EP3090019A1 - Caoutchoucs nitriles hydrogénés contenant du phénol - Google Patents

Caoutchoucs nitriles hydrogénés contenant du phénol

Info

Publication number
EP3090019A1
EP3090019A1 EP14828164.5A EP14828164A EP3090019A1 EP 3090019 A1 EP3090019 A1 EP 3090019A1 EP 14828164 A EP14828164 A EP 14828164A EP 3090019 A1 EP3090019 A1 EP 3090019A1
Authority
EP
European Patent Office
Prior art keywords
nitrile rubber
weight
hydrogenated nitrile
general formula
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14828164.5A
Other languages
German (de)
English (en)
Inventor
Werner Obrecht
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arlanxeo Deutschland GmbH
Original Assignee
Arlanxeo Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=49882961&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3090019(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Arlanxeo Deutschland GmbH filed Critical Arlanxeo Deutschland GmbH
Priority to EP14828164.5A priority Critical patent/EP3090019A1/fr
Publication of EP3090019A1 publication Critical patent/EP3090019A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C2/00—Treatment of rubber solutions
    • C08C2/02—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C2/00—Treatment of rubber solutions
    • C08C2/06—Wining of rubber from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • 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).
  • Mooney viscosity ML 1 + 4 at 100 ° C.
  • 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.
  • 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.
  • DE-A-3 921 264 describes the preparation of HNBR which, after peroxidic crosslinking, provides low compression set vulcanizates.
  • 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.
  • DE-A-3 921 264 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.
  • 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.
  • 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.
  • the improvement of the economy of the process and the avoidance of wastewater pollution by leached emulsifier reclaimed 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • US Pat. No. 4 mm The examples of US Pat. No.
  • 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.
  • 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).
  • octadecyl 3- (3,5-di-t.butyl-4-hydroxyphenyl) propionate
  • 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) prop
  • 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.
  • information on the dependence of the storage stability of the nitrile rubber on the type and amount of anti-aging agents is missing.
  • 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.
  • EP-A-1 369 436 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.
  • additional precipitating agents alkali metal salts of inorganic acids can be used.
  • precipitation aids such as gelatin, polyvinyl alcohol, cellulose, carboxylated cellulose and cationic and anionic polyelectrolytes or mixtures thereof can be added.
  • 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.
  • a correspondingly structured Ci2-Ci6-alkylthiol acts as a "chain transfer agent” and is thus incorporated as an end group in the polymer chains.
  • chain transfer agent acts as a "chain transfer agent” and is thus incorporated as an end group in the polymer chains.
  • latex coagulation it is stated in each case that any coagulants can be used.
  • inorganic coagulants calcium chloride and aluminum chloride are mentioned and used.
  • 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.
  • 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.
  • 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.
  • ICZ ion index
  • c (Ca 2+ ), c (Na + ) and c (K + ) indicate the concentration of calcium, sodium and potassium ions in nitrile rubber in ppm.
  • 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.
  • 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.
  • 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 ( + )
  • 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.
  • 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.
  • 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.
  • a number of anti-aging agents are listed, which are added to the Nitrilkautschukuatex before coagulation, wherein quantities are missing.
  • 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.
  • 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.
  • 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.
  • EP 2 238 175 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.
  • 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.
  • 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 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.
  • 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,
  • R, 1, ⁇ 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the hydrogenated nitrile rubber according to the invention contains at least one substituted phenol of the general formula (I),
  • 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,
  • 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%.
  • 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 ,
  • 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.
  • 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 cycl
  • 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 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.
  • 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 ⁇ , ⁇ -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%).
  • hydrogenated nitrile rubbers having a degree of hydrogenation ranging from 90 to 100% are used.
  • 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.
  • 1,3-butadiene isoprene and mixtures thereof.
  • Very particular preference is given to 1,3-butadiene.
  • ⁇ , ⁇ -unsaturated nitrile any known ⁇ , ⁇ -unsaturated nitrile can be used for preparing the nitrile rubbers of the invention, preference is given to (C 3 -C 5 ) - ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particularly preferred is acrylonitrile.
  • one or more further copolymerizable monomers may be, for example, aromatic vinyl monomers, preferably styrene, ⁇ -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-conjugate
  • hydroxyl-containing monomers may be used as copolymerizable termonomers, preferably hydroxyalkyl (meth) acrylates.
  • hydroxyalkyl (meth) acrylates preferably hydroxyalkyl (meth) acrylates.
  • 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-
  • 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'-epoxyh
  • carboxy-containing, copolymerizable termonomers can be used as further copolymerizable monomers, for example ⁇ , ⁇ -unsaturated monocarboxylic acids, their esters, ⁇ , ⁇ -unsaturated dicarboxylic acids, their mono- or diesters or their corresponding anhydrides or amides.
  • Acrylic acid and methacrylic acid may preferably be used as ⁇ , ⁇ -unsaturated monocarboxylic acids. It is also possible to use esters of ⁇ , ⁇ -unsaturated monocarboxylic acids, preferably their alkyl esters and alkoxyalkyl esters. The alkyl esters, in particular CpCig alkyl esters of the ⁇ , ⁇ -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.
  • alkoxyalkyl esters of ⁇ , ⁇ -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.
  • cyanoalkyl acrylate and cyanoalkyl methacrylate in which the C atom number of the cyanoalkyl group is 2-12, preferably ⁇ -cyanoethyl acrylate, ⁇ -cyanoethyl acrylate and cyanobutyl methacrylate.
  • 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 ⁇ , ⁇ -unsaturated carboxylic acid esters, such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.
  • Beta.-unsaturated dicarboxylic acids preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
  • ⁇ , ⁇ -unsaturated dicarboxylic acids 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,
  • n-butyl acrylate is used.
  • alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate.
  • methoxyethyl acrylate is used.
  • esters of ⁇ for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxymethyl) acrylamide and urethane (meth) acrylate are used.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid monoesters examples 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
  • 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
  • Citracon Acidmonoalkylester preferably Monomethylcitraconat, Monoethylcitraconat, Monopropylcitraconat and mono-n-butyl citraconate;
  • Citraconic monocycloalkyl esters preferably monocyclopentylcitraconate, monocyclohexyl citraconate and monocycloheptylcitraconate;
  • Citracon Acidmonoalkylcycloalkylester preferably Monomethylcyclopentylcitraconat and Monoethylcyclohexylcitraconat;
  • Citracon 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
  • 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.
  • polyunsaturated compounds are acrylates, methacrylates or itaconates of polyols, e.g.
  • 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.
  • acrylamides e.g. Methylenebisacrylamide, hexamethylene-1, 6-bisacrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane or 2-acrylamido-ethyl acrylate.
  • 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 ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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.
  • corresponding proportions of the repeating units of the conjugated diene (s) and / or the repeat units of the ⁇ , ⁇ -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.
  • 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 ⁇ , ⁇ -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.
  • nitrile rubbers the repeat units of acrylonitrile, 1,3-butadiene and one or more ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid, their esters or amides, and in particular repeat units of an alkyl ester of an ⁇ , ⁇ -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.
  • 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.
  • 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.
  • nitrile rubbers having a storage stability LSI of not more than 5 Mooney units 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 w
  • 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.
  • 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.
  • 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.
  • 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.
  • X are the same or different and are hydrogen, halogen, pseudohalogen, SnCl 3 or
  • n 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
  • 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.
  • 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.
  • 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)
  • 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),
  • 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 0, 1 or 2
  • 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.
  • 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.
  • 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.
  • 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 ⁇ - 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)
  • 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 ; Ru
  • 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
  • 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, hal
  • 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 dialkyl
  • 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.
  • halogen preferably fluorine, Ci-Cio-alkyl, Ci-Cio-alkoxy or C6-C24-aryl
  • 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.
  • halogen in particular fluorine, chlorine, bromine or iodine
  • 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).
  • 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,
  • 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
  • phosphinite includes, for example, triphenyl phosphinite, tricyclohexyl phosphinite, triisopropyl phosphinite and methyl diphenyl pho
  • phosphite includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.
  • stibane includes triphenylstiban, tricyclohexylstiban and trimethylstiban.
  • sulfonate includes, for example, trifluoromethanesulfonate, tosylate and mesylate.
  • thioether includes, for example, CH 3 SCH 3 , C 6 H 5 SCH 3 , CH 3 OCH 2 CH 2 SCH 3 and tetrahydrothiophene.
  • 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 ( ⁇ -, ⁇ - and ⁇ -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.
  • 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),
  • 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
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • catalysts falling under the general formula (C) and having the structures (6) (Grubbs (I) catalyst) and (7) (Grubbs (II) catalyst) wherein Cy is cyclohexyl.
  • X 1 , X 2 and L may have the same general, preferred and particularly preferred meanings as in the general formula (C),
  • n 0, 1 or 2
  • n 0, 1, 2, 3 or 4 and
  • R ' are the same or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl,
  • Catalyst (8a) is also referred to as a Nolan catalyst.
  • 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
  • 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.
  • 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).
  • 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
  • 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.
  • 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
  • radicals R 10 and R 11 may be identical or different and denote i-propyl, neopentyl, adamantyl or mesityl.
  • imidazoline or imidazolidine radicals (Im) have the previously mentioned structures (5a-5f), where Mes is in each case 2,4,6-trimethylphenyl.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • radicals R 2 , R 3 , R 4 and R 5 are identical or different and may be hydrogen, organic or inorganic radicals.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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),
  • 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 -
  • 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”.
  • 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.
  • 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.
  • 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 12 has the meanings given for the general formula (D2),
  • n 0, 1, 2 or 3
  • R 6 is hydrogen
  • M represents ruthenium
  • X 1 and X 2 are chlorine at the same time
  • R 1 is an isopropyl radical
  • n 0
  • 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)
  • catalysts of the following structures (18) (“Grela catalyst”) (19), wherein each Mes is 2,4,6-trimethylphenyl.
  • 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
  • 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.
  • the support is preferably a poly (styrenedivinylbenzene) copolymer (PS-DVB).
  • PS-DVB poly (styrenedivinylbenzene) copolymer
  • 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.
  • 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.
  • M is ruthenium or osmium
  • X 1 and X are the same or different and represent anionic ligands
  • R are the same or different and represent organic radicals
  • the catalysts of the general formula (E) are known in principle (see, for example, Angew. Chem. Int.
  • 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).
  • 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.
  • radicals R "in the general formula (E) are preferably identical and are phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.
  • 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,
  • X 3 is an anionic ligand
  • ⁇ - is a non-coordinating anion
  • n 0, 1, 2, 3, 4 or 5.
  • 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.
  • 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,
  • R 19 and R 20 are the same or different and are hydrogen or substituted or unsubstituted
  • catalysts of the general formulas (K), (N) or (Q) are also suitable.
  • 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,
  • Z 1 and Z are the same or different and represent neutral electron donors
  • alkyl independently of one another H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate,
  • 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.
  • 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
  • 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.
  • 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.
  • Z 1 and Z 2 are a single bidentate ligand.
  • 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
  • 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.
  • 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
  • L has a structure of the above-described general formulas (4a) or (4b), in particular of the formulas (5a) to (5f).
  • 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.
  • 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.
  • 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.
  • 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,
  • R 25 -R 32 are identical or different and are hydrogen, halogen, hydroxyl, aldehyde, keto, thiol,
  • 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
  • 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.
  • RI general formula
  • 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),
  • 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).
  • 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)
  • X and X, L and L, n, n ' and R-R have the meanings given for the general formulas (R2a) and (R2b).
  • these ruthenium or osmium carbene catalysts are five-coordinate.
  • R 15 -R 32 are identical or different and denote hydrogen, halogen, hydroxyl, aldehyde, keto,
  • These radicals may each be optionally substituted by one or more alky
  • n 0 or 1
  • 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.
  • C3-C5-cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • 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.
  • 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).
  • 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).
  • M represents ruthenium
  • X 1 and X 2 are simultaneously halogen
  • n 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),
  • n 0 or 1
  • A represents oxygen, sulfur, C (C r Cio-alkyl) 2, -C (Ci-Ci 0 alkyl) 2 -C (Ci-Ci 0 alkyl) 2 -,
  • M represents ruthenium
  • n 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,
  • R-R have the general or preferred meanings given for the general formulas (R2a) and (R2b),
  • n 0 or 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).
  • 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
  • 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
  • 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,
  • L is an electron donating ligand attached to X 1 via carbon-carbon and / or
  • Carbon-heteroatom bonds may be linked.
  • 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.
  • Y is preferably oxygen.
  • R is preferably H, halogen, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, amido, alkylsulfonyl, arylsulfonyl, alkylthio, arylthio or sulfonamido.
  • 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.
  • R 1 is H or an alkoxy group and R 2 is hydrogen.
  • R 3 is preferably an alkyl, aryl, heteroaryl, alkylcarbonyl or arylcarbonyl group.
  • R 3 is particularly preferably isopropyl, sec-butyl and methoxyethyl.
  • EWG preferably represents an aminosulfonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, aminocarbonyl, arylsulfonyl, alkylcarbonyl, aryloxycarbonyl, halogen or haloalkyl group.
  • 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.
  • 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.
  • 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,
  • R 8 and R 9 are the same or different and Ci_g is alkyl or Ce-n aryl.
  • M 1 represents rhodium (Rh) or ruthenium (Ru),
  • M 2 represents ruthenium (Ru) or a lanthanide
  • M 1 is rhodium (Rh)
  • M 2 is ruthenium (Ru) or a lanthanide
  • 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,
  • 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.
  • L 1 is selected from trimethylphosphane, triethylphosphine, triphenylphosphine
  • 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.
  • the hydrogenation is usually carried out in a solvent, preferably an organic solvent.
  • 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.
  • nitrile rubber is usually dissolved in at least one solvent.
  • 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.
  • 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 + Kunststoffe, Vol. 42 (1989), No. 2 107-10 (part 1) and in rubbers + rubber, plastics, Vol. 42. (1989), No. 3, pp. 194-197.
  • the reactor 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.
  • the hydrogenation can be carried out with the addition of a phosphine or diphosphane as a co-catalyst.
  • 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 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),
  • R are the same or different and have the same meanings as in the general
  • k 0 or 1
  • X represents a straight-chain or branched alkanediyl, alkenediyl or alkinediyl group.
  • 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-eth
  • 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.
  • 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.
  • heteroaryl radicals are pyridinyl, oxazolyl, benzofuranyl, dibenzofuranyl and quinolinyl.
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • 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 , ⁇ ( ⁇ - ⁇ O) 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)
  • 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.
  • diphosphanes which can also be used according to the invention are further published in Chem. Eur. J. 2008, 14, 9491-9494. For example:
  • 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.
  • nitrile rubber 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.
  • 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.
  • 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 invention furthermore relates to vulcanizable mixtures comprising at least one hydrogenated nitrile rubber according to the invention and at least one crosslinking system.
  • vulcanizable mixtures may preferably contain one or more further typical rubber additives.
  • 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.
  • 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.
  • crosslinking yield can be increased.
  • additives 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.
  • 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).
  • DTDM dimorpholyl disulfide
  • MB SS 2-morpholino dithiobenzothiazole
  • caprolactam disulfide caprolactam disulfide
  • DPTT dipentamethylene thiuram tetrasulfide
  • TMTD tetramethyl thiuram disulfide
  • 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.
  • 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.
  • 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.
  • SDEC sodium diethyldithiocarbamate
  • SDBC sodium dibutyldithiocarbamate
  • ZDMC
  • thiurams e.g. Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Dimethyldiphenylthiuramdisulfid, Tetrabenzylthiuramdisulfid, Dipentamethylenthiuram- tetrasulfid or Tetraethylthiuramdisulfid (TETD) are used.
  • thiazoles e.g. 2-mercaptobenzothiazole (MBT), dibenzthiazyl disulfide (MBTS), zinc mercaptobenzothiazole (ZMBT) or copper 2-mercaptobenzothiazole.
  • 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.
  • CBS Cyclohexyl-2-benzothiazyl sulfenamide
  • TBBS N-tert-butyl-2-benzthiazyl sulfenamide
  • DCBS N, N'-dicyclohexyl-2-benzthiazyl sulfenamide
  • MFS 2-morpholin
  • xanthates e.g. Natriumdibutylxanthogenat, Zinkisopropyldibutylxanthogenat or Zinkdibutylxanthogenat be used.
  • guanidine derivatives e.g. Diphenylguanidine (DPG), di-o-tolylguanidine (DOTG) or o-Tolylbiguanid (OTBG) can be used.
  • DPG Diphenylguanidine
  • DDG di-o-tolylguanidine
  • OTBG o-Tolylbiguanid
  • dithiophosphates such as zinc di can (C2 -Ci6) alkyldithiophosphate Kupferdi (C 2 - Ci6) alkyldithiophosphate and Dithiophosphorylpolysulfid be used.
  • dithiophosphates such as zinc di can (C2 -Ci6) alkyldithiophosphate Kupferdi (C 2 - Ci6) alkyldithiophosphate and Dithiophosphorylpolysulfid be used.
  • caprolactam for example, dithio-bis-caprolactam can be used.
  • thiourea derivatives for example, ⁇ , ⁇ '-diphenylthiourea (DPTU), diethylthiourea (DETU) and ethylene thiourea (ETU) can be used.
  • DPTU ⁇ , ⁇ '-diphenylthiourea
  • DETU diethylthiourea
  • ETU ethylene thiourea
  • 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.
  • 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).
  • 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.
  • 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.
  • polyamine crosslinkers (ii) examples 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.
  • crosslinking accelerator any known to those skilled in the art can be used in combination with the polyamine crosslinker, preferably a basic crosslinking accelerator.
  • 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.
  • aldehydocin crosslinking accelerators such as, for example, n-butylaldehydoaniline.
  • At least one bi- or polycyclic aminic base is particularly preferably used as crosslinking accelerator.
  • DBU 8-diazabicyclo [5.4.0] undec-7-ene
  • DBN 5-diazabicyclo [4.3.0] -5-nonene
  • DBCO 4-diazabicyclo [2.2.2] octane
  • TBD 1,5,7-triazabicyclo [4.4.0] dec-5-ene
  • MTBD dec-5-ene
  • 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 are 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.
  • 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), ⁇ , ⁇ '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.
  • 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
  • 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.
  • 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.
  • Fibers 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.
  • 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.
  • the internal mixer 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention makes it possible to obtain vulcanizates having the desired property profile.
  • Capillary column HP-5, length: 30 m; Inner diameter 0.32 mm; Film thickness: 0.25 ⁇
  • Injection amount 1 ⁇ .
  • 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).
  • a defined amount of 1, 2-dichlorobenzene as an internal standard (0.25 mg dissolved in 2 ml of acetone) was added and mixed.
  • 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.
  • 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.
  • 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.
  • 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).
  • the storage stabilities (LS) were determined as the difference of the Mooney viscosity values before and after hot air storage:
  • Example 1.6 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
  • 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.
  • 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.
  • 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
  • Vulkanox® KB or Vulkanox® BKF were based on the solid contained in the latex and are stated in% by weight.
  • the solids content of the latices was adjusted to 20% by weight by adding the appropriate amount of deionized water.
  • aqueous solutions of sodium chloride and magnesium chloride were used for the coagulation of the NBR latexes.
  • 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.
  • 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.
  • 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. ".
  • 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.
  • nitrile rubbers were thermally dried to residual moisture contents ⁇ 1% by weight after mechanical dehydration and comminution by means of fluid bed drying.
  • a fluidized bed dryer (fast dryer TG 200) from Kurt Retsch (Haan / Dusseldorf), which was equipped with a drying container of 6 L content.
  • 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 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.%.
  • 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.
  • the polymer solution 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 isolation of the hydrogenated nitrile rubbers from chlorobenzene solution was carried out batchwise at atmospheric pressure by steam distillation.
  • a stirrable glass 20 L-planschliff notioner was used with jacket heating.
  • the feeding of water vapor took place via a bottom valve.
  • 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.
  • the pH of the aqueous phase was maintained in the pH range of 7.7 to 8.3 throughout the distillation process.
  • 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.
  • 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).
  • the specimens necessary for the Vulkanisat charactermaschine 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.
  • 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 ( ⁇ 2oo ⁇ 17 , 5 MPa and ⁇ 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 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%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne de nouveaux caoutchoucs nitriles hydrogénés qui possèdent une teneur en phénol spéciale, un procédé pour les fabriquer, des mélanges vulcanisables les contenant, ainsi que les produits vulcanisés ainsi obtenus. Ces produits vulcanisés se caractérisent par des modules et des valeurs de déformation résiduelle après compression particulièrement bon(ne)s ainsi que par de très bonnes stabilités au stockage.
EP14828164.5A 2013-12-30 2014-12-29 Caoutchoucs nitriles hydrogénés contenant du phénol Withdrawn EP3090019A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14828164.5A EP3090019A1 (fr) 2013-12-30 2014-12-29 Caoutchoucs nitriles hydrogénés contenant du phénol

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13199834 2013-12-30
PCT/EP2014/079370 WO2015101599A1 (fr) 2013-12-30 2014-12-29 Caoutchoucs nitriles hydrogénés contenant du phénol
EP14828164.5A EP3090019A1 (fr) 2013-12-30 2014-12-29 Caoutchoucs nitriles hydrogénés contenant du phénol

Publications (1)

Publication Number Publication Date
EP3090019A1 true EP3090019A1 (fr) 2016-11-09

Family

ID=49882961

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14828164.5A Withdrawn EP3090019A1 (fr) 2013-12-30 2014-12-29 Caoutchoucs nitriles hydrogénés contenant du phénol

Country Status (7)

Country Link
US (1) US20160376421A1 (fr)
EP (1) EP3090019A1 (fr)
JP (2) JP6457538B2 (fr)
KR (1) KR102240055B1 (fr)
CN (1) CN105992797B (fr)
TW (1) TWI649335B (fr)
WO (1) WO2015101599A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102022399B1 (ko) * 2015-09-09 2019-09-18 주식회사 엘지화학 탄소 나노튜브 분산액 및 이의 제조방법
CN105602022B (zh) * 2016-01-29 2018-03-23 福建出入境检验检疫局检验检疫技术中心 一种苯酚测定用标准橡胶样品的制备方法
US10703868B2 (en) * 2016-07-13 2020-07-07 Dae Ho Jeong Composition for flooring containing coconut fibers and method for manufacturing flooring using same
CN111107985B (zh) * 2017-09-20 2022-06-07 阿朗新科德国有限责任公司 具有高热导率的可固化的hnbr组合物
KR102567856B1 (ko) 2017-11-10 2023-08-16 니폰 제온 가부시키가이샤 수소화 니트릴 고무의 제조 방법
CN110605803B (zh) * 2019-09-19 2021-09-24 山东京博中聚新材料有限公司 一种生产丁基橡胶的后处理方法
CN111607021A (zh) * 2020-06-30 2020-09-01 内蒙合成化工研究所 一种连续离心工艺去除橡胶类聚合物中灰分的方法
JP6911987B1 (ja) * 2020-08-31 2021-07-28 日本ゼオン株式会社 電気化学素子用分散剤組成物、電気化学素子用導電材分散液、電気化学素子電極用スラリー、電気化学素子用電極及び電気化学素子
JP6911985B1 (ja) 2020-08-31 2021-07-28 日本ゼオン株式会社 電気化学素子用分散剤組成物、電気化学素子用導電材分散液、電気化学素子電極用スラリー組成物及びその製造方法、電気化学素子用電極、並びに電気化学素子
WO2023238066A1 (fr) * 2022-06-08 2023-12-14 Danfoss A/S Matériau hnbr à faible extraction présentant une adhérence à des polyamides

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5258467A (en) * 1992-09-02 1993-11-02 Polysar Rubber Corporation Catalytic solution hydrogenation of nitrile rubber
US5397839A (en) * 1993-12-13 1995-03-14 Advanced Elastomer Systems, L.P. Polyester-hydrogenated diene rubber compositions
JP3770285B2 (ja) * 1996-09-27 2006-04-26 日本ゼオン株式会社 カルボキシル化ニトリル基含有高飽和共重合体ゴム
JPH10279734A (ja) * 1997-03-31 1998-10-20 Nippon Zeon Co Ltd エチレン性不飽和カルボン酸金属塩含有加硫性ゴム組成物
DE10066134B4 (de) * 2000-11-27 2006-09-14 Basf Coatings Ag Mischsystem für Pulverlacke
CA2369900A1 (fr) * 2002-01-31 2003-07-31 Bayer Inc. Produit de vulcanisation de polymere nitrilique ameliore et procede pour sa production
DE102005042265A1 (de) * 2005-09-06 2007-03-08 Lanxess Deutschland Gmbh Vernetzbare Zusammensetzungen, daraus erhältliche thermoplastische Elastomere und deren Verwendung
DE102007024008A1 (de) * 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh Nitrilkautschuke
CN101925614B (zh) * 2008-01-29 2013-08-07 朗盛德国有限责任公司 任选包含烷硫基端基并且任选氢化的丁腈橡胶
CN101945896B (zh) * 2008-01-29 2013-07-24 朗盛德国有限责任公司 任选包含烷硫基端基并且任选氢化的丁腈橡胶
EP2147931A1 (fr) * 2008-07-24 2010-01-27 LANXESS Inc. Procédé pour l'hydrogénation continue des liaisons de module carbone-carbone dans un polymère non saturé
EP2368917B1 (fr) 2010-03-25 2013-01-09 LANXESS International SA Processus pour la production d'eau et de caoutchoucs de nitrile hydrogéné sans solvant
CN102516567A (zh) * 2011-12-02 2012-06-27 福建师范大学 一种补强防老腈类弹性体的配位交联方法
CN103146041B (zh) * 2013-03-18 2015-02-25 东华大学 一种氢化羧基丁腈橡胶基阻尼复合材料及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015101599A1 *

Also Published As

Publication number Publication date
JP2017504696A (ja) 2017-02-09
CN105992797A (zh) 2016-10-05
JP6457538B2 (ja) 2019-01-23
KR102240055B1 (ko) 2021-04-15
CN105992797B (zh) 2018-11-16
US20160376421A1 (en) 2016-12-29
JP2018145434A (ja) 2018-09-20
WO2015101599A1 (fr) 2015-07-09
TW201546096A (zh) 2015-12-16
KR20160105833A (ko) 2016-09-07
TWI649335B (zh) 2019-02-01

Similar Documents

Publication Publication Date Title
WO2015101599A1 (fr) Caoutchoucs nitriles hydrogénés contenant du phénol
EP2484700B1 (fr) Caoutchoucs nitriles fonctionnalisés et leur fabrication
EP2152760A1 (fr) Caoutchoucs nitrile
EP3090000B1 (fr) Caoutchouc au nitrile hydrogéné contenant de l'oxyde de phosphane ou de diphosphane
EP2889326B1 (fr) Caoutchoucs nitriles stables au stockage et leur procédé de fabrication
EP3090017B1 (fr) Caoutchouc de nitrile hydrogéné contenant du phénol
EP3090002B1 (fr) Caoutchouc au nitrile hydrogéné contenant de l'oxyde de phosphane ou de diphosphane
EP3090001B1 (fr) Caoutchouc au nitrile hydrogéné contenant du sulfure de phosphane ou de diphosphane

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160801

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170804

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210504

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20210915