight, preferably from 10 to 55% by weight, more preferably from 15 to 50% by weight, based on the total polymer. The proportions of the conjugated diene and α, β-unsaturated nitrile repeat units in the nitrile rubbers according to the invention or the fully or partially hydrogenated nitrile rubbers according to the invention in each case add up to 100% by weight.

The additional monomers may be present in amounts of 0 to 40% by weight, preferably 0 to 30% by weight, more preferably 0 to 26% by weight, based on the total polymer. In this case, corresponding proportions of the repeating units of the conjugated diene (s) and / or the repeat units of the α, β-unsaturated nitriles are replaced by the proportions of these additional monomers, the proportions of all repeating units of the monomers remaining in each case to 100% by weight. > have to sum up.

If esters of (meth) acrylic acid are used as additional monomers, this is usually carried out in amounts of from 1 to 25% by weight. If α, β-unsaturated mono- or dicarboxylic acids are used as additional monomers, this is usually carried out in amounts of less than 10% by weight.

Nitrile rubbers according to the invention which have repeating units of acrylonitrile and 1,3-butadiene are preferred. Also preferred are nitrile rubbers having repeating units of acrylonitrile, 1,3-butadiene and one or more other copolymerizable monomers. Likewise preferred are nitrile rubbers, the repeat units of acrylonitrile, 1,3-butadiene and one or more α, β-unsaturated mono- or dicarboxylic acid, their esters or amides, and in particular repeat units of an alkyl ester of an α, β-unsaturated carboxylic acids, very particularly preferably methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Octyl (meth) acrylate or lauryl (meth) acrylate.

The nitrile rubbers according to the invention or the fully or partially hydrogenated nitrile rubbers according to the invention have excellent storage stability.

The nitrogen content is determined in the nitrile rubbers according to the invention or the wholly or partially hydrogenated nitrile rubbers according to the invention according to DIN 53 625 according to Kjeldahl. Due to the content of polar comonomers, the nitrile rubbers are usually soluble in methyl ethyl ketone at 20 ° C> 85 wt.%.

The glass transition temperatures of the hydrogenated nitrile rubbers according to the invention are in the range from -70.degree. C. to + 10.degree. C., preferably in the range from -60.degree. C. to 0.degree. The hydrogenated nitrile rubbers according to the invention have Mooney viscosities ML 1 + 4 at 100 ° C. of from 10 to 150 Mooney units (MU), preferably from 20 to 100 MU. The Mooney viscosity of the nitrile rubbers or of the hydrogenated nitrile rubbers is determined in a shear disk viscometer according to DIN 53523/3 or ASTM D 1646 at 100 ° C. In each case, the unvulcanized rubbers are examined after drying and aging. The Mooney viscosities of the nitrile rubbers or of the hydrogenated nitrile rubbers after drying and before aging are designated as MV 0.

To determine the storage stability of the unvulcanized nitrile rubbers or of the unvulcanized hydrogenated nitrile rubbers, the Mooney viscosities are determined. The values for the Mooney viscosity determined after storage of the nitrile rubber or hydrogenated nitrile rubber at 100 ° C. for 48 hours are referred to as MV 1. The values for the Mooney viscosity determined after storage at 100 ° C. for 72 hours are referred to as MV 2. The storage stabilities (LS) were determined as the difference in the values of the Mooney viscosity after and before storage at 100 ° C.

LS 1 (48h / 100 ° C) = MV 1 - MV 0

LS 2 (72h / 100 ° C) = MV 2 - MV 0

The storage stability of hydrogenated nitrile rubber (LS 2) is good if the Mooney viscosity at 72 ° C storage at 100 ° C (LS 2 = MV 2 - MV 0) does not change by more than 5 Mooney units. This is fulfilled for the hydrogenated nitrile rubbers according to the invention.

The storage stability of nitrile rubber (LS 1) is good if the Mooney viscosity changes after 48 hours of storage at 100 ° C (LSI = MV 1 - MV 0) by no more than 5 Mooney units.

For the preparation of the hydrogenated nitrile rubbers according to the invention, it has been found useful to use nitrile rubbers having a storage stability LSI of not more than 5 Mooney units, but this is not mandatory but contributes to the broad applicability of the process. To determine the Mooney viscosities for the purpose of calculating the storage stability according to the abovementioned formulas, it has proven useful to prepare rolled skins of the hydrogenated nitrile rubbers. Typically, these skins are obtained by tumbling 100 g of the corresponding rubber at room temperature on a conventional roll mill (eg Schwabenthan Polymix 110) at a gap width of 0.8-1.0 mm. The speeds of rotation are 25 minutes 730 min ^-1 . The skins are used to produce rectangular cutouts (40-50 g) and are stored on aluminum trays (10 cm / 5 cm) whose bottom is coated with Teflon foil in the circulating air drying oven The circulating air drying cabinet is unchanged compared to normal air. Process for the preparation of the nitrile rubbers which can be used to prepare the hydrogenated nitrile rubbers of the invention:

Nitrile rubbers containing at least one substituted phenol of the general formula (I) can be prepared by mixing a nitrile rubber with a substituted phenol of the general formula (I).

The amount of the substituted phenol of the general formula (I) which is added to the nitrile rubber can be varied within a wide range by those skilled in the art. It should only be considered that the amount is chosen so that the amount of substituted phenol in the hydrogenated nitrile rubber, which is obtained by hydrogenation and subsequent work-up of the nitrile rubber, in the range of 0.01 wt.% To less than 0.45 wt. %, preferably from 0.05% by weight to 0.43% by weight, particularly preferably from 0.1% by weight to 0.41% by weight and in particular from 0.15% by weight to 0.4% by weight , in each case based on the hydrogenated nitrile rubber. Since the degree of removal of the phenol from the hydrogenated nitrile rubber depends on the dewatering, i. Drying method may differ, no fixed specifications are required here. The person skilled in the art knows how to adjust the conditions accordingly. Nitrile rubbers which contain a substituted phenol of the general formula (I) in the range from 0.5 to 1% by weight, based on the nitrile rubber, have proven useful. The preparation of the nitrile rubber is typically carried out via emulsion polymerization to form a nitrile rubber latex and subsequent coagulation of the nitrile rubber. This is well known to the skilled person. The latex coagulation of the nitrile rubber preferably takes place according to the process generally described in EP-A-1 369 436. The addition of the phenol of the general formula (I) is typically carried out in the nitrile rubber latex formed after the emulsion polymerization prior to coagulation. It has proven useful to add the substituted phenol of the general formula (I) as an aqueous dispersion. The concentration of this aqueous dispersion is typically in a range of 2.50-70% by weight, preferably 5-60% by weight. It is also possible to add the substituted phenol to the monomer-containing latex at the end of the polymerization either in a solvent or in monomer (butadiene, acrylonitrile or in a butadiene / acrylonitrile mixture) prior to monomer removal (monomer degassing). Preference is given to adding in butadiene, acrylonitrile or a butadiene / acrylonitrile mixture, wherein the concentration of the substituted phenol in the monomer 0.5-30 wt.%, Preferably 1-20 wt.%. is. The addition of the substituted phenol is also possible in combination with a topping agent and / or in combination with another non-steam-volatile aging inhibitor.

Optionally, the nitrile rubber is degraded prior to hydrogenation by metathesis. Should after the metathesis a readjustment of the amount of substituted phenol of the general formula (I) If desired, it is possible to add further substituted phenols of general formula (I) to the nitrile rubber after the metathesis and before the hydrogenation.

Process for the preparation of the hydrogenated nitrile rubbers according to the invention:

Hydrogenated nitrile rubbers containing at least one substituted phenol of the general formula (I) in an amount in the range from 0.01% by weight to less than 0.45% by weight, preferably from 0.05% by weight to 0.43% by weight , particularly preferably from 0.1% by weight to 0.41% by weight and in particular from 0.15% by weight to 0.4% by weight> can be prepared by reacting nitrile rubbers comprising at least one phenol of the general formula ( I), preferably in an amount in the range of 0.5 to 1 wt.%), Based on the nitrile rubber, subjected to hydrogenation in solution, then the solvent removed, preferably by a steam distillation, and the hydrogenated nitrile rubber isolated, preferably in the form crumbles by sieving, and dehydrated, whereby the content of substituted phenol of general formula (I) to the amount in the range of 0.01 wt.% O to less than 0.45 wt.%>, Preferably from 0.05 wt. %> to 0.43 wt.%>, particularly preferably from 0.1 wt.%) to 0.41 wt.%> And esp especially from 0.15% by weight to 0.4% by weight.

In a proven embodiment, the final dehydration of the hydrogenated nitrile rubber is carried out by fluidized bed drying at temperatures of 100 ° C to 180 ° C, preferably at 110 ° C to 150 ° C, wherein of the substituted phenol of general formula (I) 20-98 % By weight), based on the amount of the substituted phenol in the nitrile rubber used for the hydrogenation, can be removed.

In a particular embodiment, the fully or partially hydrogenated nitrile rubber according to the invention in the dried state volatile constituents <1.0 wt.%>, Wherein the at least one substituted phenol of the general formula (I) in an amount in the range of 0.01 wt. %> to less than 0.45% by weight> is present.

All analytical methods for the determination of the corresponding contents of phenols of the general formula (I), the volatiles u.a. are disclosed in the general part of the examples.

hydrogenation:

The hydrogenation is usually carried out in the presence of at least one hydrogenation catalyst, typically based on the noble metals rhodium, ruthenium, osmium, palladium, platinum or iridium, with rhodium, ruthenium and osmium being preferred.

It is possible to use rhodium-containing complex catalysts of the general formula (A)

Rh (X) _n (L) _m (A) in which

X are the same or different and are hydrogen, halogen, pseudohalogen, SnCl ₃ or

Carboxylate means

n is 1, 2 or 3, preferably 1 or 3,

L are the same or different and are based on mono- or bidentate ligands

Phosphorus, arsenic or antimony,

m as far as L stands for monodentate ligands, equal to 2, 3 or 4, or as far as L for bidentate

Ligand is equal to 1 or 1, 5 or 2 or 3 or 4. In the general formula (A), X is the same or different and is preferably hydrogen or chlorine.

L in the general formula (A) is preferably a phosphine or diphosphane corresponding to the general formulas (I-a) and (I-b) shown above, including the general, preferred and particularly preferred meanings mentioned therein.

Particularly preferred catalysts of the general formula (A) are tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride, tris (dimethylsulfoxide) rhodium (III) chloride, hydridorhodium tetrakis (triphenylphosphine) and the corresponding compounds in which triphenylphosphine is wholly or partly replaced by tricyclohexylphosphine.

Ruthenium-containing complex catalysts can also be used. These are e.g. in DE-A 39 21 264 and EP-A-0 298 386. They typically have the general formula (B)

wherein

X are the same or different and represent hydrogen, halogen, SnCl, CO, NO or R ⁶ -COO,

L ^{1 are the} same or different and are hydrogen, halogen, R ^{6 is} -COO, NO, CO or a cyclopentadienyl ligand of the following general formula (2),

wherein _2?

R ¹ to R ^{5 are} identical or different and denote hydrogen, methyl, ethyl, propyl, butyl, hexyl or phenyl or alternatively two adjacent radicals from R ¹ to R ^{5 are} bridged, so that an indenyl or Fluorenylsystem results, L ^{2 is} a phosphane , Diphosphane or Arsan and

n is 0, 1 or 2,

m 0, 1, 2 or 3,

z is 1, 2, 3 or 4, and

R ^{6 represents} a radical having 1 to 20 C atoms, which may be branched or unbranched, bridged or unbridged and / or partially aromatic, and preferably denotes C 1 -C ⁴ -alkyl.

Examples of L ¹ ligands in the general formula (B) of the cyclopentadienyl ligand type of the general formula (2) include cyclopentadienyl, pentamethylcyclopentadienyl, ethyltetramethylcyclopentadienyl, pentaphenylcyclopentadienyl, dimethyltriphenylcyclopentadienyl, indenyl and fluorenyl. The benzene rings in the L-ligands of the indenyl and fluorenyl type can be represented by C 1 -C 6 -alkyl radicals, in particular methyl, ethyl and isopropyl, C 1 -C 6 -alkoxy radicals, in particular methoxy and ethoxy, aryl radicals, in particular phenyl, and halogens, in particular fluorine and chlorine, be substituted. Preferred L-ligands of the cyclopentadienyl type are the respectively unsubstituted radicals cyclopentadienyl, indenyl and fluorenyl. In the L 1 ligand in the general formula (B) of the type (R ⁶ -COO), R ⁶ comprises, for example, straight-chain or branched, saturated hydrocarbon radicals having 1 to 20, preferably 1 to 12, in particular 1 to 6, C atoms, cyclic, saturated Hydrocarbon radicals having 5 to 12, preferably 5 to 7 C-atoms, further aromatic hydrocarbon radicals having 6 to 18, preferably 6 to 10 C-atoms, or aryl-substituted alkyl radicals, preferably a straight-chain or branched C 1 -C 6 _-alkyl radical and a C _ö -Cig aryl radical, preferably phenyl.

The above-described radicals R ⁶ in (R ⁶ -COO) in the ligand L ^{1 of} the general formula (B) may optionally be substituted by hydroxy, C 1 -C 6 -alkoxy, C 1 -C 6 -carbalkoxy, fluorine, chlorine or di-C 1 -C 4 -alkyl. Alkylamino, be substituted, the cycloalkyl, aryl and aralkyl radicals beyond by CI-C _Ö - alkyl, alkyl, cycloalkyl and aralkyl groups may contain keto groups. Examples of the radical R ⁶ are methyl, ethyl, propyl, iso-propyl, tert. Butyl, cyclohexyl, phenyl, benzyl and trifluoromethyl. Preferred radicals R ⁶ are methyl, ethyl and tert. Butyl.

The L ² ligand in the general formula (B) is preferably a phosphane or diphosphane corresponding to the above-described general formulas (1-a) and (1-b) including the general, preferred and particularly preferred meanings mentioned therein or for an arsine the general formula (3) R- As R ⁹ (3)

R ⁸

Preferred ligands L ^{2 of} the general formula (3) are triphenylarsan, ditolylphenylarsan, tris (4-ethoxyphenyl) -arsan, diphenylcyclohexylarsan, dibutylphenylarsan and diethylphenylarsan.

Preferred ruthenium-containing catalysts of the general formula (B) are selected from the following group, where "Cp" is cyclopentadienyl, ie C ₅ H ₅ ^" ," Ph "is phenyl," Cy "is cyclohexyl and" dppe "is 1, 2 bis (diphenylphosphino) ethane: RuCl ₂ (PPh ₃ ) ₃ ; RuHCl (PPh ₃ ) ₃ ; RuH ₂ (PPh ₃ ) ₃ ; RuH ₂ (PPh ₃ ) ₄ ; RuH ₄ (PPh ₃ ) ₃ ; RuH (CH ₃ COOH) (PPh ₃ ) ₃ ; RuH (C ₂ H ₅ COO) (PPh ₃ ) ₃ ; RuH (CH ₃ COO) ₂ (PPh ₃ ) ₂ ; RuH (NO) ₂ (PPh ₃ ) ₂ ; Ru (NO) ₂ (PPh ₃ ) ₂ ; RuCl (Cp) (PPh ₃ ) ₂ ; RuH (Cp) (PPh ₃ ) ₂ ; Ru (SnCl ₃ ) (Cp) (PPh ₃ ) ₂ ; RuCl (μ ⁵ -C ₉ H ₇ ) (PPh ₃ ) ₂ ; RuH ^ ⁵ - C ₉ H ₇ ) (PPh ₃ ) ₂ ; Ru (SnCl ₃ ) (^ - C ₉ H ₇ ) (PPh ₃ ) ₂ ; RuCl (^ - C ₁₃ H ₉ ) (PPh ₃ ) ₂ ; RuH (^ - C ₁₃ H ₉ ) (PPh ₃ ) ₂ ; RuCl (μ ⁵ -C ₉ H ₇ ) (dppe); RuHCl (CO) (PCy ₃ ); RuH (NO) (CO) (PCy ₃ ) ₃ ; RuHCl (CO) ₂ (PPh ₃ ) ₂ ; RuCl ₂ (CO) (dppe) RuHCl (CO) (PCy ₃ ), RuHCl (CO) (dppe) ₂ ,

RuH (CH ₃ COO) (PPh ₃ ) ₃ ; RuH (CH ₃ COO) ₂ (PPh ₃ ) ₂ ; and RuH (CH ₃ COO) (PPh ₃ ) ₃ .

Further suitable catalysts are those of the general formula (C)

wherein

M osmium or ruthenium means

X ¹ and X ^{2 are} identical or different and two ligands, preferably anionic ligands, L are identical or different ligands, preferably are neutral electron donors,

R are the same or different and are hydrogen, alkyl, preferably C ₁ -C 30 -alkyl,

Cycloalkyl, preferably C ₃ -C ₂ o-cycloalkyl, alkenyl, preferably C ₂ -C ₂ o-alkenyl, alkynyl, preferably C ₂ -C ₂ o-alkynyl, aryl, preferably C6-C ₂ 4-aryl, carboxylate, are preferred Ci-C ₂ o-carboxylate, alkoxy, preferably Ci-C ₂ -alkoxy, alkenyloxy, preferably C ₂ -C ₂ o-alkenyloxy, alkynyloxy, preferably C ₂ -C ₂ o-alkynyloxy, aryloxy, preferably C6-C ₂ 4-aryloxy, alkoxycarbonyl, preferably C ₂ -C ₂ o-alkoxycarbonyl, alkylamino, preferably C ₃ o-alkylamino, alkylthio, preferably Ci-C ₃ o-alkylthio, arylthio, C ₆ -C preferably ₂ 4-arylthio, Alkylsulfonyl, preferably Ci-C ₂ o-alkylsulfonyl, or alkylsulfinyl, preferably Ci-C ₂ o-alkylsulfinyl represent, where these radicals are all each optionally optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively both radicals R are bridged to a cyclic group by incorporation of the common C atom to which they are attached , which may be aliphatic or aromatic in nature, is optionally substituted and may contain one or more heteroatoms.

In one embodiment of the catalysts of the general formula (C), one radical R is hydrogen and the other radical R is C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂₀ - alkynyl, C6-C24-aryl, Ci-C ₂ o-carboxylate, Ci-C ₂ -alkoxy, C ₂ -C ₂ o-alkenyloxy, C ₂ -C ₂ o-alkynyloxy, Ce- C24 aryloxy, C ₂ -C ₂ o-alkoxycarbonyl, Ci-C3o-alkylamino, Ci-C3o-alkylthio, C6-C24-arylthio, C ₁ -C ₂₀ - alkylsulfonyl, or Ci-C ₂ o-alkylsulfinyl, where these radicals in each case by a or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals may be substituted.

In the catalysts of the general formula (C), X ¹ and X ^{2 are} identical or different and represent two ligands, preferably anionic ligands.

X ¹ and X ² may be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched C ₁ -C ₃₀ -alkyl, C ₆ -C ₂ 4-aryl, dC ₂ o-alkoxy, C ₆ -C ₂ 4-aryloxy, C ₃ -C ₂ o-alkyldiketonate, _{_C6-2} 4-aryldiketonate, C _r C o _{2-carboxylate,} Ci-C ₂ o-alkylsulphonate, C6-C24 arylsulfonate, Ci-C ₂ o-alkylthiol, C6-C24- Arylthiol, Cp C ₂ o-alkylsulfonyl, Ci-C ₂ o-alkylsulfinyl, mono- or dialkylamide, mono- or dialkylcarbamate, mono- or dialkylthiocarbamate, mono- or dialkyldithiocarbamate or mono- or dialkylsulfonamide radicals.

The abovementioned radicals X ¹ and X ² may be further substituted by one or more further radicals, for example by halogen, preferably fluorine, Ci-Cio-alkyl, Ci-Cio-alkoxy or C6-C24-aryl, where these radicals may in turn may be substituted by one or more substituents selected from the group comprising halogen, preferably fluorine, Ci-C ₅ alkyl, Ci-C ₅ alkoxy and phenyl. In a further embodiment X ¹ and X ² are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C ₅ carboxylate, Ci-C ₅ alkyl, phenoxy, C ₁ alkoxy -C5- , C ₁ -C ₅ -alkylthiol, C ₆ -C ₂ 4-arylthiol, C ₆ -C ₂ 4-aryl or C ₁ -C ₅ -alkylsulfonate.

In a further embodiment, X ¹ and X ^{2 are} identical and are halogen, especially chlorine, CF ₃ COO, CH ₃ COO, CFH ₂ COO, (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH ₃ -C ₆ H 4 -SO ₃ ), mesylate (CH ₃ SO 3) or CF 3 SO 3 (trifluoromethanesulfonate). In general formula (C), L are the same or different ligands and are preferably neutral electron donors.

The two ligands L can, for example, independently of one another, be a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibane, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine , Thioether, imidazoline or imidazolidine ligands.

The two ligands L independently of one another preferably denote a C 6 -C 24 -aryl, C 1 -C 10 -alkyl or C 3 -C 20 -cycloalkyl-phosphine ligand, a sulfonated C 6 -C 24 -aryl or sulfonated CpCio-alkyl-phosphine ligands , a C6-C24 aryl or Ci-Cio-alkyl phosphinite ligand, a C6-C24 aryl or Ci-Cio-alkylphosphonite ligand, a C6-C24 aryl or Ci-Cio-alkyl phosphite ligands , a C 6 -C 24 -aryl or CpCio-alkylarsane ligand, a C 6 -C 24 -aryl or C 1 -C 10 -alkylamine ligand, a pyridine ligand, a C 6 -C 24 -aryl or C 1 -C 10 -alkyl- Sulfoxide ligands, a C6-C24 aryl or Ci-Cio-alkyl ether ligands or a C6-C24 aryl or Ci-Cio alkylamide ligands, each of which may be substituted by a phenyl group, which in turn either unsubstituted or substituted by one or more halogen, Ci-C ₅ alkyl or Ci-C ₅ alkoxy radical (s) is substituted. The term "phosphine" includes, for example, PPh _3, P (p-Tol) _3, P (o-Tol) _3, PPh (CH ₃₎ _2, P (CF ₃₎ _3, P (p-FC ₆ H ₄₎ ₃ , P (p-CF ₃ C ₆ H ₄ ) ₃ , P (C ₆ H ₄ -SO ₃ Na) ₃ , P (CH ₂ C ₆ H ₄ -SO ₃ Na) ₃ , P (iso-propyl) ₃ , P (CHCH ₃ (CH ₂ CH ₃ )) ₃ , P (cyclopentyl) ₃ , P (cyclohexyl) ₃ , P (neopentyl) ₃ and P (neophenyl) ₃ , where "Ph" is phenyl and "Toi" is tolyl The term "phosphinite" includes, for example, triphenyl phosphinite, tricyclohexyl phosphinite, triisopropyl phosphinite and methyl diphenyl phosphinite.

The term "phosphite" includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.

The term "stibane" includes triphenylstiban, tricyclohexylstiban and trimethylstiban.

The term "sulfonate" includes, for example, trifluoromethanesulfonate, tosylate and mesylate.

The term "sulfoxide" includes, for example, (CH ₃ ) ₂ S (= O) and (C ₆ H ₅ ) ₂ S = O. The term "thioether" includes, for example, CH ₃ SCH ₃ , C ₆ H ₅ SCH ₃ , CH ₃ OCH ₂ CH ₂ SCH ₃ and tetrahydrothiophene.

The term "pyridine" is intended to include in the context of this application as a generic term all pyridine-based ligands, as mentioned, for example, by Grubbs in WO-A-03 / 011455. These include pyridine and pyridine, which is mono- or polysubstituted is in the form of the picolines (α-, β- and γ-picoline), lutidines (2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine ), Collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4- (dimethylamino) pyridine, chloropyridines, bromopyridines, nitropyridines, quinoline, pyrimidine, pyrrole, imidazole and phenylimidazole.

If one or both of the ligands L in formula (C) is an imidazoline and / or imidazolidine radical (hereinafter also referred to collectively as "im" ligand (s)), this usually has a structure of the general formulas (4a ) or (4b),

(4a) (4b)

wherein

R ⁸ , R ⁹ , R ¹⁰ , R ^{11 are the} same or different and are hydrogen, straight-chain or branched C ₁ -C 30 -alkyl, C ₃ -C ₂ 0-cycloalkyl, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂ o-alkynyl, C ₆ -C ₂₄ -aryl, C ₁ -C 20 -carboxylate, C ₁ -C 20 -alkoxy, C ₂ -C 20 -alkenyloxy, C ₂ -C 20 -alkynyloxy, C ₆ -C 20 -aryloxy, C ₂ -C ₂ o-alkoxycarbonyl , C ₂ denote o-alkylthio, C ₆ -C ₂ o-arylthio, _Ci-C2o alkylsulfonyl, C _r C2o-alkyl sulfonate, C6-C2o-aryl sulfonate or Ci-C2o alkylsulfinyl.

Optionally, one or more of R ⁸ , R ⁹ , R ¹⁰ , R ^{11 may} independently be substituted by one or more substituents, preferably straight-chain or branched C ₁ -C 10 -alkyl, C ₃ -C 9 -cycloalkyl, C ₁ -C 10 -alkoxy or C 6 -C 24 -Aryl be substituted, these aforementioned substituents may in turn be substituted by one or more radicals, preferably selected from the group halogen, in particular fluorine, chlorine or bromine, Ci-C ₅ alkyl, Ci-C ₅ alkoxy and phenyl.

For the sake of clarification, it should be added that the structures represented in the general formulas (4a) and (4b) in the context of this application with the structures (4a ') and (4b') which are frequently found in the literature for this radical and which contain the Highlight carben character of the rest, are synonymous. This also applies accordingly to the associated preferred, below illustrated structures (5a) - (5f). In the following, these radicals are summarized all referred to as "Im" - rest.

(4a ^' ) (4b ^' )

In a preferred embodiment of the catalysts of the general formula (C), R ⁸ and R ⁹ independently of one another are H, C 6 -C ₂₄ -aryl, particularly preferably phenyl, straight-chain or branched CpCio-alkyl, particularly preferably propyl or butyl, or together form together Inclusion of the carbon atoms to which they are attached, a cycloalkyl or aryl radical, where any of the abovementioned radicals may be substituted by one or more further radicals selected from the group comprising straight-chain or branched C 1 -C 10 -alkyl, Cio-alkoxy, C6-C ₂₄ aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide , Carboalkoxy, carbamate and halogen.

In a preferred embodiment of the catalysts of the general formula (C), furthermore, the radicals R ¹⁰ and R ^{11 are} identical or different and are straight-chain or branched CpCio-alkyl, particularly preferably methyl, i-propyl or neopentyl, C 3 -C 10 -cycloalkyl Adamantyl, Ce- C ₂₄ -aryl, more preferably phenyl, CpCio-alkylsulfonate, more preferably methanesulfonate, C6-Cio-arylsulfonate, more preferably p-toluenesulfonate. Optionally, the abovementioned radicals are substituted as meanings of R ¹⁰ and R ¹¹ by one or more further radicals selected from the group comprising straight-chain or branched Cp C ₅ -alkyl, in particular methyl, C 1 -C ₅ -alkoxy, aryl and a functional group from hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, in particular fluorine, chlorine and bromine.

In particular, the radicals R ¹⁰ and R ^{11 may be} identical or different and denote i-propyl, neopentyl, adamantyl, mesityl (2,4,6-trimethylphenyl), 2,6-difluorophenyl, 2,4,6-trifluorophenyl or 2, 6-diisopropylphenyl.

Particularly preferred Im radicals have the following structures (5a) to (5f), wherein Ph is in each case a phenyl radical, Bu is a butyl radical and Mes is in each case a 2,4,6-trimethylphenyl radical or Mes alternatively in all cases represents 2,6-diisopropylphenyl.

(5a) (5b)

Ph Ph Ph Ph

Mes' ~ Mes ^Mes' ^'Mes

(5c) (5d)

(5e) (5f)

Various representatives of the catalysts of formula (C) are known in principle, e.g. from WO-A-96/04289 and WO-A-97/06185.

As an alternative to the preferred Im radicals, one or both ligands L in the general formula (C) preferably also represents identical or different trialkylphosphine ligands, in which at least one of the alkyl groups represents a secondary alkyl group or a cycloalkyl group, preferably isopropyl, iso- Butyl, sec-butyl, neopentyl, cyclopentyl or cyclohexyl.

Particularly preferred in the general formula (C) is one or both ligands L for a trialkylphosphine ligand, wherein at least one of the alkyl groups represents a secondary alkyl group or a cycloalkyl group, preferably iso-propyl, iso-butyl, sec-butyl, neo-pentyl, cyclopentyl or cyclohexyl.

Particularly preferred are catalysts falling under the general formula (C) and having the structures (6) (Grubbs (I) catalyst) and (7) (Grubbs (II) catalyst) wherein Cy is cyclohexyl.

As catalysts, preference is furthermore given to using those of the general formula (Cl) wherein

X ¹ , X ² and L may have the same general, preferred and particularly preferred meanings as in the general formula (C),

n is 0, 1 or 2,

m is 0, 1, 2, 3 or 4 and

R 'are the same or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl,

Alkoxy, alkenyloxy, alkinyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl or alkylsulfinyl radicals, each of which is in each case represented by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals may be substituted.

As the preferable catalyst falling under the general formula (Cl), for example, those of the following formulas (8a) and (8b) can be used, wherein each Mes is 2,4,6-trimethylphenyl and Ph is phenyl.

These catalysts are e.g. from WO-A-2004/112951. Catalyst (8a) is also referred to as a Nolan catalyst.

Furthermore, preference is given to using catalysts of the general formula (D) as catalysts,

wherein

M is ruthenium or osmium,

X ¹ and X ^{2 are} identical or different ligands, preferably anionic ligands, Y is oxygen (O), sulfur (S), a radical NR ¹ or a radical PR ¹ , where R ^{1 has} the meanings mentioned below,

R ^{1 is} an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy,

Alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl or alkylsulfinyl radical, all of which are each optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals could be,

R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are hydrogen, organic or inorganic

Represent remnants,

R ^{6 is} hydrogen, an alkyl, alkenyl, alkynyl or an aryl radical and L is a ligand having the same meanings as mentioned for the formula (C).

The catalysts of the general formula (D) are known in principle and are described, for example, by Hoveyda et al. in US 2002/0107138 A1 and Angew. Chem. Int. Ed. 2003, 42, 4592, or Grela in WO-A-2004/035596, Eur. J. Org. Chem 2003, 963-966 and Angew. Chem. Int. Ed. Chem. 2004, 69, 6894-96 and Chem. Eur. J 2004, 10, 777-784 and in US 2007/043180. The catalysts are commercially available or can be prepared according to the cited references. In the catalysts of the general formula (D), L is a ligand which usually has an electron-donor function and can assume the same general, preferred and particularly preferred meanings as L in the general formula (C). Furthermore applies that L in the general formula (D) is preferably a P (R ⁷⁾ ₃ radical, where R ⁷ are independently C _I -C _east alkyl, C ₃ denote -CG-cycloalkyl or aryl, or an optionally substituted Imidazoline or imidazolidine residue ("Im"). C 1 -C 6 -alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethylpropyl and n-hexyl.

C 3 -C 8 cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Aryl comprises an aromatic radical having 6 to 24 skeleton carbon atoms, preferred mono-, bi- or tricyclic carbocyclic aromatic radicals having 6 to 10 skeleton carbon atoms, in particular phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

The imidazoline or Imidazolidinrest (Im) has the same general, preferred and particularly preferred structures as in the catalysts of general formula (C).

Particularly suitable are catalysts of the general formula (D) in which the radicals R ¹⁰ and R ^{11 are} identical or different and straight-chain or branched CpCio-alkyl, particularly preferably i-propyl or neopentyl, C 3 -C 10 -cycloalkyl, preferably adamantyl, C 6 -cycloalkyl C24-aryl, particularly preferably phenyl, CpCio-alkylsulfonate, particularly preferably methanesulfonate, or Cö-Cio-arylsulfonate, particularly preferably p-toluenesulfonate mean. Optionally, the abovementioned radicals are substituted as meanings of R ¹⁰ and R ¹¹ by one or more further radicals selected from the group comprising straight-chain or branched Cp C ₅ -alkyl, in particular methyl, C 1 -C ₅ -alkoxy, aryl and a functional group from the group of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.

In particular, the radicals R ¹⁰ and R ^{11 may be} identical or different and denote i-propyl, neopentyl, adamantyl or mesityl.

Particularly preferred imidazoline or imidazolidine radicals (Im) have the previously mentioned structures (5a-5f), where Mes is in each case 2,4,6-trimethylphenyl.

In the catalysts of the general formula (D) have X ¹ and X ² have the same general, preferred and particularly preferred meanings as in the catalysts of the general formula (C).

In the general formula (D), the radical R ¹ denotes an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, Arylthio, alkylsulfonyl or alkylsulfinyl radical, all of which may each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

Typically, the radical R ¹ is a Ci-C3o-alkyl, C3-C2o-Cylcoalkyl, C2-C2o-alkenyl, C2-C20 alkynyl, C ₆ -C ₂ 4-aryl, C1-C20 alkoxy, C ₂ -C ₂ o-alkenyloxy, C ₂ -C ₂ o-alkynyloxy, C ₆ -C ₂ 4-aryloxy, C ₂ -C ₂ o-alkoxycarbonyl, Ci-C2o-alkylamino, Ci-C2o-alkylthio, C6-C24-arylthio C 1 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl radical, all of which may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals. Preferably, R ^{1 is} a C 3 -C 20 -cycloalkyl radical, a C 6 -C 24 -aryl radical or a straight-chain or branched C 1 -C 30 -alkyl radical, the latter optionally being substituted by one or more double or triple bonds or else one or more heteroatoms , preferably oxygen or nitrogen, may be interrupted. Particularly preferably, R ^{1 is} a straight-chain or branched C ¹ -C 20 -alkyl radical.

The C 3 -C 20 cycloalkyl radical includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

The C 1 -C 12 -alkyl radical may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2 Methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-dodecyl act. In particular, R ^{1 is} methyl or isopropyl.

The C6-C24 aryl radical is an aromatic radical having 6 to 24 skeleton carbon atoms. Preferred mono-, bi- or tricyclic carbocyclic aromatic radicals having 6 to 10 skeletal carbon atoms are, for example, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

In the general formula (D), the radicals R ² , R ³ , R ⁴ and R ^{5 are} identical or different and may be hydrogen, organic or inorganic radicals.

In a suitable embodiment, R ² , R ³ , R ⁴ , R ^{5 are} identical or different and denote hydrogen, halogen, nitro, CF ₃ , alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy , Alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl or alkylsulfinyl radicals, all of which are each optionally substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl radicals could be. Typically, R ^2, R ^3, R ^4, R ^{5 are} identical or different and denote hydrogen, halogen, preferably chlorine or bromine, nitro, CF _3, Ci-C ₃ -alkyl, C ₃ -C ₂ o-Cylcoalkyl, C ₂ _-C2 o-alkenyl, C ₂ -C ₂₀ - alkynyl, C ₆ -C ₂₄ -aryl, C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, C ₆ - C ₂₄ aryloxy, C ₂ -C ₂₀ - alkoxycarbonyl, Ci-C ₂₀ alkylamino, Ci-C ₂₀ -alkylthio, C ₆ -C ₂₄ arylthio, C ₂₀ alkylsulfonyl or Ci-C ₂ o-alkylsulphinyl Radicals, each of which may be optionally substituted by one or more C ₁ -C 30 -alkyl, C ₁ -C ₂₀ -alkoxy, halogen, C 6 -C ₂ 4 -aryl or heteroaryl radicals.

In a particularly proven embodiment, R ² , R ³ , R ⁴ , R ⁵ are identical or different and are nitro, straight-chain or branched CpCso-alkyl, C ₅ -C ₂ o-Cylcoalkyl, straight-chain or branched Ci-C ₂₀ -alkoxy radicals or C ₆ -C ₂₄ -aryl radicals, preferably phenyl or naphthyl. The C _r C 30 -alkyl radicals and C ₁ -C 20 -alkoxy radicals may optionally be interrupted by one or more double or triple bonds or else one or more heteroatoms, preferably oxygen or nitrogen. Furthermore, two or more of the radicals R ² , R ³ , R ⁴ or R ⁵ may also be bridged via aliphatic or aromatic structures. By way of example, R ³ and R ⁴ can form a fused-on phenyl ring, including the carbon atoms to which they are bonded in the phenyl ring of the formula (D), so that a total of one naphthyl structure results. In the general formula (D), the radical R ^{6 is} hydrogen, an alkyl, alkenyl, alkynyl or an aryl radical, preferably hydrogen, a C ₁ -C 30 -alkyl, a C ₂ -C ₂ 0-alkenyl radical, a C ₂ - C ₂ o-alkynyl or C6-C ₂₄ - aryl radical. More preferably R ^{6 is} hydrogen.

Also suitable are cata-

1 2 1 2 3 4 5

wherein M, L, X, X, R, R, R, R and R may have the general, preferred and particularly preferred meanings given for the general formula (D).

The catalysts of the general formula (D l) are e.g. from US 2002/0107138 Al (Hoveyda et al.) In principle, and can be obtained according to the preparation method specified therein.

Particularly suitable catalysts of the general formula (Dl), wherein M represents ruthenium,

X ¹ and X ^{2 are} simultaneously halogen, in particular chlorine at the same time,

R ^{1 represents} a straight-chain or branched C ¹ -C 12 -alkyl radical,

R ² , R ³ , R ⁴ , R ^{5 are} those mentioned for the general formula (D) general and preferred

Own meanings and

L is the general and preferred formula (D)

Has meanings.

Particularly suitable are catalysts of the general formula (Dl), wherein

M represents ruthenium,

X ¹ and X ² are chlorine at the same time,

R ^{1 is} an isopropyl radical,

R ² , R ³ , R ⁴ , R ^{5 are} all hydrogen and

L represents an optionally substituted imidazolidine radical of the formulas (4a) or (4b),

(4a) (4b)

wherein

R ⁸ , R ⁹ , R ¹⁰ , R ^{11 are} identical or different and are hydrogen, straight-chain or branched C ₁ -C ₃₀ -alkyl, C ₃ -C ₂ 0-cycoalkyl, C ₂ -C ₂ 0-alkenyl, C ₂ -C ₂ o-alkynyl, C ₆ -C ₂ 4-aryl, Ci-C ₂₀ carboxylate, C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ -

Alkynyloxy, C ₆ -C ₂₄ aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, Ci-C ₂₀ -alkylthio, C ₆ -C ₂ - arylthio, Ci-C ₂₀ alkylsulfonyl, Ci-C ₂₀ alkyl sulfonate, C ₆ - C ₂₄ -arylsulfonate or Ci-C ₂ o-alkylsulfinyl, where the abovementioned radicals in each case by one or more substituents, preferably straight-chain or branched Ci-Cio-alkyl, C ₃ -C ₈ -cycloalkyl, Ci-Cio-alkoxy or C ₆ -C ₂₄ -aryl may be substituted, wherein these abovementioned substituents in turn by one or more radicals, preferably selected from the group halogen, in particular chlorine or bromine, Ci-C ₅ alkyl, Ci-C ₅ alkoxy and phenyl substituted could be.

Especially suitable is a catalyst which falls under the general structural formula (D1) and has the formula (9), wherein each Mes is 2,4,6-trimethylphenyl.

This catalyst (9) is also referred to in the literature as "Hoveyda catalyst".

Further suitable catalysts are those which fall under the general structural formula (D1) and have the formulas (10), (11), (12), (13), (14), (15), (16) or (17) where Mes is 2,4,6-trimethylphenyl.

(12) (1 3)

(16) (17)

Suitable is w

wherein

M, L, X ¹ , X ² , R ¹ and R ^{6 have} the general and preferred meanings given for the formula (D),

R ^{12 are the} same or different and have the general and preferred meanings mentioned for R ² , R ³ , R ⁴ and R ⁵ in formula (D), with the exception of hydrogen, and n is 0, 1, 2 or 3. The catalysts of the general formula (D2) are known in principle, for example, from WO-A-2004/035596 (Grela) and can be obtained by the preparation process indicated there.

Particularly suitable catalysts of the general formula (D2), wherein

M represents ruthenium,

R ^{1 represents} a straight-chain or branched C ¹ -C 12 -alkyl radical,

R ^{12 has} the meanings given for the general formula (D2),

n is 0, 1, 2 or 3,

R ^{6 is} hydrogen and

L has the meanings given for the general formula (D).

Especially suitable are catalysts of the general formula (D2) in which

M represents ruthenium,

X ¹ and X ² are chlorine at the same time,

R ^{1 is} an isopropyl radical,

n is 0 and

L represents an optionally substituted imidazolidine radical of the formula (4a) or (4b) in which R ⁸ , R ⁹ , R ¹⁰ , R ^{11 are} identical or different and those mentioned for the particularly preferred catalysts of the general formula (Dl)

Own meanings.

Especially suitable are catalysts of the following structures (18) ("Grela catalyst") (19), wherein each Mes is 2,4,6-trimethylphenyl.

(18) (19)

Also suitable is a dendritically structured catalyst of the general formula (D3),

X ¹

X-Si-X ² (D3)

l ³ where X ¹ , X ² , X ³ and X ⁴ each have a structure of general formula (20) attached via the methylene group shown on the right to the silicon of formula (D3) and

Wonn

M, L, X 1, X 2, R 1, R 2, R 3, R 5 and R 6 may have the general and preferred meanings given for the general formula (D).

The catalysts of the general formula (D3) are known from US 2002/0107138 Al and can be prepared according to the information given there.

Also suitable is a catalyst of the formula (D4),

wherein the symbol represents a carrier.

The support is preferably a poly (styrenedivinylbenzene) copolymer (PS-DVB). The catalysts according to formula (D4) are known in principle from Chem. Eur. J. 2004 10, 777-784 and are obtainable by preparation methods described therein.

All of the aforementioned catalysts of the type (D), (D1), (D2), (D3) and (D4) can either be used as such in the hydration reaction or else be applied to a solid support and immobilized. Suitable solid phases or carriers are those materials which, on the one hand, are inert to the metathesis reaction mixture and, on the other hand, do not impair the activity of the catalyst. For immobilization of the catalyst it is possible to use, for example, metals, glass, polymers, ceramics, organic polymer beads or also inorganic sol gels, carbon black, silica, silicates, calcium carbonate and barium sulfate. Also suitable are catalysts of the general formula (E),

in which

M is ruthenium or osmium,

-2

X ¹ and X are the same or different and represent anionic ligands,

R ^{"are the} same or different and represent organic radicals,

In an optionally substituted imidazoline or Imidazolidinrest represents and

Represents an anion. The catalysts of the general formula (E) are known in principle (see, for example, Angew. Chem. Int.

Ed. 2004, 43, 6161-6165).

X ¹ and X ² in the general formula (E) may have the same general, preferred and particularly preferred meanings as in the formulas (C) and (D).

The Im radical usually has a structure of the general formulas (4a) or (4b) which have already been mentioned for the catalyst type of the formulas (C) and (D) and may also have all the structures mentioned there as preferred, in particular the of the formulas (5a) - (5f). The radicals R "in the general formula (E) are identical or different and denote a straight-chain or branched C 1 -C 30 -alkyl, C ₅ -C 30 -cycloalkyl or aryl radical, where the C 1 -C 30 -alkyl radicals are optionally substituted by a or a plurality of double or triple bonds or else one or more heteroatoms, preferably oxygen or nitrogen, Aryl comprises an aromatic radical having 6 to 24 skeleton carbon atoms Preferred mono-, bi- or tricyclic carbocyclic aromatic radicals having 6 to 10 skeleton carbon atoms For example, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl may be mentioned.

The radicals R "in the general formula (E) are preferably identical and are phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.

Also suitable are catalysts of the general formula (F)

wherein

M is ruthenium or osmium,

R ¹³ and independently of one another are hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl,

C ₆ -C ₂ 4-aryl, C _r C ₂ o-carboxylate, C _r C ₂ o -alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, C ₆ -C 24 aryloxy, C ₂ -C ₂₀ Alkoxycarbonyl, C 1 -C 20 -alkylthio, C 1 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl,

X ^{3 is} an anionic ligand,

a neutral π-bonded ligand, whether mono- or polycyclic,

a ligand from the group of phosphanes, sulfonated phosphines, fluorinated phosphines, functionalized phosphines with up to three aminoalkyl, ammonium alkyl, alkoxyalkyl, alkoxycarbonylalkyl, Hydrocarbonylalkyl-, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, Arsans, stibanes, ethers, amines, amides, imines, sulfoxides, thioethers and pyridines,

γ- is a non-coordinating anion and

n is 0, 1, 2, 3, 4 or 5.

Also suitable are catalysts of the general formula (G)

wherein

M ² molybdenum means

R ¹⁵ and R ¹⁶ are identical or different and are hydrogen, Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C20 alkynyl, C ₆ -C ₂ 4-aryl, Ci-C ₂ o-carboxylate, C ₂ -alkoxy, C ₂ -C ₂ o-alkenyloxy, C ₂ -C ₂ o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C2o-alkylthio, C1-C20 - C20 alkylsulfonyl or C1- Alkylsulfinyl, are the same or different and represent a substituted or a halogen-substituted C 1 -C 20 -alkyl, C 6 -C 24 -aryl, C 6 -C 30 -aralkyl radical or silicone-containing analogs thereof.

Also suitable are catalysts of the general formula (H)

wherein

M is ruthenium or osmium,

X ¹ and ^X: are identical or different and represent anionic ligands, all of which in the general formulas (C) and (D) above for X ¹ and X ² can accept said meanings,

represents identical or different ligands which can assume all the meanings of L given in the general formulas (C) and (D),

R ¹⁹ and R ^{20 are the} same or different and are hydrogen or substituted or unsubstituted

Alkyl.

Also suitable are catalysts of the general formulas (K), (N) or (Q)

(K) (N)

(Q)

in which

M osmium or ruthenium means

X ¹ and X ^{2 are} identical or different and are two ligands, preferably anionic ligands, L represents a ligand, preferably a neutral electron donor,

• 2

Z ¹ and Z are the same or different and represent neutral electron donors,

independently of one another H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate,

Alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulfonyl or alkylsulfinyl, each substituted by one or more radicals selected from alkyl, halogen, alkoxy, aryl or heteroaryl.

The catalysts of the general formulas (K), (N) and (Q) are known in principle, e.g. from WO 2003/01 1455 A1, WO 2003/087167 A2, Organometallics 2001, 20, 5314 and Angew. Chem. Int. Ed. 2002, 41, 4038. The catalysts are commercially available or can be synthesized by the production methods indicated in the abovementioned references.

In the catalysts of general formulas (K), (N) and (Q), Z ¹ and Z ^{2 are the} same or different and represent neutral electron donors. These ligands are usually weakly coordinating. Typically, these are optionally substituted heterocyclic groups. These may be five or six-membered monocyclic groups having from 1 to 4, preferably 1 to 3 and more preferably 1 or 2 heteroatoms or two or polycyclic structures of 2, 3, 4 or 5 such five or six membered monocyclic groups all of the abovementioned groups are optionally substituted by one or more alkyl, preferably C 1 -C 10 -alkyl, cycloalkyl, preferably C 3 -C 9 -cycloalkyl, alkoxy, preferably C 1 -C 10 -alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C 6 -C 24- Aryl, or heteroaryl, preferably C5-C23 heteroaryl radicals, each again by one or more groups, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C ₅ alkyl, Ci-C ₅ alkoxy and Phenyl may be substituted.

Examples of Z ¹ and Z ² include nitrogen-containing heterocycles such as pyridines, pyridazines, bipyridines, pyrimidines, pyrazines, pyrazolidines, pyrrolidines, piperazines, indazoles, quinolines, purines, acridines, bisimidazoles, picolylimines, imidazolidines and pyrroles.

Z ¹ and Z ² may also be bridged together to form a cyclic structure. In this case, Z ¹ and Z ² are a single bidentate ligand.

In the catalysts of the general formulas (K), (N) and (Q) L can assume the same general, preferred and particularly preferred meanings as L in the general formulas (C) and (D). In the catalysts of the general formulas (K), (N) and (Q), R and R are identical or different and are alkyl, preferably C 1 -C 30 -alkyl, particularly preferably C 1 -C 20 -alkyl, cycloalkyl, preferably C 3 -C 20 -oxo- Cycloalkyl, particularly preferably C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, particularly preferably C2-C16-alkenyl, alkynyl, preferably C2-C2o-alkynyl, particularly preferably C2-C16-alkynyl, aryl, preferably C6-C24 -Aryl, carboxylate, preferably C 1 -C 20 -carboxylate, alkoxy, preferably C 1 -C 20 -alkoxy, alkenyloxy, preferably C 2 -C 20 -alkenyloxy, alkynyloxy, preferably C 2 -C 20 -alkynyloxy, aryloxy, preferably C 6 -C 24 -aryloxy, alkoxycarbonyl, preferably C 2 -C 20 -alkoxycarbonyl, alkylamino, preferably C 1 -C 30 -alkylamino, alkylthio, preferably C 1 -C 30 -alkylthio, arylthio, preferably C 6 -C 24 -arylthio, alkylsulfonyl, preferably C 1 -C 20 -alkylsulphonyl, or alkylsulfinyl, preferably C 1 -C 20 Alkylsulphinyl, wherein the abovementioned substituents by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radical e may be substituted.

In the catalysts of general formulas (K), (N) and (Q), X ¹ and X ^{2 are the} same or different and may have the same general, preferred and particularly preferred meanings as previously for X ¹ and X ² in the general formula (C) indicated.

Especially suitable are catalysts of the general formulas (K), (N) and (Q), in which

M is ruthenium,

X ¹ and X ^{2 are} both halogen, in particular chlorine,

R ¹ and R ^{2 are the} same or different and are five- or six-membered monocychsche groups having 1 to 4, preferably 1 to 3 and particularly preferably 1 or 2 heteroatoms or bi- or polycyclic structures of 2, 3, 4 or 5 such five- or six-membered monocyclic groups, all of the abovementioned groups being preferred by one or more alkyl, preferably C 1 -C 10 -alkyl, cycloalkyl, preferably C 3 -C 9 -cycloalkyl, alkoxy, preferably C 1 -C 10 -alkoxy, halogen

Chlorine or bromine, aryl, preferably C6-C24-aryl, or heteroaryl, preferably C5-C23 heteroaryl radicals may be substituted,

R ²¹ and R ^{22 are} identical or different and are C ₁ -C 30 -alkyl C ₃ -C 20 -cycloalkyl, C ₂ -C 20 -alkenyl, C ₂ -C 20 -alkynyl, C ₆ -C ₂ 4-aryl, dC ₂ o-carboxylate, dC ₂ -alkoxy, C ₂ -C ₂ o-alkenyloxy, _C2 - C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C3o-alkylamino, Cp

C 30 alkylthio, C ₆ -C ₂ 4 arylthio, dC ₂ o-alkylsulphonyl, Ci-C ₂ o-alkylsulphinyl, and

L has a structure of the above-described general formulas (4a) or (4b), in particular of the formulas (5a) to (5f).

Especially suitable is a catalyst which falls under the general formula (K) and has the structure (21),

Wonn

R ²³ and R ^{24 are} identical or different and H, halogen, straight-chain or branched C 1 -C 20 -alkyl, C 1 -C 20 -heteroalkyl, C 1 -C 10 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 24 -aryl, preferably phenyl, Formyl, nitro, nitrogen heterocycles, preferably pyridine, piperidine and pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbomoyl, carbamido, thioformyl, amino, dialkylamino, trialkylsilyl and trialkoxysilyl. The abovementioned radicals C 1 -C 20 -alkyl, C 1 -C 20 -heteroalkyl, C 1 -C 10 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 24 -aryl, preferably phenyl, formyl, nitro, nitrogen heterocycles, preferably pyridine, piperidine and pyrazine , Carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbomoyl, carbamido, thioformyl, amino, trialkylsilyl and trialkoxysilyl can each again by one or more radicals halogen, preferably fluorine, chlorine or bromine, Ci-C ₅ alkyl, Ci-C ₅ alkoxy or phenyl.

Especially suitable is a catalyst in which R ²³ and R ^{24 are} hydrogen ("Grubbs III catalyst").

Also particularly suitable are catalysts of structures (22a) or (22b), wherein R ²³ and R ^{24 have} the same meanings as given in formula (21), except hydrogen.

(22a) (22b)

Suitable catalysts falling within the general formulas (K), (N) and (Q) have the following structural forms (23) to (34), wherein Mes stands for 2,4,6-trimethylphenyl.

(23) (24)

(25) (26)

(27) (28)

Also suitable are catalysts (R) which have the general structural element (R 1), the carbon atom marked with a "*" being bound to the catalyst skeleton via one or more double bonds,

and in which

R ²⁵ -R ^{32 are} identical or different and are hydrogen, halogen, hydroxyl, aldehyde, keto, thiol,

CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate,

Dithiocarbamate, amino, amido, imino, silyl, sulfonate (-SO ₃ ), -OSO ₃ ^" , -PO ₃ ^" or OPO ₃ ^" or for alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate , Alkoxy, alkenyloxy, alkinyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl, these radicals each in each case optionally being substituted by one or more alkyl , Halogen, alkoxy, aryl or heteroaryl radicals may be substituted, or alternatively, in each case two directly adjacent radicals from the group of R ²⁵ -R ³² , including the ring carbon atoms to which they are attached, form by bridging a cyclic group, preferably an aromatic system, or alternatively, R ^{8 is} optionally bridged with another ligand of the ruthenium or osmium carbene complex catalyst, 0 or 1, and

Oxygen, sulfur, C (R ³³ R ³⁴ ), NR ³⁵ , -C (R ³⁶ ) = C (R ³⁷ ) -, -C (R ³⁶ ) (R ³⁸ ) -C (R ³⁷ ) (R ³⁹ ) - in which R-R are the same or different and each may have the same meanings as the radicals R ²⁵ -R ³² .

The catalysts of the invention have the structural element of the general formula (RI), wherein the carbon atom marked with a "*" is bound to the catalyst skeleton via one or more double bonds If two or more double bonds are bonded to the catalyst backbone, these double bonds can be cumulated or conjugated.

Such catalysts (R) are described in EP-A-2 027 920. The catalysts (R) having a structural element of the general formula (R1) include, for example, those of the following general formulas (R2a) and (2b),

(R2a) (R2b)

wherein

M is ruthenium or osmium,

X ¹ and X ^{2 are} identical or different and represent two ligands, preferably anionic ligands,

L ¹ and L ^{2 represent} identical or different ligands, preferably neutral electron donors, where L ^{2 may} alternatively be bridged with the radical R ⁸ , n is 0, 1, 2 or 3, preferably 0, 1 or 2, n 'is 1 or 2, preferably 1, and

R ²⁵ -R ³² , m and A have the same meanings as in the general formula (Rl).

In the catalysts of the general formula (R2a), the structural element of the general formula (R1) is a double bond (n = 0) or 2, 3 or 4 cumulative double bonds (at n = 1, 2 or 3) to the central metal of the complex catalyst bound. In the catalysts of the general formula (R2b) according to the invention, the structural element of the general formula (R1) is bonded via conjugated double bonds to the metal of the complex catalyst. In both cases, there is a double bond in the direction of the central metal of the complex catalyst at the C atom marked with a "*".

The catalysts of the general formula (R2a) and (R2b) thus comprise catalysts in which the following general structural elements (R3) - (R9)

(R3) (R4) (R5) (R6)

(R10a) (R10b)

1 2 1 2 25 39

wherein X and X, L and L, n, n ^' and R-R have the meanings given for the general formulas (R2a) and (R2b). Typically, these ruthenium or osmium carbene catalysts are five-coordinate.

In the structural element of the general formula (Rl) are

R ¹⁵ -R ^{32 are} identical or different and denote hydrogen, halogen, hydroxyl, aldehyde, keto,

Thiol, CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulfonate (-SO ₃ ), -OSO ₃ ^" , -

PO ₃ ^"or OPO _^3" or are alkyl, preferably C1-C20 alkyl, especially CI-C _Ö - alkyl, cycloalkyl, preferably C3-C2o-cycloalkyl, in particular C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o- Alkenyl, alkynyl, preferably C 2 -C 20 -alkynyl, aryl, preferably C 6 -C 24 -aryl, in particular phenyl, carboxylate, preferably C 1 -C 20 -carboxylate, alkoxy, preferably C 1 -C 20 -alkoxy, alkenyloxy, preferably C 2 -C 20 -alkenyloxy, Alkynyloxy, preferably C2-C20-

Alkynyloxy, aryloxy, preferably C6-C24-aryloxy, alkoxycarbonyl, preferably C2-C20-alkoxycarbonyl, alkylamino, preferably Ci-C3o-alkylamino, alkylthio, preferably C1-C30-alkylthio, arylthio, preferably C6-C24-arylthio, alkylsulfonyl, preferred C 1 -C 20 -alkylsulfonyl, alkylsulfinyl, preferably C 1 -C 20 -alkylsulfinyl, dialkylamino, preferably di (C 1 -C 20 -alkyl) amino, alkylsilyl, preferably C 1 -C 20 -alkylsilyl, or alkoxysilyl, preferably C 1 -C 20 -alkoxysilyl radicals These radicals may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively in each case two directly adjacent radicals from the group of R ²⁵ -R ³² , including the Ring carbon atoms to which they are attached, by bridging a cyclic group, preferably an aromatic system, form, or alternatively R ^{8 is} optionally bridged with another ligand of the ruthenium or osmium carbene complex catalyst,

m is 0 or 1 and

A represents oxygen, sulfur, C (R ³³⁾ (R ^34), NR ³⁵ -C (R ³⁶⁾ = C (R ³⁷⁾ - or

C (R ³⁶ ) (R ³⁸ ) -C (R ³⁷ ) (R ³⁹ ) - in which R ³³ -R ^{39 are} identical or different and each may have the same preferred meanings as the radicals R'-R ⁸ . Ci-C _ö alkyl in the structural element of the general formula (Rl) is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl , 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethylpropyl and n-hexyl.

In the structural element of the general formula (R1), C3-C5-cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

In the structural element of the general formula (R 1), C 6 -C 2 -aryl comprises an aromatic radical having 6 to 24 skeletal carbon atoms. Preferred mono-, bi- or tricyclic carbocyclic aromatic radicals having 6 to 10 skeletal carbon atoms are, for example, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

The radicals X ¹ and X ² in the structural element of the general formula (Rl) have the same general, preferred and particularly preferred meanings that are mentioned for catalysts of the general formula (C).

In the general formulas (R2a) and (R2b) or analogously (R10a) and (R10b), the radicals L ¹ and L ^{2 are} identical or different ligands, preferably neutral electron donors, and may have the same general, preferred and particularly preferred Have meanings that are called for the catalysts of general formula (C).

Preference is given to catalysts of the general formulas (R2a) or (R2b) with a general formula

Structural unit (Nl), where

M represents ruthenium,

X ¹ and X ^{2 are} simultaneously halogen,

n is 0.1 or 2 in the general formula (R2a) or

n '1 is in the general formula (R2b)

L ¹ and L ^{2 are the} same or different and have the general or preferred meanings given for the general formulas (R 2a) and (R b),

R ²⁵ -R ^{32 are} identical or different and have the general or preferred meanings given for the general formulas (R 2a) and (R b),

m is either 0 or 1,

and, if m = 1

A represents oxygen, sulfur, C (C _r Cio-alkyl) _2, -C (Ci-Ci ₀ alkyl) ₂ -C (Ci-Ci ₀ alkyl) ₂ -,

-C (Ci-Cio-alkyl) = C (Ci-Cio-alkyl) - or -N (C _r Ci ₀ -alkyl). Very particular preference is given to catalysts of the formulas (R2a) or (R2b) having a general structural unit (R1), where

M represents ruthenium,

X ¹ and X ^: both mean chlorine,

n is 0.1 or 2 in the general formula (R2a) or

n '1 is in the general formula (R2b)

L ^{1 represents} an imidazolidine radical of the formulas (5a) to (5f),

L ^{z is} a sulfonated phosphane, phosphate, phosphinite, phosphonite, arsine, stiban,

Ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine radical, an imidazoline or imidazolidine radical of the formulas (5a) to (5f) or a phosphine ligand, in particular PPh ₃ , P ( p-Tol) ₃ , P (o-Tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p-FC ₆ H ₄ ) ₃ , P (p-CF ₃ C ₆ H ₄ ) ₃ , P (C ₆ H ₄ -SO ₃ Na) ₃ , P (CH ₂ C ₆ H ₄ -SO ₃ Na) ₃ , P (iso-propyl) ₃ ,

P (CHCH ₃ (CH ₂ CH ₃ )) ₃ , P (cyclopentyl) ₃ , P (cyclohexyl) ₃ , P (neopentyl) ₃ and P (neophenyl) ₃ ,

R-R have the general or preferred meanings given for the general formulas (R2a) and (R2b),

m is either 0 or 1,

and, if m = 1

A represents oxygen, sulfur, C (C _r Cio-alkyl) _2, -C (C _r Cio-alkyl) ₂ -C (Ci-Cio-alkyl) ₂ -,

-C (Ci-Cio-alkyl) = C (Ci-Cio-alkyl) - or -N (C _r Cio-alkyl).

For the case that the radical R is bridged with another ligand of the catalyst of the formula R, the following structures of the general formulas (R13a) and (R13b) are obtained, for example, for the catalysts of the general formulas (R2a) and (R2b)

(R13a) (R13b)

Wonn

Y is oxygen, sulfur, a radical NR ⁴¹ or a radical PR ⁴¹ , where R ^{41 has} the meanings mentioned below, R and R are the same or different and represent an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl or alkylsulfinyl radical, all of which may each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,

p is 0 or 1 and

Y ² when p = 1, for - (CH ₂ ) _r - with r = 1, 2 or 3, -C (= 0) -CH ₂ -, -C (= 0) -, -N = CH-,

N (H) -C (= O) - or alternatively the entire structural unit "-Y ¹ (R ⁴⁰ ) - (Y ² ) _p -" for (-N (R ⁴⁰ ) = CH-CH ₂ -), ( -N (R ⁴⁰ , R ⁴¹ ) = CH-CH ₂ -), and

wherein M, X 1, X 2, L 1, R 25 -R 32, A, m and n have the same meanings as in the general formulas (RIOa) and (RlOb).

(43) (44) (45)

(49) (50) (51)

The preparation of catalysts of the general formula (R) is known from EP-A-2 027 920.

Also suitable are catalysts according to the general formula (T).

wherein X ¹ and X ^{2 are the} same or different and are anionic ligands, or alternatively linked together via carbon-carbon and / or carbon-heteroatom bonds,

Y is a neutral two-electron donor selected from O, S, N and P,

R is H, halogen, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl (RCO ₂ ), cyano, nitro, amido, amino, aminosulfonyl, N-heteroarylsulfonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, Arylsulfinyl, alkylthio, arylthio or sulfonamide,

R ¹ and R ^{2 are} H, Br, I, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, amino, heteroaryl, alkylthio, arylthio, or

Sulfonamido are

R ^{3 is} alkyl, aryl, heteroaryl, alkylcarbonyl, arylcarbonyl, thiocarbonyl, or aminocarbonyl,

EWG is an electron-withdrawing group which is selected from the group consisting of aminosulfonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, arylsulfinyl,

Arylcarbonyl, alkylcarbonyl, aryloxycarbonyl, aminocarbonyl, amido, sulfonamido, chloro,

Fluorine, H, or haloalkyl and

L is an electron donating ligand attached to X ¹ via carbon-carbon and / or

Carbon-heteroatom bonds may be linked.

These catalysts of the general formula (T) are known from US 2007/0043180

Catalysts of the general formula (I), wherein X ¹ and X ² are selected are preferably made of an ionic ligand in the form of halides, carboxylates, and aryloxides. X ¹ and X ² are particularly preferably both halides, in particular both are chlorides. In the general formula (T), Y is preferably oxygen. R is preferably H, halogen, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, amido, alkylsulfonyl, arylsulfonyl, alkylthio, arylthio or sulfonamido. In particular, R is H, Cl, F or a Ci.g alkoxycarbonyl group. R ¹ and R ² are identical or different and are preferably H, alkoxy, aryl, aryloxy, alkoxycarbonyl, amido, alkylthio, arylthio or a sulfonamido group. In particular, R ^{1 is} H or an alkoxy group and R ² is hydrogen. In the general formula (T), R ^{3 is} preferably an alkyl, aryl, heteroaryl, alkylcarbonyl or arylcarbonyl group. R ^{3 is} particularly preferably isopropyl, sec-butyl and methoxyethyl. In the general formula (T), EWG preferably represents an aminosulfonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, aminocarbonyl, arylsulfonyl, alkylcarbonyl, aryloxycarbonyl, halogen or haloalkyl group. More preferably, EWG is a C1-2 N-alkylaminosulfonyl, C2-12 N-heteroarylsulfonyl, C1.12 aminocarbonyl, C6-12 arylsulfonyl, C1.12 alkylcarbonyl, C6-12 arylcarbonyl, Ce-12 aryloxycarbonyl, Cl, F or trifluoromethyl group. In the general formula (T), L represents an electron donating ligand selected from phosphines, amino, aryloxides, carboxylates or carbene heterocyclic radicals which may be bonded to X ¹ via carbon-carbon and / or carbon-heteroatom bonds.

Particularly suitable is a catalyst of general formula (T), wherein L represents a heterocyclic carbene ligand or a phosphine (P (R ⁸ ) ₂ (R ⁹ ) having the following structures:

(6a) (6b) (6c) (6d)

wherein

R ⁴ and R ^{5 are the} same or different and represent Ce-n aryl and

R ⁶ and R ^{7 are} identical or different and H, halogen, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl,

Arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, amino, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylthio or sulfonamido and

R ⁸ and R ^{9 are the} same or different and Ci_g is alkyl or Ce-n aryl.

Also suitable are bimetallic complexes of the general formula (U)

M ¹ _a M ² _b X _m (L ¹ ) _n (U)

wherein

M ^{1 represents} rhodium (Rh) or ruthenium (Ru),

M ^{2 represents} ruthenium (Ru) or a lanthanide,

where M ^{1 is} rhodium (Rh), M ^{2 is} ruthenium (Ru) or a lanthanide, and when M ^{1 is} ruthenium (Ru), M ^{2 is} a lanthanide,

X are the same or different and are H, Cl or Br,

L ^{1 is} an organophosphine (PR ¹ R ² R ³ ), diphosphane (R ¹ R ² P (CH ₂ ) _n PR ³ R ⁴ ), organoarsan (AsR ¹ R ² R ³ ) or other organic compounds containing nitrogen, sulfur, oxygen Atoms or mixtures thereof, where R ¹ , R ² , R ³ and R ^{4 are} identical or different and are C 1 -C 6 -alkyl, C 6 -C 12 -cycloalkyl, aryl, C 7 -C 12 -aralkyl or aryloxy groups,

1 ^ a <ß,

1 ^ b <2,

3 <m <6 and

6 ^ η ^ 15 is.

These catalysts of the general formula (U) are known in principle from US Pat. No. 6,084,033. , _n

-61-

Particularly suitable catalysts are those of the general formula (U) in which M ^{1 is} rhodium and M ^{2 is} ruthenium. Also particularly suitable are catalysts of the general formula (U) in which M ^{2 is} a lanthanide, in particular Ce or La. In particularly suitable catalysts of the general formula (U), X are identical or different and are H or Cl. Particularly suitable are catalysts of the general formula (U) in which L ^{1 is} selected from trimethylphosphane, triethylphosphine, triphenylphosphine, triphenoxyphosphine, tri (p-methoxyphenyl) phosphine, diphenylethylphosphane, 1,4-di- (diphenylphosphano) butane, 1, 2 Di (diphenylphosphino) ethane, triphenylarsane, dibutylphenylarsan, diphenylethylarsan, triphenylamine, triethylamine, N, N-dimethylaniline, diphenylthioether, dipropylthioether, Ν, Ν'-tetramethylethylenediamine, acetylacetone, diphenylketones, and mixtures thereof.

Further catalysts which can be used are described in the following documents: US Pat. No. 3,700,637, DE-A-25 39 132, EP-A 134 023, DE-A 35 41 689, DE 3540918, EP-A-0 298 386, DE-A 3529252, DE-A 3433 392, US-A 4,464,515, US 4,503,196 and EP-A-1 720 920.

Quantity of hydrogenation catalyst:

For the hydrogenation of the nitrile rubber, the hydrogenation catalyst can be used in a wide range of amounts. Usually, the catalyst is used in an amount of from 0.001 to 1.0% by weight, preferably from 0.01 to 0.5% by weight, in particular from 0.05 to 0.3% by weight, based on the nitrile rubber to be hydrogenated.

Other hydrogenation conditions:

The performance of the hydrogenation is well known to those skilled in the art, e.g. from US 6,683,136A. Solvent:

The hydrogenation is usually carried out in a solvent, preferably an organic solvent. As organic solvents, e.g. Acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, 1,3-dioxane, benzene, toluene, methylene chloride, chloroform, monochlorobenzene and dichlorobenzene suitable. Monochlorobenzene has proven particularly useful because it is a good solvent both for nitrile rubbers having different nitrile contents and for the corresponding resulting hydrogenated nitrile rubbers.

Concentration of nitrile rubber:

For hydrogenation, nitrile rubber is usually dissolved in at least one solvent. The concentration of the nitrile rubber in the hydrogenation is generally in the range 1 to 30% by weight, preferably in the range 5 to 25% by weight, more preferably in the range 7 to 20% by weight. The pressure in the hydrogenation is usually in the range from 0.1 bar to 250 bar, preferably from 5 bar to 200 bar, more preferably from 50 bar to 150 bar. The temperature is typically in the range of 0 ° C to 180 ° C, preferably 20 ° C to 160 ° C, more preferably 50 ° C to 150 ° C. The reaction time is usually 2 to 10 h.

In the hydrogenation, the double bonds present in the nitrile rubber used are preferably greater than 94.5 to 100%, more preferably 95 to 100%, most preferably 96 to 100%, in particular 97 to 100% and most preferably 98 to 100%) hydrogenated. Hydrogenated nitrile rubbers having a residual content of double bonds ("RDB") in the range from 0 to 0.9% are also accessible, and the hydrogenation is monitored on-line by determination of the hydrogen uptake or by Raman (EP-A-0 897 933 A suitable IR method for the off-line determination of the degree of hydrogenation is further described by D. Brück in Kautschuke + Gummi, Kunststoffe, Vol. 42 (1989), No. 2 107-10 (part 1) and in rubbers + rubber, plastics, Vol. 42. (1989), No. 3, pp. 194-197.

After reaching the degree of hydrogenation, the reactor is depressurized. Residuals of hydrogen are usually removed by a nitrogen purge. Before the removal of the solvent and isolation of the hydrogenated nitrile rubber from the organic phase, the hydrogenation catalyst can be removed, but need not. A preferred method for rhodium recovery is described, for example, in US-A-4,985,540.

Co-catalysts:

The hydrogenation can be carried out with the addition of a phosphine or diphosphane as a co-catalyst. These are typically present in amounts of from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight, more preferably from 0.5 to 4% by weight, very preferably from 0.75 to 3.5 % By weight and in particular from 1 to 3% by weight, based on the nitrile rubber to be hydrogenated.

Suitable phosphine cocatalysts are those of the general formula (1-a),

R

P (1-a)

R R

in which

R are the same or different and are alkyl, alkenyl, alkadienyl, alkoxy, aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkadienyl, halogen or trimethylsilyl, and as diphosphane co-catalyst are those of general formula (1-b),

Wonn

R are the same or different and have the same meanings as in the general

Formula (1-a),

k is 0 or 1 and

X represents a straight-chain or branched alkanediyl, alkenediyl or alkinediyl group.

The radicals R can be unsubstituted, monosubstituted or polysubstituted in both formula (1-a) and (1-b).

Such phosphanes or diphosphines of the general formulas (1-a) and (1-b) can be prepared by methods known to the person skilled in the art or can be obtained commercially. Alkyl radicals in the radicals R 'of the phosphanes or diphosphines of the general formulas (Ia) and (I-b) are usually understood as meaning straight-chain or branched C 1 -C 30 -alkyl radicals, preferably C 1 -C 24 -alkyl radicals, particularly preferably C 1 -Cig radicals. CpCig alkyl includes, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl , 1-ethylpropyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1 , 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl 1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl and n octadecyl.

Alkenyl radicals in the radicals R 'of the phosphanes or diphosphines of the general formulas (1-a) and (1-b) are usually C2-C3o-alkenyl radicals, preferably C2-C2o-alkenyl radicals. Particularly preferably, an alkenyl radical is a vinyl radical or an allyl radical.

Alkadienyl radicals in the radicals R of the phosphanes or diphosphanes of the general formulas (1-a) and (1-b) are usually understood to mean C pCso-alkadienyl radicals, preferably C 4 -C 20 -alkadienyl radicals. Particularly preferably, an alkadienyl radical is butadienyl or pentadienyl. Alkoxy radicals in the radicals R of the phosphanes or diphosphines of the general formulas (Ia) and (I-b) are usually understood as meaning C 1 -C 20 -alkoxy radicals, preferably C 1 -C 10 -alkoxy radicals, more preferably methoxy , Ethoxy, n-propoxy, iso -propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy and n-hexoxy.

Aryl radicals in the radicals R 'of the phosphanes or diphosphines of the general formulas (1-a) and (1-b) are usually understood as meaning C ₅ -C 24 -aryl radicals, preferably C 6 -C 14 -aryl radicals, particularly preferably C 6 -C 12 aryl radicals. Examples of C ₅ -C 24 aryl are phenyl, 0-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl and fluorenyl.

Heteroaryl radicals in the radicals R of the phosphanes or diphosphines of the general formulas (1-a) and (1-b) have the same meaning as stated above for aryl radicals, but one or more of the skeletal carbon atoms by a Heteroatom selected from the group nitrogen, sulfur and oxygen, are replaced. Examples of such heteroaryl radicals are pyridinyl, oxazolyl, benzofuranyl, dibenzofuranyl and quinolinyl.

All of the abovementioned alkyl, alkenyl, alkadienyl and alkoxy radicals can be unsubstituted, monosubstituted or polysubstituted, for example by C ₅ -C 24 -aryl radicals, preferably phenyl (in the case of alkyl radicals in this case, for example, arylalkyl, preferably a phenylalkyl radical), Halogen, preferably fluorine, chlorine or bromine, CN, OH, NH ₂ or NR " ₂ radicals, where R" is in turn C1-C30-alkyl or C ₅ -C ₂ 4-aryl.

Both the aryl radicals and the heteroaryl radicals are either unsubstituted, mono- or polysubstituted, for example by straight-chain or branched CpCso-alkyl (resulting so-called alkylaryl radicals), halogen, preferably fluorine, chlorine or bromine, sulfonate (SC ^ Na), straight-chain or denoted C 1 -C 30 -alkoxy, preferably methoxy or ethoxy, hydroxyl, NH ₂ or N (R ") ₂ radicals, where R" again denotes straight-chain or branched CpCso-alkyl or C ₅ -C 24 -aryl, or by further C ₅ -C 24 aryl or heteroaryl radicals, with which bisaryl radicals, preferably biphenyl or binaphthyl, heteroaryl-aryl radicals, aryl-heteroaryl radicals or bisheteroaryl radicals result. Again, these C5-C24 aryl or heteroaryl substituents are again either unsubstituted or mono- or polysubstituted by all the abovementioned substituents.

Cycloalkyl radicals in the radicals R of the phosphanes or diphosphanes of the general formulas (1-a) and (1-b) are usually understood as meaning a C 3 -C 20 -cycloalkyl radical, preferably a C 3 -C 9 -cycloalkyl radical, more preferably cyclopentyl and cyclohexyl , Cycloalkenyl radicals in the radicals R of the phosphanes or diphosphines of the general formulas (1 a) and (1-b) are identical or different and have a C =C double bond in the ring skeleton and are usually C ₅ -C 9 cycloalkenyl, preferably Cyclopentenyl and cyclohexenyl.

Cycloalkadienyl radicals in the radicals R of the phosphanes or diphosphanes of the general formulas (1-a) and (1-b) are identical or different, have two C =C double bonds in the ring skeleton and are usually C ₅ -Cg cycloalkadienyl, preferred for cyclopentadienyl or cyclohexadienyl.

The abovementioned cycloalkyl, cycloalkenyl and cycloalkadienyl radicals are also unsubstituted, monosubstituted or polysubstituted, for example by straight-chain or branched C 1 -C 30 -alkyl (resulting in so-called alkylaryl radicals), halogen, preferably fluorine, chlorine or bromine, sulfonate ( SC ^ Na), straight-chain or branched C 1 -C 30 -alkoxy, preferably methoxy or ethoxy, hydroxyl, NH ₂ or NR " ₂ radicals, where R" is again straight-chain or branched C 1 -C 30 -alkyl or C ₅ -C ₂₄ -aryl means, or by C ₅ -C 24 -aryl or aryl or heteroaryl radicals, which in turn are either unsubstituted or mono- or polysubstituted by all the abovementioned substituents.

The halogen radicals in the radicals R 'of the phosphanes or diphosphines of the general formulas (1-a) and (1-b) are identical or different and are fluorine, chlorine or bromine. Particularly preferred phosphines of the general formula (1-a) are trialkyl, tricycloalkyl, triaryl, trialkaryl, triaralkyl, diaryl, monoalkyl, diaryl, monocycloalkyl, dialkyl, monoaryl, dialkyl, monocycloalkyl or dicycloalkyl. monoaryl-phosphines, wherein all of the abovementioned radicals are in turn either unsubstituted, mono- or polysubstituted by the abovementioned substituents.

Particular preference is given to phosphanes of the general formula (1-a) in which the radicals R are the same or different and are phenyl, cyclohexyl, cyclohexenyl, cyclopentyl, cyclopentadienyl, phenylsulfonate or cyclohexylsulfonate. Very particularly preferred phosphanes of the general formula (1-a) are PPh ₃ , Ρ (ρ-ΤO) 3, P (o-tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p -FC ₆ H ₄ ) ₃ , P (p-CF ₃ C ₆ H ₄ ) 3, P (C ₆ H ₄ -SO ₃ Na) 3, P (CH ₂ C ₆ H ₄ -SO ₃ Na) 3, P (iso-Pr) _3, P (CHCH ₃ (CH ₂ CH ₃₎₎ 3, P (cyclopentyl) _3, P (cyclohexyl) _3, P (neopentyl) _3, P (C ₆ H ₅ CH ₂₎ (C ₆ H ₅ ) ₂ , P (NCCH ₂ CH ₂ ) ₂ (C ₆ H ₅ ), P [(CH ₃ ) ₃ C] ₂ Cl, P [(CH ₃ ) ₃ C] ₂ (CH ₃ ), P (tert .-Bu) ₂ (BIPH), P (C ₆ H _U) ₂ C1, P (CH ₃₎ (OCH ₂ CH ₃₎ _2, P (CH ₂ = CHCH ₂₎ _3, P (C ₄ H ₃ 0) ₃ , P (CH ₂ OH) ₃ , P (m-CH ₃ OC ₆ H ₄ ) ₃ , P (C ₆ F ₅ ) ₃ , P [(CH ₃ ) ₃ Si] ₃ , P [(CH ₃ O) ₃ C ₆ H ₂ ] 3 where Ph is phenyl, Toi is tolyl, biph is biphenyl, Bu is butyl and Pr is propyl. Particularly preferred is triphenylphosphine.

In the diphosphines of the general formula (1-b), k is 0 or 1, preferably 1. X in the general formula (1-b) is a straight-chain or branched alkanediyl, alkenediyl or alkinediyl group, preferably a straight-chain or branched C ₁ -C ₂₀ -alkanediyl, C ₂ -C ₂₀ -alkenediyl or C ₂ C ₂ o-alkynediyl group, particularly preferred for a straight-chain or branched CpCg-alkanediyl, C ₂ -C 6-alkenediyl or C ₂ -C 6 -alkynediyl group.

Ci-Cs-alkanediyl represents a straight-chain or branched alkanediyl radical having 1 to 8 carbon atoms. Particularly preferred is a straight-chain or branched alkanediyl radical having 1 to 6 carbon atoms, in particular having 2 to 4 carbon atoms. Preferred are methylene, ethylene, propylene, propane-1,2-diyl, propane-2,2-diyl, butane-1,3-diyl, butane-2,4-diyl, pentane-2,4-diyl and 2- methyl-pentan-2,4-diyl.

C2-C6-alkenediyl represents a straight-chain or branched alkenediyl radical having 2 to 6 carbon atoms. Preference is given to a straight-chain or branched alkenediyl radical having 2 to 4, particularly preferably 2 to 3, carbon atoms. Preferred are: vinyls, allylene, prop-en-1, 2-diyl and but-2-en-l, 4-diyl.

C 2 -C 6 -alkynediyl represents a straight-chain or branched alkynediyl radical having 2 to 6 carbon atoms. Preference is given to a straight-chain or branched alkynediyl radical having 2 to 4, more preferably 2 to 3, carbon atoms. Preferably mentioned are: ethynediyl and propynediyl.

Particularly preferred diphosphanes of the general formula (1-b) are Cl ₂ PCH ₂ CH ₂ PCI ₂ , (C ₆ Hn) ₂ PCH ₂ P (C ₆ H _u ), (CH ₃ ) ₂ PCH ₂ CH ₂ P (CH ₃ ) ₂ , (C ₆ H ₅ ) ₂ PCCP (C ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₂ PCH = CHP (C ₆ H ₅ ) ₂ , (C ₆ F ₅ ) ₂ P (CH ₂ ) ₂ P (C ₆ F ₅ ) ₂ , (C ₆ H ₅ ) ₂ P (CH ₂ ) ₂ P (C ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₂ P (CH ₂ ) ₃ P (C ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₂ P (CH ₂ ) ₄ P (C ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₂ P (CH ₂ ) ₅ P (C ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₂ PCH (CH ₃ ) CH (CH ₃ ) P (C ₆ H ₅ ) ₂ and (C ₆ H ₅ ) ₂ PCH (CH 3) CH ₂ P (C ₆ H ₅ ) ₂ .

Particular diphosphanes which can also be used according to the invention are further published in Chem. Eur. J. 2008, 14, 9491-9494. For example:

If the hydrogenation is carried out in the context of the process according to the invention with the addition of a phosphine or diphosphane, these are typically added in amounts of from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight, more preferably 0.5 to 4% by weight, most preferably , "

-67-

0.75 to 3.5 wt.% And in particular 1 to 3 wt.%, Based on the nitrile rubber to be hydrogenated.

Based on 1 equivalent of the hydrogenation catalyst, the phosphine or diphosphane is used in an amount in the range of 0.1 to 10 equivalents, preferably in the range of 0.2 to 5 equivalents and more preferably in the range of 0.3 to 3 equivalents.

The weight ratio of the added phosphine or diphosphane to the hydrogenation catalyst is usually (1-100): 1, preferably (3-30): 1, in particular (5-15): l.

It is also possible to subject the nitrile rubber to a metathesis reaction prior to hydrogenation to reduce the molecular weight of the nitrile rubber. The metathesis of nitrile rubbers is well known to the person skilled in the art. Further, if metathesis occurs, it is possible to conduct the subsequent hydrogenation in situ, i. in the same reaction mixture in which metathesis degradation was previously carried out and without the need to isolate the degraded nitrile rubber. The hydrogenation catalyst is simply added to the reaction vessel.

Subsequent to the hydrogenation, the removal of the solvent is carried out either by a dry workup, preferably via a drum drying process or a screw process, or by a wet workup, preferably via a steam distillation, more preferably via a steam distillation with subsequent drying of the isolated rubber crumb by means of a fluidized bed dryer or in an expeller-expander dryer.

Dry workup processes are, for example, the drum drying process described in DE-A-4032598 and the screw processes described in WO-A-2011/023763 and in EP-A-2368917.

A wet work-up by means of a steam distillation is also suitable for the separation of the solvent used in the hydrogenation, if the subsequent drying of the isolated water-moist rubber crumb takes place in a fluidized-bed dryer or in an expeller-expander dryer. Such drying methods are well known to those skilled in the art.

The above work-up procedures are in each case carried out so that the substituted phenol of the general formula (I) which is contained in the hydrogenated nitrile rubber is known to be from 20 to 98% by weight, based on the amount of the substituted phenol of the general formula (I), from the hydrogenation nitrile rubber used is removed. The fluid bed drying is particularly suitable, preferably a continuous implementation of the fluidized bed drying. For this crumbs of hydrogenated nitrile rubber with water contents of 5 to 50 wt.% With air flows through, which have a temperature of 100 to 180 ° C, in particular 110 ° C to 150 ° C. The residence time is 1 to 15 minutes, whereby it is also possible to work with a temperature profile during fluidized-bed drying.

A hydrogenated nitrile rubber having a Mooney viscosity (ML 1 + 4 @ 100 ° C.), measured according to ASTM standard D 1646, in the range from 1 to 50 is obtained. This corresponds approximately to a weight average molecular weight M _w in the range from 2,000 to 400,000 g / mol. Preferably, the Mooney viscosity (ML 1 + 4 @ 100 ° C) is in the range of 5 to 30. This corresponds approximately to a weight average molecular weight M _w in the range of about 20,000 - 200,000. The hydrogenated nitrile rubbers obtained further have a polydispersity PDI = M _w / M _n , where M _{w is} the weight average and M _{n is} the number average molecular weight, in the range of 1-5 and preferably in the range of 1.5-3.

Vulcanizable mixtures:

The invention furthermore relates to vulcanizable mixtures comprising at least one hydrogenated nitrile rubber according to the invention and at least one crosslinking system. These vulcanizable mixtures may preferably contain one or more further typical rubber additives.

These vulcanizable mixtures are prepared by mixing at least one hydrogenated nitrile rubber (i) according to the invention with at least one crosslinking system (ii) and optionally one or more further additives

The crosslinking system contains at least one crosslinker and optionally one or more crosslinking accelerators.

Usually, the hydrogenated nitrile rubber according to the invention is first mixed with all selected additives and only as the last, the crosslinking system of at least one crosslinker and optionally a crosslinking accelerator mixed.

Suitable crosslinkers are, for example, peroxidic crosslinkers such as bis (2,4-dichlorobenzyl) peroxide, dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcylohexane, tert Butyl perbenzoate, 2,2-bis (t-butylperoxy) butene, 4,4-di-tert-butyl peroxynonyl valerate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, tert-butyl Butyl cumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3.

It may be advantageous, in addition to these peroxidic crosslinkers, to use further additives with the aid of which the crosslinking yield can be increased. Examples include triallyl isocyanurate, triallyl cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, zinc diacrylate , Zn-dimethacrylate, 1, 2-polybutadiene or N _j N -m-phenylenedimaleimide suitable. The total amount of crosslinker (s) is usually in the range from 1 to 20 phr, preferably in the range from 1.5 to 15 phr and more preferably in the range from 2 to 10 phr, based on the unhydrogenated, fully or partially hydrogenated nitrile rubber.

As crosslinkers it is also possible to use sulfur in elementary soluble or insoluble form or sulfur donors.

Suitable sulfur donors are, for example, dimorpholyl disulfide (DTDM), 2-morpholino dithiobenzothiazole (MB SS), caprolactam disulfide, dipentamethylene thiuram tetrasulfide (DPTT), and tetramethyl thiuram disulfide (TMTD).

In the case of sulfur vulcanization of the unhydrogenated, completely or partially hydrogenated nitrile rubbers according to the invention, it is also possible to use further additives with the aid of which the crosslinking yield can be increased. In principle, however, the crosslinking can also take place with sulfur or sulfur donors alone.

Conversely, the crosslinking of the unhydrogenated, fully or partially hydrogenated nitrile rubbers according to the invention can also be carried out only in the presence of the abovementioned additives, i. without the addition of elemental sulfur or sulfur donors.

As additives with the aid of which the crosslinking yield can be increased, e.g. Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthogenates, guanidine derivatives, caprolactams and thiourea derivatives.

Examples of dithiocarbamates which may be used are: ammonium dimethyldithiocarbamate, sodium diethyldithiocarbamate (SDEC), sodium dibutyldithiocarbamate (SDBC), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZBEC ), Zinc penta- methylene dithiocarbamate (Z5MC), tellurium diethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel dimethyldithiocarbamate and zinc diisononyl dithiocarbamate.

As thiurams, e.g. Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Dimethyldiphenylthiuramdisulfid, Tetrabenzylthiuramdisulfid, Dipentamethylenthiuram- tetrasulfid or Tetraethylthiuramdisulfid (TETD) are used.

As thiazoles, e.g. 2-mercaptobenzothiazole (MBT), dibenzthiazyl disulfide (MBTS), zinc mercaptobenzothiazole (ZMBT) or copper 2-mercaptobenzothiazole.

As sulfenamide derivatives, e.g. N-Cyclohexyl-2-benzothiazyl sulfenamide (CBS), N-tert-butyl-2-benzthiazyl sulfenamide (TBBS), N, N'-dicyclohexyl-2-benzthiazyl sulfenamide (DCBS), 2-morpholinothiobenzothiazole (MBS), N-oxydiethylene thiocarbamyl N-tert-butylsulfenamide or Oxydiethylenthiocarbamyl-N-oxyethylensulfenamid be used.

As xanthates, e.g. Natriumdibutylxanthogenat, Zinkisopropyldibutylxanthogenat or Zinkdibutylxanthogenat be used.

As guanidine derivatives, e.g. Diphenylguanidine (DPG), di-o-tolylguanidine (DOTG) or o-Tolylbiguanid (OTBG) can be used.

As dithiophosphates such as zinc di can _(C2 -Ci6) alkyldithiophosphate Kupferdi (C ₂ - Ci6) alkyldithiophosphate and Dithiophosphorylpolysulfid be used. As caprolactam, for example, dithio-bis-caprolactam can be used.

As thiourea derivatives, for example, Ν, Ν'-diphenylthiourea (DPTU), diethylthiourea (DETU) and ethylene thiourea (ETU) can be used.

Also suitable as additives are, for example, zinc diamine diisocyanate, hexamethylene tetramine, 1,3-bis (citraconimidomethyl) benzene and cyclic disulfanes.

The additives and crosslinking agents mentioned can be used both individually and in mixtures. The following substances for crosslinking the nitrile rubbers are preferably used: sulfur, 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, zinc dibenzyldithiocarbamate, dipentamethylenethiuram tetrasulfide, zinc dialkyl dithiophosphate, dimorpholyl, tellurium diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dimethyldithiocarbamate and dithio-bis-caprolactam. The crosslinking agents and aforementioned additives can each be used in amounts of about 0.05 to 10 phr, preferably 0.1 to 8 phr, in particular 0.5 to 5 phr (single dose, in each case based on the active substance). In a sulfur crosslinking, it is possible in addition to the crosslinking agents and additives mentioned above to use other inorganic or organic substances, such as zinc oxide, zinc carbonate, lead oxide, magnesium oxide, saturated or unsaturated organic fatty acids and their zinc salts, polyalcohols, amino alcohols, such as Example triethanolamine and amines such as dibutylamine, dicyclohexylamine, cyclohexylethylamine and polyetheramines.

If the hydrogenated nitrile rubbers according to the invention are those which contain repeating units of one or more carboxy-containing termonomers, crosslinking can also take place via the use of a polyamine crosslinker, preferably in the presence of a crosslinking accelerator. The polyamine crosslinker is not limited so long as it is (1) a compound containing either two or more amino groups (optionally also in salt form) or (2) a species which is present during the crosslinking reaction in -situ forms a compound having two or more amino groups. An aliphatic or aromatic hydrocarbon compound is preferably used in which at least two hydrogen atoms are replaced by either amino groups or by hydrazide structures (the latter a structure, --C (= 0) NHNH ₂ ))

Examples of such polyamine crosslinkers (ii) are:

Aliphatic polyamines, preferably hexamethylenediamine, hexamethylenediamine carbamate, tetramethylenepentamine, hexamethylenediamine cinnamaldehyde adduct or hexamethylenediamine dibenzoate;

Aromatic polyamines, preferably 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-methylenedianiline, m-phenylenediamine, p-phenylenediamine or 4,4'-methylenebis (o-chloroaniline) ;

Compounds having at least two hydrazide structures, preferably isophthalic dihydrazide, adipic dihydrazide or sebacic dihydrazide. Particularly preferred are hexamethylenediamine and hexamethylenediamine carbamate.

The amount of the polyamine crosslinker in the vulcanizable mixture is usually in the range of 0.2 to 20 parts by weight, preferably in the range of 1 to 15 parts by weight and more preferably in the range of 1.5 to 10 wt. Parts based on 100 parts by weight of the hydrogenated nitrile rubber.

As a crosslinking accelerator, any known to those skilled in the art can be used in combination with the polyamine crosslinker, preferably a basic crosslinking accelerator. usable are, for example, tetramethylguanidine, tetraethylguanidine, diphenylguanidine, di-o-tolylguanidine (DOTG), o-tolylbiguanidine and di-o-tolylguanidine salt of dicathecolboronic acid. It is also possible to use aldehydocin crosslinking accelerators, such as, for example, n-butylaldehydoaniline. At least one bi- or polycyclic aminic base is particularly preferably used as crosslinking accelerator. These are known to the person skilled in the art. Particularly suitable are l, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), l, 5-diazabicyclo [4.3.0] -5-nonene (DBN), l, 4-diazabicyclo [2.2.2] octane (DABCO), 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-l, 5,7-triazabicyclo [4.4.0] dec-5-ene (MTBD) ,

The amount of crosslinking accelerator in this case is usually in a range from 0.5 to 10 parts by weight, preferably from 1 to 7.5 parts by weight, in particular from 2 to 5 parts by weight, based on 100% by weight. Parts of the hydrogenated nitrile rubber.

The vulcanizable mixture based on the hydrogenated nitrile rubber according to the invention may in principle also contain scorch retarders which differ in a vulcanization with sulfur or with peroxides:

Vulcanization with sulfur uses: cyclohexyl thiophthalimide (CTP), Ν, Ν 'dinitrosopentamethylenetetramine (DNPT), phthalic anhydride (PTA) and diphenylnitrosamine. Cyclohexylthiophthalimide (CTP) is preferred.

Vulcanization with peroxides uses compounds such as those mentioned in WO-A-97/01597 and US-A-4,857,571 to delay scorch. Preference is given to sterically hindered p-dialkylaminophenols, in particular Ethanox 703 (Sartomer). The other common rubber additives include, for example, the typical and known in the art substances such as fillers, filler activators, antiozonants, anti-aging agents, antioxidants, processing aids, extender oils, plasticizers, reinforcing materials and mold release agents. As fillers, for example, carbon black, silica, barium sulfate, titanium dioxide, zinc oxide, calcium oxide, calcium carbonate, magnesium oxide, alumina, iron oxide, aluminum hydroxide, magnesium hydroxide, aluminum silicates, diatomaceous earth, talc, kaolins, bentonites, carbon nanotubes, Teflon (the latter preferably in powder form), or Silicates are used. The fillers are usually used in amounts ranging from 5 to 350 parts by weight, preferably from 5 to 300 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber. Suitable filler activators are, in particular, organic silanes, such as, for example, bis (triethoxy-silyl-propyl-tetrasulfide), bis (tri-ethoxy-silyl-propyl-disulfide), vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane , N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, hexadecyltrimethoxysilane or

(Octadecyl) methyldimethoxysilane into consideration. Other filler activators are, for example, surfactants such as triethanolamine and ethylene glycols having molecular weights of 74 to 10,000 g / mol. The amount of filler activators is usually in the range of 0 to 10 phr based on 100 phr of the nitrile rubber.

As mold release agents there are e.g. saturated or partially unsaturated fatty and oleic acids and their derivatives (fatty acid esters, fatty acid salts, fatty alcohols, fatty acid amides), which are preferably used as a mixture component, further applicable to the mold surface products, such as products based on low molecular weight silicone compounds, based on fluoropolymers and products Products based on phenolic resins into consideration. The amount of mold release agent is usually in the range of 0 to 10 phr, and preferably 0.5 to 5 phr, based on 100 phr of the nitrile rubber. Reinforcing with glass strengtheners (fibers) according to the teachings of US-A-4,826,721 is also possible, as well as reinforcement by cords, fabrics, fibers of aliphatic and aromatic polyamides (Nylon®, Aramid®), polyesters and natural fiber products.

Mixing of the components to produce the vulcanizable mixtures typically occurs either in the internal mixer or on a roll. At the time of starting, the internal mixer is charged with the nitrile rubber of the invention, which is usually present in a bale shape and is first comminuted, after a suitable period of time, which the person skilled in the art can easily determine the addition of the additives, and typically at the end of the crosslinking system Mixing is under the control of temperature with the proviso that the mix remains for a suitable time at a temperature in the range of 100 to 150 ° C. After a suitable mixing period, the internal mixer is vented After a further period of time, the internal mixer is emptied to obtain the vulcanizable mixture, and all of the abovementioned periods are usually in the range of a few minutes and can easily be determined by a person skilled in the art, depending on the M to be prepared be determined. Are rollers as _{? 4}

Mixing unit used, can be proceeded in an analogous manner and order of addition.

The invention further provides a process for the preparation of vulcanizates based on the hydrogenated nitrile rubbers according to the invention, characterized in that the vulcanizable mixtures containing the hydrogenated nitrile rubber according to the invention are subjected to vulcanization. Usually, the vulcanization is carried out at temperatures in the range of 100 ° C to 200 ° C, preferably at temperatures of 120 ° C to 190 ° C and most preferably from 130 ° C to 180 ° C.

Preferably, the vulcanization is carried out in a molding process.

The vulcanizable mixture is further processed by means of extruders, injection molding machines, rolls or calenders. The preformed mass which is thus obtainable is then typically vulcanized in presses, autoclaves, hot air systems or in so-called automatic mat vulcanization plants, temperatures of from 120.degree. C. to 200.degree. C., preferably from 140.degree. C. to 190.degree. The vulcanization time is typically 1 minute to 24 hours, and preferably 2 minutes to 1 hour. Depending on the shape and size of the vulcanizates, a second vulcanization by re-heating may be necessary to achieve complete vulcanization.

The invention accordingly provides the vulcanizates obtainable in this way, preferably present as a molding, based on the hydrogenated nitrile rubbers of the invention. These vulcanizates may be in the form of a belt, roll coverings, a gasket, a cap, a plug, a hose, flooring, sealing mats or plates, profiles or membranes. Specifically, it may be an O-ring seal, flat gasket, shaft seal, gasket, gasket, dust cap, plug seal, thermal insulation hose (with and without PVC additive), oil cooler hose, air intake hose, power steering hose, shoe sole or parts thereof or a pumping membrane.

Surprisingly, the present invention makes it possible to obtain vulcanizates having the desired property profile. Examples:

I Analytical Methods

The methods described below have been used in the case of the specific examples contained in this application, but are equally regarded as a disclosure of the corresponding methods for the general description of this application

The quantitative determination of 2,6-di-tert-butyl-p-cresol (Vulkanox® KB) in nitrile rubber or in hydrogenated nitrile rubber is carried out by gas chromatography using an internal standard (naphthalene). For the determination, 3 to 5 g of polymer with an accuracy of 0.01 g in 40 mL of a toluene / THF mixture (volume ratio 1: 1) dissolved with stirring in a sealable Erlenmeyer flask. 20.0 mg of naphthalene (dissolved in 5 ml of toluene) are added to the solution as an internal standard and distributed uniformly by stirring. By addition of 80 ml of methanol, the polymer is precipitated. The serum is analyzed by gas chromatography (Agilent Technologies in Waldbronn, Germany, device 6890) with the following instrument settings:

Capillary column: HP-5, length: 30 m; Inner diameter 0.32 mm; Film thickness: 0.25 μιη Inj ektionsmenge: 1 μΐ,

Injection temperature: 320 ° C

Oven temperature program: 100 ° C, heating rate: 10 ° C / min> 300 ° C

Detector temperature: 300 ° C

Under these conditions, a retention time of 3.4 minutes is found for 2,6-di-tert-butyl-p-cresol and a retention time of 6.44 minutes for naphthalene. In independent measurements, the response ratio of 2,6-di-tert-butyl-p-cresol to naphthalene is determined under the same conditions as the basis for calculating the content of 2,6-di-tert-butyl-p-cresol.

The quantitative determination of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) (Vulkanox® BKF) in nitrile rubber is carried out by gas chromatography using an internal standard (n-docosan). For the determination, 3 to 5 g of polymer with an accuracy of 0.01 g in 40 mL of a toluene / THF mixture (volume ratio 1: 1) dissolved with stirring in a sealable Erlenmeyer flask. 50.0 mg of n-docosan (dissolved in 5 ml of toluene) are added to the solution as an internal standard and distributed uniformly by stirring. By addition of 80 ml of methanol, the polymer is precipitated. The serum is analyzed by gas chromatography (Agilent Technologies in Waldbronn, Germany, device 6890) with the following instrument settings: ",

-76-

Capillary column: HP-5, length: 30 m; Inner diameter 0.32 mm; Film thickness: 0.25 μιη

Injection amount: 1 μΐ.

Injection temperature: 320 ° C

Oven temperature program: 240 ° C, 10 min., Heating rate: 20 ° C / min> 300 ° C

Detector temperature: 300 ° C

Under these conditions, a retention time of 5.96 min is found for 2,2-methylenebis (4-methyl-6-tert-butylphenol) and a retention time of 3.70 min for n-docosane.

In independent measurements, the response ratio of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) to n-docosane is used as the basis for calculating the content of 2,2-methylene bis (under the same conditions). 4-methyl-6-tert-butylphenol).

The volatiles were determined according to ISO 248, 4th edition in the version of 15.06.2005.

The chlorobenzene contents of hydrogenated nitrile rubbers were determined after drying by cutting 2.5 g of hydrogenated nitrile rubber to pieces as large as corncakes and weighing to + 1 mg accurately into a sealable 100 ml glass jar. The hydrogenated nitrile rubber is completely dissolved in 25 ml of acetone with shaking (about 2-3 h). To this solution, a defined amount of 1, 2-dichlorobenzene as an internal standard (0.25 mg dissolved in 2 ml of acetone) was added and mixed. By adding 40 ml of methanol, the polymer is coagulated. Then the vessel is made up to 100 ml with methanol.

The chlorobenzene is determined by gas chromatography (HP 5890 II) using a quartz capillary column and flame ionization detection. The quartz capillary column is characterized by the following features: length: 25 m; Diameter: 0.32 mm, coverage: polydimethylsiloxane, layer thickness: 1.05 microns. For the determination, 5 ml of the polymer-free solution are injected into the gas chromatochrograph (injector temperature: 270 ° C.). The carrier gas is hydrogen at a flow rate of 2 ml / min. used. The column temperature is increased from 60 ° C starting temperature to 110 ° C at 10 ° C / min and then to 310 ° C at 25 ° C / min. The column is 8 min. kept at 310 ° C. Under these conditions, for chlorobenzene and 1, 2-dichlorobenzene retention times of 2.344 min. or 5.294 min found. To calculate the chlorobenzene content, the area ratios of defined chlorobenzene and 1, 2-dichlorobenzene amounts are determined in independent measurements.

To determine the gel content, 250 mg of the hydrogenated nitrile rubber were dissolved in 25 ml of methyl ethyl ketone at 25 ° C. for 24 hours with stirring. The insoluble fraction was through _ηη

Ultracentrifugation at 20000U / min separated at 25 ° C, dried and determined by gravimetry. The gel content is given in wt.% Based on the weight. For the products according to the invention, it is <2.5% by weight. For the determination of the calcium content, 0.5 g of the nitrile rubbers were digested by dry ashing at 550 ° C. in a platinum crucible with subsequent dissolution of the ash in hydrochloric acid. After appropriate dilution of the digestion solution with deionized water, the calcium content was determined by ICP-OES (inductively coupled plasma-optical emission spectrometry) at a wavelength of 317.933 nm against calibration matrix adapted calibration solutions. Depending on the concentration of the elements in the digestion solution or sensitivity of the measuring instrument used, the concentrations of the sample solutions for the respective wavelengths used were adapted to the linear range of the calibration (B. Welz "Atomic Absorption Spectrometry", 2nd Ed., Verlag Chemie, Weinheim 1985 ). The chlorine content of the nitrile rubbers according to the invention is determined as follows on the basis of DIN EN 14582, method A. The nitrile rubber sample is digested in a pressure vessel according to Parr in a melt of sodium peroxide and potassium nitrate. Sulfite solution is added to the resulting melt and acidified with sulfuric acid. In the solution thus obtained, the resulting chloride is determined by potentiometric titration with silver nitrate solution and calculated as chlorine.

The Mooney viscosities of the unvulcanized nitrile rubbers or of the unvulcanized hydrogenated nitrile rubbers were determined in a shear disk viscometer in accordance with DIN 53523/3 or ASTM D 1646 at 100 ° C. The Mooney viscosities of the dried, unaged nitrile rubbers or unhydrated hydrogenated nitrile rubbers are referred to below as MV 0.

To determine the storage stability of the unvulcanized nitrile rubbers or of the unvulcanized hydrogenated nitrile rubbers, roller skins are stored in a circulating air drying cabinet, the oxygen content in this circulating air drying cabinet being unchanged from normal air, and then the Mooney viscosities are determined. The rolled skins of the unvulcanized nitrile rubbers or of the unvulcanized hydrogenated nitrile rubbers are obtained by reacting 100 g of the corresponding rubber at room temperature on a roll mill (Schwabenthan Polymix 110) at a gap width of 0.8-1.0 mm (rotational speeds: 25 min 730 min ^{). 1} are rolled). of the skins rectangular cutouts are cut 40-50 g, and (on aluminum trays 10cm / 15 cm), whose floor is covered with Teflon film, stored in a circulating air drying cabinet. the determined after 48 hours storage at 100 ° C values of Mooney Viscosity was designated as MV 1. The values of the Mooney viscosity determined after 72 hours storage at 100 ° C. ""

- / ö- were called MV 2. The storage stabilities (LS) were determined as the difference of the Mooney viscosity values before and after hot air storage:

LS 1 (48h / 100 ° C) = MV 1 - MV 0

LS 2 (72 h / 100 ° C) = MV 2 MV 0

The storage stability of nitrile rubber (LS 1) is typically sufficient as long as the Mooney viscosity changes after 48 hours of storage at 100 ° C (LSI = MV 1 - MV 0) by no more than 5 Mooney units.

The storage stability of hydrogenated nitrile rubber (LS 2) is sufficient as long as the Mooney viscosity does not change by more than 5 Mooney units when stored at 100 ° C for 72 hours (LS 2 = MV 2 - MV 0).

II example series

A tabular overview of the examples carried out is given in Table 1. The thermal drying of the nitrile rubber and the hydrogenated nitrile rubber was carried out in a vacuum oven, hereinafter abbreviated to "VTS", and / or by fluid bed drying, hereinafter abbreviated to "FB". In Table 1, the experiments which yield hydrogenated nitrile rubbers according to the invention are marked with "*." In the "molecular weight regulator" column, "LXS" stands for a tertiary dodecylmercaptan ("TDM") from Lanxess Deutschland GmbH and "CP" for a tert Dodecylmercaptan of the Chevron Phillips.

As can be read Table 1 is explained below in a case:

The nitrile rubber prepared via emulsion polymerization in Example 1.6 (see Table 4) and provided with the corresponding specified aging inhibitor is used firstly to carry out drying of the substituted phenol-containing NBR in the vacuum drying oven in Example 2.6 (see Table 5) and then in the process hydrogenated NBR containing the substituted phenol and either by dry-bed drying according to Example 4.5 in a vacuum drying oven or according to Example 5.6 * (see Table 8). Table 1: Overview of the experiments carried out

1.2 LXS KB 0.40 NaCl 2.2 - - -

1.3 LXS KB 0.45 NaCl 2.3 - - -

1.4 LXS KB 0.5 NaCl 2.4 - - -

1.5 LXS KB 0.6 NaCl 2.5 - 4.5 5.5 *

1.6 LXS KB 0.7 NaCl 2.6 - 4.6 5.6 *

1.7 LXS KB 0.8 NaCl 2.7 3.7 - 5.7 *

1.8 LXS KB 0.90 NaCl 2.8 - - 5.8 *

1.9 LXS KB 1.20 NaCl 2.9 3.9 - -

1.10 CP KB 0.25 MgCl ₂ 2.10 - - -

1.11 CP KB 0.40 MgCl ₂ 2.11 - - -

1.12 CP KB 0.45 MgCl ₂ 2.12 - 4.12 6.12 *

1.13 CP KB 0.5 MgCl ₂ 2.13 - - -

1.14 CP KB 0.6 MgCl ₂ 2.14 - - -

1.15 CP KB 0.7 MgCl ₂ 2.15 - - -

1.16 CP KB 0.8 MgCl ₂ 2.16 3.16 - 6.16 *

1.17 CP KB 0.9 MgCl ₂ 2.17 - 4.17 -

1.18 CP KB 1.20 MgCl ₂ 2.18 3.18 4.18 -

1.19 CP KB 1.75 MgCl ₂ 2.19 - - -

1.20 CP BKF 0.8 MgCl ₂ 2.20 3.20 - -

1.21 CP BKF 1.2 MgCl ₂ 2.21 3.21 - -

II.l Preparation of NBR latices A and B

Based on the recipes given in Table 2 below, two NBR latices (A and B) were prepared by emulsion polymerization. The two manufacturing recipes differ only in terms of the used tert. Dodecylmercaptans (Lanxess Germany GmbH or Chevron Phillips). All starting materials are given in parts by weight based on 100 parts by weight of the monomer mixture.

Table 2: Feedstocks for the preparation of NBR latexes A and B

Approach / latex A B

Parts by weight parts by weight

Butadiene 56 56

Acrylonitrile 44 44

Total amount of water 200 200

Erkantol® BXG ^1} 2.8 2.8

Baykanol® PQ ²⁾ 0.84 0.84

Sodium salt of a mixture of mono- and disulfonated naphthalenesulfonic acids with Isobutylenoligomersubstituenten Erkantol ^® BXG)

Sodium salt of methylene-bis-Naphthalinssulfonat (Baykanol ^® PQ, Lanxess Germany GmbH) Aldrich Order: 21.622 to 4

Aldrich order number: T5,830-0

Aldrich order number: 15,795-3

Tert. Dodecylmercaptan: C ^ -Mercaptangemisch (Sulfole ^® 120; Chevron Phillips Chemical Co.)

Tert. Dodecylmercaptan: C ^ mercaptan of Lanxess Germany GmbH

In Table 2 are for tert. Dodecyl mercaptan given two numerical values. This means that the total amount of tert. Dodecylmercaptan was added in two portions. The first portion of tert. Dodecylmercaptan was initially introduced in the batch before the polymerization, while the remaining amount was added at a polymerization conversion of 15%.

The preparation of the NBR latices A and B was carried out batchwise in a 2 m ³ autoclave with stirrer. Each batch used 350 kg of the monomer mixture and a total of 700 kg of water. In 600 kg of this amount of water, the emulsifiers Erkantol ^® BXG (9.8 kg), Baykanol ^® PQ (2.94 kg) and the potassium salt of coconut fatty acid (1.96 kg) were charged with 180 g of potassium hydroxide in an autoclave and rinsed with a stream of nitrogen , After completion of the nitrogen purge, the destabilized monomers (196 kg of butadiene and 154 kg of acrylonitrile) and aliquots of the tert. Dodecyl mercaptan (1.54 kg in batch A and 1.16 kg in batch B) was added to the reactor. Thereafter, the reactor was sealed. The residual amount of water (100 kg) was used to prepare the aqueous solutions of tris (a-hydroxyethyl) amine, potassium peroxodisulfate and the stopper solutions. By adding aqueous solutions of 950 g of potassium peroxodisulfate (corresponding to the 0.27 parts by weight of Table 1) and 530 g of tris (a-hydroxy-ethyl) amine (corresponding to 0.15 parts by weight of Table 1) the polymerization was started at 20 ° C and held at this temperature over the entire period. The course of polymerization was followed in each case by gravimetric conversion determinations. at Polymerization conversions of 15% were according to Table 1 1.54 kg tert. Dodecyl mercaptan from Lanxess (batch A) or 1.16 kg tert. Dodecylmercaptans from Chevron Phillips (batch B) corresponding to 0.44 or 0.33 parts by weight. After a polymerization time of 7 hours, the polymerizations were stopped by adding an aqueous solution of sodium dithionite / N, N-diethylhydroxylamine (DEHA) and potassium hydroxide. The polymerization conversions were 75% (latex A) and 76% (latex B). Unreacted monomers and other volatiles were removed by steam distillation.

The characteristic data of the latices thus obtained are summarized in Table 3. Table 3: Characteristic data of the NBR latices A and B

II.2 Processing of the NBR latices A and B

Before the coagulation of the NBR latices A and B with different amounts of 4-methyl-2,6-teri-butyl phenol was (Vulkanox ^® KB Lanxess GmbH Germany; structure according to the invention) and 2,2-methylene-bis- (4 methyl-6-tert-butylphenol) (Vulkanox BKF ^® from Lanxess Germany GmbH, not according to the invention phenolic anti-aging agent) Table 3 correspondingly offset. For this purpose, 50% dispersions of Vulkanox ^® KB and Vulkanox BKF ^® were used in water.

The aqueous dispersions of Vulkanox ^® KB or of Vulkanox BKF ^® based on the following formulation, wherein the preparation at 95 to 98 ° C was carried out with the aid of an Ultraturrax:

360 g deionized water (DW water)

40 g alkylphenol (emulsifier NP ^® 10 Lanxess Germany GmbH) 400 g Vulkanox.RTM KB or Vulkanox.RTM BKF Lanxess Germany GmbH

The additions of Vulkanox® KB or Vulkanox® BKF were based on the solid contained in the latex and are stated in% by weight. Before coagulation of the latexes containing Vulkanox® KB or Vulkanox® BKF, the solids content of the latices was adjusted to 20% by weight by adding the appropriate amount of deionized water. For the coagulation of the NBR latexes, aqueous solutions of sodium chloride and magnesium chloride were used. The aqueous sodium chloride solution was 20%, using normal industrial water (not deionized and thus containing calcium ions) for the production. The aqueous magnesium chloride solution was 26%, using normal industrial water (not deionized and thus containing calcium ions) for the production.

The concentration of the salt solutions and the amounts of salt used for the precipitation were calculated in each case without water of crystallization and are based on the solid contained in the latex. The anti-aging agents used for the stabilization of the nitrile rubbers and their amounts, the salts used for latex coagulation, the concentration of salt solutions, the amounts of salts based on the NBR rubber, the coagulation temperature, the temperature in the wash and the duration of the wash are tabulated in Table 4 summarized.

Table 4: Additions of Vulkanox® KB or BKF and work-up of the NBR latices A and B ("BW" means process water)

1.15 B KB 0.7 MgCl ₂ 26 2.37 60 BW 60 5.0

1.16 B KB 0.8 MgCl ₂ 26 2.37 60 BW 60 8.0

1.17 B KB 0.9 MgCl ₂ 26 2.37 60 BW 60 5.0

1.18 B KB 1.20 MgCl ₂ 26 2.37 60 BW 60 8.0

1.19 B KB 1.75 MgCl ₂ 26 2.37 60 BW 60 8.0

1.20 B BKF 0.8 MgCl ₂ 26 2.37 60 BW 60 8.0

1.21 B BKF 1.2 MgCl ₂ 26 2.37 60 BW 60 8.0

The work-up of the NBR latexes was carried out batchwise in a stirred, open container with 200 1 capacity, which had an inflow and outflow. The drainage could be shut off by means of two laterally mounted rails by means of a sieve (mesh size 2 mm) so that the rubber crumbs obtained in the latex coagulation were not flushed out during the wash.

For the coagulation a latex amount was used, which was calculated so that at 100% yield each 25 kg of solid were obtained. The latex was placed in the coagulation tank, heated to 60 ° C and coagulated with stirring by slow addition of the aqueous salt solution. After completion of the latex coagulation, the rubber crumbs were washed by dilution washing without prior separation of the serum. For crumb washing, normal calcium ion-containing tap water ("BW") heated to 60 ° C. was used with a constant flow rate (200 l / h) of wash water The subsequent thermal drying of the nitrile rubbers summarized in Table 5 was carried out batchwise in a vacuum drying oven at 70 ° C. to a residual moisture content of <1.0% by weight characterized by determining the contents of 4-methyl-2,6-but-butylphenol, 2,2-methyl-bis (4-methyl-6-tert-butylphenol), calcium and chlorine and their storage stability (LS 1) ( Table 5).

Table 5 shows that the amounts of 4-methyl-2,6-tert-butylphenol and 2,2-methylenebis (4-methyl-6-tert-butylphenol) added to the latices are shown by drying in a vacuum oven recovered at a recovery rate of 92 to 103% in the reclaimed and dried nitrile rubber; thus less than 10% of the amounts of 4-methyl-2,6-tert-butylphenol and 2,2-methylene-bis (4-methyl-6-tert-butylphenol) are lost under the selected drying conditions. ".

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Table 5: Properties of unvulcanized nitrile rubbers (drying in VTS)

Table 5 also shows that nitrile rubber has sufficient storage stability LS 1 (increase in Mooney viscosity after 48 hours storage at 100 ° C. <5 Mooney units) if the content of 4-methyl-2 detectable analytically in the nitrile rubber is 6-tert-butylphenol in the range of 0.5 to 1.49 wt.% Is.

In a further series of experiments, selected nitrile rubbers were thermally dried to residual moisture contents <1% by weight after mechanical dehydration and comminution by means of fluid bed drying. For this purpose, a fluidized bed dryer (fast dryer TG 200) from Kurt Retsch (Haan / Dusseldorf), which was equipped with a drying container of 6 L content. For the drying, in each case 0.5 kg of the moist nitrile rubber was used. The flow rate of the hot air was kept constant at 100 m ³ / h in all experiments. The temperature and residence times of fluid bed drying were varied (Table 6).

Table 6: Properties of nitrile rubbers A (fluid bed drying)

Table 6 shows that the drying over the fluidized bed when using 4-methyl-2,6-tert-butylphenol as a phenolic antioxidant according to the invention, a reduction to 42 to 53%, d. H. when using the fluidized bed drying go under the chosen conditions 47 to 58% of the amounts of 4-methyl-2,6-tert-butylphenol lost. The loss of 2,2-methylene-bis- (4-methyl-6-tert-butylphenol) is under the same work-up and drying conditions only about 1 wt.%.

II.3 Preparation of hydrogenated nitrile rubbers

II.3.1 Hydrogenation

Table 1 gives an overview of the preparation conditions of the nitrile rubbers used for the hydrogenation and the name of the hydrogenated nitrile rubbers not according to the invention or hydrogenated according to the invention. Nitrile rubbers which were thermally dried in a vacuum drying oven were used for the hydrogenation.

The hydrogenations were carried out at a hydrogen pressure of 190 bar at a temperature of 120 ° C to 130 ° C and at solids concentrations of 17.5 wt.%, Wherein all Hydrogenation bars 0.15% by weight of tris (triphenylphosphine) rhodium (I) chloride (Evonik-Degussa) based on 100 g of nitrile rubber (phr) as catalyst and 0.2 phr of triphenylphosphine (Merck Schuchardt OHG, Order No. 8.08270) were used as cocatalyst. In the hydrogenations, 5.25 kg each of nitrile rubber were dissolved in a 40 liter autoclave in 24.25 kg of chlorobenzene. Prior to the hydrogenation, the polymer solution was successively treated once with nitrogen (20 bar) and twice with hydrogen (20 bar) with stirring (170 rpm) and then released. The reaction mixture was heated to 120 ° C and pressurized with 190 bar of hydrogen. In the next step, 10.5 g of cocatalyst triphenylphosphane were added as a solution in 250 g of chlorobenzene. The hydrogenation was started by adding 7.875 g of tris (triphenylphosphine) rhodium (I) chloride dissolved in 250 g of chlorobenzene. As the reaction decreased, the internal temperature was gradually raised to 130 ° C. The course of the hydrogenation was monitored online by determining the hydrogen uptake. The hydrogenation was stopped at hydrogenation levels of 99.4 + 0.2% by cooling the reaction mixture. Then the lugs were relaxed. Residuals of hydrogen were removed by passage of nitrogen. The exact degrees of hydrogenation were after completion of the hydrogenation after in rubber + rubber. Plastics, Vol. 42 (1989), no. 2, 107-110 and rubber + rubber. Plastics, Vol. 42 (1989), no. 3, 194-197 described methods. A rhodium separation was carried out according to US Pat. No. 4,985,540 in Examples 6.12 * and 6.16 *. For this, the polymer solutions were diluted to a solids concentration of 5.0% by weight prior to rhodium recovery.

II.3.2 Isolation of hydrogenated nitrile rubbers from the chlorobenzene solution

The isolation of the hydrogenated nitrile rubbers from chlorobenzene solution was carried out batchwise at atmospheric pressure by steam distillation. For this purpose, a stirrable glass 20 L-planschliffbehälter was used with jacket heating. The feeding of water vapor took place via a bottom valve. Furthermore, the 20 L flat-section vessel had devices for continuous metering of a chlorobenzene HNBR solution, a 2% aqueous solution of a water-soluble carboxyl-containing polymer (Orotan® / Rohm and Haas), a 2% aqueous calcium chloride solution and dilute sodium hydroxide solution ( 0.5%).

The chlorobenzene solutions of the hydrogenated nitrile rubbers were diluted to a solids concentration of 10% by weight in the examples in which no rhodium separation took place. The concentration of the chlorobenzene solutions of products 6.12 * and 6.16 * (with rhodium separation) was 5% by weight>. The chlorobenzene solutions were heated to 95-100 ° C in all examples prior to metering in the 20 L flat ground. ""

-o / -

By adding the sodium hydroxide solution, the pH of the aqueous phase was maintained in the pH range of 7.7 to 8.3 throughout the distillation process.

8 L of deionized water were introduced into the 20 L flat-section vessel and heated to 98-100 ° C. by jacket heating before water vapor was introduced. Then, the addition of the chlorobenzene solution of the hydrogenated nitrile rubber (0.5 kg HNBR solid / h) and the aqueous solutions of Orotan® and calcium chloride were started at a stirring speed of 2000 rpm. The rates of Orotan® and calcium chloride dosing were adjusted so that at each time point 0.3 part by weight of Orotan® and 0.15 part by weight of calcium chloride, based in each case on 100 parts by weight of the amount present in the stripping vessel hydrogenated nitro rubber. The steam distillation was carried out at atmospheric pressure at 98-100 ° C. The distilling off vapors of chlorobenzene and water vapor were condensed and collected. The dosage of the HNBR solution was stopped as soon as each 1.5 kg of HNBR was present in the stripping vessel. Thereafter, the steam distillation was continued for 0.5 h. The hydrogenated nitrile rubber was present in the aqueous dispersion in the form of rubber crumbs in the diameter range 3 to 10 mm. After opening the surface grinding container, the rubber crumbs were removed by means of a sieve. The adherent water was removed by dripping and squeezing. The non-inventive thermal drying of the hydrogenated nitrile rubbers was carried out in a vacuum oven at 70 ° C while introducing air of 23 ° C to constant weight.

The thermal drying of the hydrogenated nitrile rubbers was carried out by fluidized bed drying under the conditions given in Table 8.

On the dried HNBR samples, the contents of volatile components, the content of 2,6-di-tert-butyl-p-cresol, the chlorobenzene content, the gel content and the storage stability were determined and the loss of 2,6-di-tert. Calculated butyl-p-cresol. II.3.3 Properties of Unvulcanized Hydrogenated Nitrile Rubbers (HNBR)

The properties of the non-vulcanized hydrogenated nitrile rubbers not according to the invention are summarized in Table 7. ""

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Table 7: Characteristic properties of the non-vulcanized hydrogenated nitrile rubbers not according to the invention

Table 7 shows that when dried in a vacuum oven, the losses of 2,6-di-tert-butyl-p-cresol are between 0 and 6%. The hydrogenated nitrile rubbers not according to the invention obtained in this way have a content of 2,6-di-tert-butyl-p-cresol in the range from 0.45 to 1.15% by weight after storage at 100 ° C. for 3 days (LS 2). sufficient storage stability. The contents of volatile fractions are in the range from 0.1 to 0.3% by weight, the chlorobenzene contents are in the range <50 to 106 ppm and the gel contents in the range of 0.73-1.20% by weight>.

The drying of the hydrogenated nitrile rubbers according to the invention was carried out in a fluidized bed dryer (rapid dryer TG 200) from Kurt Retsch (Haan / Dusseldorf). The container had a content of 6 L, which was loaded with 0.5 kg each of the rubber crumb. The flow rate of the hot air was kept constant at 100 m ³ / h in all experiments. The temperature and residence times of fluid bed drying were varied (Table 8).

The rubber crumb processed according to the invention by fluidized bed drying has the properties summarized in Table 8. Conditions in the fluidized bed drying and properties of the resulting uncured hydrogenated nitrile rubbers according to the invention (each characterized by "*")

Table 8 shows that in the fluid bed drying of hydrogenated nitrile rubber, the recovery rates of 2,6-di-tert-butyl-p-cresol are in the range of 20-69%; Accordingly, the losses of 2,6-di-tert-butyl-p-cresol 31 - 80%>. The hydrogenated nitrile rubbers obtained according to the invention have contents of 2,6-di-tert-butyl-p-cresol in the range from 0.16 to 0.4% by weight. The contents of volatile fractions are in the range from 0.1 to 0.3% by weight, the chlorobenzene contents are in the range <50 to 175 ppm and the gel contents in the range from 0.78 to 1.47% by weight>. The hydrogenated nitrile rubbers according to the invention are stable on storage after storage for 3 days at 100 ° C. (LS 2).

II.4 Preparation, Composition and Characterization of Vulcanizable Mixtures Based on Hydrogenated Nitrile Rubbers (HNBR)

In order to evaluate the vulcanizate properties of the hydrogenated nitrile rubbers, rubber mixes of the type shown in Table 9 were used in an internal mixer of 1.5 l internal volume (GK 1.5 from Werner & Pfleiderer, Stuttgart) preheated to 50 ° C. with intermeshing kneading elements (PS 5A blade geometry) prepared composition. The addition of the mixture components was carried out according to the order given in Table 9 (except Component 8. "Peroxide") The admixture of the peroxide was carried out in a second mixing step on a cooled roll at a skin temperature <50.degree.

Table 9: Composition of the vulcanizable mixture

To evaluate the processing behavior of the rubber mixtures, the Mooney viscosities were determined on the unvulcanized rubber mixtures at 100 ° C. (MLI + 4/100 ° C.) and at 120 ° C. (MLI + 4/120 ° C.) according to ASTM D1 646 (Tables 10 , 11 and 12). Vulcanization and vulcanizate properties:

The specimens necessary for the Vulkanisatcharakterisierung were by press vulcanization of the mixtures at 180 ° C / 18 min. obtained under a hydraulic pressure of 120 bar. Before the characterization, the specimens were stored for 17 h at 150 ° C in an oven under air after vulcanization.

The following properties were determined on the vulcanizates on the basis of the following standards:

DIN 53505: Shore A hardness at 23 ° C and 70 ° C

DIN 53504: Tension values at 50% elongation (σ ₅₀ ), 100% elongation (σιοο), 200% elongation (σ ₂₀ ο) and 300%) Elongation (σ 300); Tensile strength and elongation at break (£ _b )

DIN 53512: Rebound resilience at 23 ° C and 70 ° C

DIN 53517: compression set (DVR) or compression set (CS) Determination at 23 ° C after

Storage of a 25% compressed cylindrical specimen (original dimensions height: 6.3 mm, diameter: 13 mm) at 70h / 23 ° C or 70h / 150 ° C Table 10: Vulcanizate properties of hydrogenated nitrile rubbers not according to the invention

Table 10 shows that the vulcanizates of the non-inventive hydrogenated nitrile rubbers containing 2,6-di-tert-butyl-p-cresol in the range 0.45-1.15 wt.%, A low level of modulus values (σ 2oo <17 , 5 MPa and σ 300 <26.1 MPa) and worse compression set values> 35%. Further, Table 10 shows that as the content of 2,6-di-tert-butyl-p-cresol increases, both the modulus level and the compression set deteriorate.

Table 11: Vulcanizate properties of the hydrogenated nitrile rubbers according to the invention

(marked with "*")

Inventive Examples 5.5 * 5.6 * 5.7 * 5.8 * 6.12 * 6.16 *

2,6-di-tert-butyl-p-cresol in HNBR wt.% 0.31 0.24 0.40 0.23 0.31 0.16

Unvulcanized rubber mixes

Compound viscosity (MLl + 4/100 ° C) ME 118 121 119 121 121 120

Compound viscosity (MLl + 4/120 ° C) ME 85 87 86 87 87 86

vulcanizate

Shore A hardness (23 ° C) 72 72 73 72 72 73

Shore A hardness (70 ° C) 69 69 69 69 69 70

Rebound resilience at 23 ° C% 28 28 27 28 28 28 Rebound resilience at 70 ° C% 54 55 53 55 55 53 σ ₅ ο MPa 2.2 2.1 2.1 2.3 2.4 2.3 σ loo MPa 5.8 5.7 5.7 5.9 6 , 1 5,8 σ 2oo MPa 18,9 18,9 18,0 19,8 19,0 19,7 σ 300 MPa 28,6 27,9 27 28,8 27,9 28,8

Tensile strength MPa 29.4 29.5 29.2 30.1 29.3 29.4

Elongation at break £ _b % 315 335 340 325 330 310

Compression Set (70 h / 150 ° C)% 31.7 30.7 34 29.5 30.8 28.5

Table 11 shows that based on the hydrogenated nitrile rubbers according to the invention with contents of 2,6-di-tert-butyl-p-cresol in the range 0.16-0.40 wt.% Vulkanisate obtained, the better properties than the non-inventive Examples of Table 10 have. In detail we found: G2oo> 18.0 MPa and G3oo> 27.0 MPa as well as lower, better compression set values <34%.

In the following series (Table 12) Vulkanox® KB in amounts of 0.5 and 1.0 phr was added to the hydrogenated nitrile rubber 5.5 * prepared according to the invention prior to vulcanization and the influence of these additives on the vulcanizing rate properties was determined. The conditions of mixture preparation, vulcanization and vulcanizate testing were identical to those described above.

In the experiments of Table 12, it is shown that by adding 2,6-di-tert-butyl-p-cresol, the vulcanizing rate properties (modulus level and compression set) of hydrogenated nitrile rubber are degraded.

Table 12: Influence of Vulkanox® KB additives on the vulcanizate properties of hydrogenated nitrile rubber

Examples 6.5 * 6.6 6.7

Addition of 2,6-di-tert-butyl-p-cresol wt.% 0 0.5 1.0

vulcanizate

Shore A Hardness (23 ° C) 72 71 70

Shore A Hardness (70 ° C) 69 69 67

Rebound resilience at 23 ° C% 28 34 34

Rebound resilience at 70 ° C% 54 55 55 σ so MPa 2,2 2,2 2,0 σ loo MPa 5,8 5,3 4,7 σ 200 MPa 18,9 18,0 16,2 σ 300 MPa 28,6 27,6 25,3

Tensile strength MPa 29.4 28.7 29.1

Elongation at break £ b% 315 331 364

Compression Set (70 h / 150 ° C)% 31.7 36.2 40.6

Claims

claims:

1. hydrogenated nitrile rubber containing at least one substituted phenol of the general formula (I) in an amount in the range of 0.01 wt.% To less than 0.45 wt.%, Preferably from 0.05 wt.%) To 0.43 wt %, more preferably from 0.1% by weight to 0.41% by weight and in particular from 0.15% by weight to 0.4% by weight, based in each case on the hydrogenated nitrile rubber,

wherein

R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} identical or different and are hydrogen, hydroxy, a linear, branched, cyclic or aromatic hydrocarbon radical having 1 to 8 C atoms and additionally one, two or three heteroatoms, which are preferably oxygen, wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ^{5 is} not hydrogen.

2. hydrogenated nitrile rubber according to claim 1, characterized in that

3. hydrogenated nitrile rubber according to claim 2, characterized in that two or three of the radicals R ¹ , R ² , R ³ , R ⁴ and R ^{5 is} hydrogen and the remaining three or two of the radicals R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} identical or different and hydroxy, a linear or branched CpCg alkyl radical, more preferably methyl, ethyl, propyl, n-butyl or t-butyl, a linear or branched CpCg alkoxy, more preferably methoxy, ethoxy or propoxy , a C3-C8 cycloalkyl radical, more preferably cyclopentyl or cyclohexyl, or a phenyl radical. A hydrogenated nitrile rubber according to claim 1, characterized in that the at least one substituted phenol of the general formula (I) is selected from the group consisting of the compounds mentioned in the fol.

A hydrogenated nitrile rubber according to any one of claims 1 to 4, characterized in that it comprises repeating units derived from at least acrylonitrile and 1,3-butadiene, preferably either exclusively derived from acrylonitrile and 1,3-butadiene or derived from acrylonitrile, 1,3-butadiene and one or more α, β-unsaturated mono- or dicarboxylic acid (s), their esters or amides, in particular exclusively derived from acrylonitrile and 1,3-butadiene or derived from acrylonitrile, 1,3-butadiene and one or more alkyl esters of one α, β-unsaturated carboxylic acid selected from the group methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t- Butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and lauryl (meth) acrylate.

Hydrogenated nitrile rubber according to one of claims 1 to 5, characterized in that the storage stability LS2 of the hydrogenated nitrile rubber defined by

LS 2 (72h / 100 ° C) = MV 2 - MV 0

in which

MVO the Mooney viscosity ML 1 + 4 @ 100 ° C determined according to ASTM D 1646 of the hydrogenated

Nitrile rubber means and

MV2 the Mooney viscosity ML l + 4 @ 100 ° C determined according to ASTM D 1646 of the same hydrogenated nitrile rubber after 72 hours storage at 100 ° C means a value less than 5.

Hydrogenated nitrile rubber according to one of claims 1 to 6, characterized in that the degree of hydrogenation of the hydrogenated nitrile rubber in a range greater than 94.5 to 100%, preferably in a range of 95 to 100%, particularly preferably in a range of 96 to 100% ), most preferably in a range of 97 to 100%> and in particular in a range of 98 to 100%.

Hydrogenated nitrile rubber according to one of claims 1 to 6, characterized in that the degree of hydrogenation of the hydrogenated nitrile rubber is greater than or equal to 99.1%.

Process for the preparation of hydrogenated nitrile rubbers according to one of Claims 1 to 8, characterized in that nitrile rubbers containing at least one substituted phenol of the general formula (I), preferably in an amount in the range from 0.5 to 1% by weight, are obtained nitrile rubber is hydrogenated in solution, then the solvent is removed and the hydrogenated nitrile rubber is isolated and dewatered, reducing the content of substituted phenol of general formula (I) to the amount of 0.01% by weight> less than 0.45 % By weight, preferably in the range from 0.05% by weight to 0.43% by weight), more preferably from 0.1% by weight to 0.41% by weight and in particular 0.15% by weight % to 0.4% by weight.

A method according to claim 9, characterized in that as the hydrogenation catalyst tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride, tris (dimethylsulfoxide) rhodium (III) chloride, Hydridorhodiumtetrakis (triphenylphosphane ) or the corresponding compounds in which triphenylphosphine is wholly or partly replaced by tricyclohexylphosphine. A method according to spoke 9 or 10, characterized in that the separation of the solvent either by a dry workup, preferably via a drum drying process or a screw process, or by a wet workup, preferably via a steam distillation, more preferably via a steam distillation with subsequent drying of the isolated rubber crumb using a fluid bed dryer or in an expeller-expander dryer.

A method according to spoke 11, characterized in that the workup procedures are each carried out so that the substituted phenol of the general formula (I) contained in the hydrogenated nitrile rubber to 20-98 wt.%, Based on the amount of the substituted phenol of the general formula (I ) is removed from the nitrile rubber used for the hydrogenation.

A method according to spoke 11, characterized in that the fluidized bed dryer is operated continuously, preferably by crumbs of hydrogenated nitrile rubber having water contents of 5 to 50 wt.% With air flowing through, the temperature of 100 to 180 ° C, in particular 110 ° C have up to 150 ° C.

Vulcanisable mixtures containing at least one hydrogenated nitrile rubber according to one of claims 1 to 8 and at least one crosslinking system comprising at least one crosslinker and optionally one or more crosslinking accelerators.

A process for the preparation of vulcanizates, characterized in that vulcanizing a vulcanizable mixture according to spoke 14, preferably in the context of a shaping process, preferably at a temperature in the range of 100 ° C to 200 ° C, particularly preferably from 120 ° C to 190 ° C and more preferably from 130 ° C to 180 ° C.

Vulcanizates obtainable by the process according to claim 15, preferably in the form of shaped bodies, particularly preferably in the form of a belt, roller coverings, a gasket, a cap, a stopper, a hose, flooring, sealing mats or plates, profiles or membranes.