EP3090016A1 - Caoutchoucs nitriles stables au stockage et procédé pour les fabriquer - Google Patents

Caoutchoucs nitriles stables au stockage et procédé pour les fabriquer

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Publication number
EP3090016A1
EP3090016A1 EP14828481.3A EP14828481A EP3090016A1 EP 3090016 A1 EP3090016 A1 EP 3090016A1 EP 14828481 A EP14828481 A EP 14828481A EP 3090016 A1 EP3090016 A1 EP 3090016A1
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EP
European Patent Office
Prior art keywords
nitrile rubber
acrylate
nitrile
weight
meth
Prior art date
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EP14828481.3A
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German (de)
English (en)
Inventor
Werner Obrecht
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Arlanxeo Deutschland GmbH
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Arlanxeo Deutschland GmbH
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Priority to EP14828481.3A priority Critical patent/EP3090016A1/fr
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Classifications

    • 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
    • C08L9/04—Latex
    • 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
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • the invention relates to novel phenolic nitrile rubbers, a process for their preparation, vulcanizable mixtures comprising the novel nitrile rubbers and vulcanizates obtainable therefrom.
  • Nitrile rubbers also abbreviated to "NBR”, are understood to mean rubbers which are copolymers or terpolymers of at least one ⁇ , ⁇ -unsaturated nitrile monomer, at least one conjugated diene monomer and optionally one or more further copolymerizable monomers.
  • Nitrile rubbers are used in a wide variety of applications, such as automotive seals, hoses, belts and damping elements, stators, borehole seals and valve seals used in oil production, as well as many parts of the aerospace, electrical, mechanical and marine industries.
  • mixtures of the nitrile rubber with different components of the mixture, in particular with sulfur and with vulcanization accelerators are needed.
  • the rubber mixtures In order to avoid premature scorching during the preparation of the mixture, the rubber mixtures must have a long scorch time.
  • the storage stability of the nitrile rubber, the vulcanization rate of the rubber mixtures and the properties of the vulcanizates, in particular the module level at 300% elongation must not be impaired
  • NBR is prepared by emulsion polymerization, initially obtaining an NBR latex.
  • the NBR solid is isolated from this latex by coagulation.
  • salts and acids are used for coagulation.
  • monovalent metal ions eg in the form of sodium chloride
  • polyvalent metal ions eg in the form of calcium chloride, magnesium chloride or aluminum sulfate (Kolloid-Z. 154, 154 (1957) )
  • polyvalent metal ions leads to a more or less large inclusion of the emulsifier in the product (Houben-Weyl (1961), Methods of Org.
  • aliphatic mercaptans having a carbon number> 6, preferably 6-12 are used for the molecular weight control in the emulsion polymerization of butadiene and butadiene derivatives and for the copolymerization of butadiene with other monomers such as acrylonitrile.
  • the mercaptans are added portionwise or continuously during the course of the polymerization. In this way, the formation of gel in the polymerization is avoided.
  • the use of anti-aging agents is not mentioned. Therefore, no measures for improving the modulus level and the compression set of vulcanizates of nitrile rubber by an anti-aging agent and its amount can be derived. From US Pat. No.
  • DD 154 702 does not specify the use of anti-aging agents. Accordingly, DD 154 702 gives no indications of the influence of aging inhibitors on the storage stability, the processing safety and the vulcanization rate of rubber compounds and on the influence of anti-aging agents on the properties of unvulcanized nitrile rubbers.
  • 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 used. Again, sodium chloride is used as the preferred water-soluble salt. The coagulum is mechanically separated, optionally washed with water and the remaining water removed.
  • DE-OS 30 43 688 it is also the goal of DE-OS 30 43 688 to reduce the amount of electrolyte necessary for the latex coagulation as much as possible.
  • in the electrolytic coagulation of latices in addition to the inorganic coagulant as adjuvants, either plant-derived proteinaceous materials or polysaccharides, e.g. Strength and
  • 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 processing and on the influence of these anti-aging agents on the properties of
  • Nitrile rubber and its vulcanizates are not found.
  • 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-A-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 in the form of a powder having particle diameters in the range of 0.3 to 4 mm, which is optionally added before the drying with zinc soaps as Antiagglomeratinsmittel.
  • 4,383,108 discloses that the latex is stabilized before coagulation by adding 1.5 parts by weight of a "phosphite of polyalkylphenol.” Details of the influence of the aging inhibitor on properties of nitrile rubber, such as storage stability, Processing safety, vulcanization rate and module level at 300% elongation are not found.
  • US Pat. No. 5,708,132 describes the preparation of storage-stable and rapidly vulcanizing nitrile rubbers, wherein the nitrile rubber latex is mixed before coagulation with a mixture of a hydrolysis-susceptible and a hydrolysis-resistant aging inhibitor.
  • hydrolysis-susceptible aging inhibitor alkylated aryl phosphites, in particular tris (nonylphenyl) phosphite, are used.
  • hydrolysis-resistant aging inhibitors sterically hindered phenols, especially octadecyl-3,5-di-t.butyl-4-hydroxyhydro cinnemate (Ultranox® 276) are called.
  • 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
  • Z5 precipitants As additional precipitating agents, alkali metal salts of inorganic acids can be used. Also precipitation aids such as gelatin, polyvinyl alcohol, cellulose, carboxylated cellulose and cationic and anionic polyelectrolytes or mixtures thereof can be added. Subsequently, the resulting fatty and resin acids are washed out with aqueous alkali metal hydroxide solutions and the polymer subjected to shearing until a
  • Nitrile rubbers with low residual emulsifier contents and cation contents are obtained. There are no indications for the targeted production of nitrile rubbers with certain technological properties. The influence of aging inhibitors on the product properties such as storage stability, processing safety and vulcanization rate of rubber compounds is not investigated.
  • the pH of the aqueous THF solution should be> 5, preferably> 5.5, more preferably> 6.
  • US 4,965,323 there are no indications of the type and amount of the anti-aging agent to be used in the preparation of the nitrile rubber.
  • 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 preferred embodiment is a nitrile rubber which is substantially halogen-free and is obtained by reacting the latex coagulation in the presence of a nonionic surfactant and using halogenated rubber.
  • 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.
  • nitrile rubbers produced in this way they have a favorable property profile, a good processability of the rubber mixtures, and a low profile Allow mold contamination during processing.
  • the resulting vulcanizates should have a good combination of low temperature and oil resistance and have good mechanical properties. It is further claimed that the nitrile rubbers have a short scorching time, a high crosslinking density can be achieved, and the vulcanization rate is high, in particular with NBR types for injection molding processing.
  • EP-A-0 692 496 With respect to the use of anti-aging agents, nothing is said in the specifications of EP-A-0 692 496, EP-A-0 779 301 and EP-A-0 779 300.
  • the examples show that the aging inhibitor used is an alkylated phenol which is not further defined in the chemical structure. Further, it can be seen from the examples that 2 parts of the alkylated phenol are used. It can be assumed that these are weight parts. The reference value remains open (based on monomer or polymer).
  • 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 + ), 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 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 when the latex coagulation is carried out in the presence of at least one salt based on aluminum, calcium, magnesium, potassium, sodium or lithium, coagulation or washing in the presence of a Ca salt or wash water containing Ca ions 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 In the general part of DE 102007024008 a number of anti-aging agents are listed, which are added to the Nitrilkautschukuatexx prior to coagulation, which is missing in the general part 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; the amounts of 2,6-di-tert-butyl-p-cresol used were not varied in the investigations.
  • DE 102007024010 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 + ) and c (K + ) represent the concentration of calcium
  • Magnesium, sodium and potassium ions in nitrile rubber are in ppm, 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.
  • Such 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.
  • 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 special index with respect to the contents of sodium, potassium, magnesium and calcium ions contained in the nitrile rubber (ion index).
  • ion index a number of anti-aging agents are listed, which are added to the Nitrilkautschuklatex prior to coagulation, which generally lacking in the form of quantities. From the examples it is apparent that the investigations were carried out with 2,2-methylene-bis (4-methyl-6-tert-butylphenol), the amount in a range of 0, 1 to 0.8 wt.% Based on Solid rubber was varied.
  • EP 2 238 175 A describes nitrile rubbers with high storage stability which are obtained by latex coagulation with alkali salts in combination with gelatin and by special conditions in latex coagulation and the subsequent crumb washing.
  • the nitrile rubbers have special characteristics with respect to the amounts of sodium, potassium, magnesium and calcium ions (ion indices) remaining in the nitrile rubber.
  • the general part enumerates a number of anti-aging agents which are added to the nitrile rubber latex prior to coagulation, details of which are lacking. It can be seen from the example section that the investigations were carried out with a constant amount of 2,6-di-tert-butyl-p-cresol (1.0% by weight, based on solid rubber).
  • EP 2 238 176 A describes nitrile rubbers with high storage stability, which are obtained by latex coagulation with alkaline earth salts in combination with polyvinyl alcohol.
  • the nitrile rubbers have particular content with respect to the content of sodium, potassium, magnesium and calcium ions remaining in the nitrile rubber (ion index).
  • EP 2 238 176 A enumerates a number of anti-aging agents which are added to the nitrile rubber latex prior to coagulation, details of which are not given. It can be seen from the example section that the investigations were carried out with a constant amount of 2,6-di-tert-butyl-p-cresol (1.0% by weight, based on solid rubber). The influence of the remaining in dry nitrile rubber 2,6-di-tert-butyl-p-cresol on the properties of nitrile rubber, its mixtures and vulcanizates no conclusions can be drawn.
  • EP 1 331 074 A describes the preparation of mixtures based on nitrile-containing rubbers with a reduced tendency to mold contamination by injection molding.
  • the object is achieved by nitrile rubber or hydrogenated nitrile rubber having a fatty acid acid content in the range of 0.1-0.5 wt.%.
  • the influence of different mixture components on the form contamination behavior is investigated, i.a. of di-tert-butyl-p-cresol, which is varied in amounts of 0.1-0.5 parts by weight.
  • the object of the present invention was thus to provide a storage-stable nitrile rubber whose rubber mixtures simultaneously have a high processing safety and a high vulcanization rate and which in the vulcanized state additionally has an improved level of stress at 300% elongation and a very good elongation at break.
  • a nitrile rubber with the above property profile is obtained when it contains a specific substituted phenol in a certain amount.
  • This new nitrile rubber with the desired property profile becomes accessible one prepares the nitrile rubber after its preparation by emulsion polymerization and before working up with the corresponding special substituted phenol in a certain amount and then isolated with drying, preferably using a fluidized bed dryer.
  • the present invention thus provides a nitrile rubber containing at least one substituted phenol of the general formula (I) in an amount in the range from 0.25 to ⁇ 0.9% by weight, preferably from 0.3 to 0.85% by weight, particularly preferably from 0.4% by weight to 0.85% by weight, very particularly preferably from 0.4% by weight to less than or equal to 0.81% by weight and in particular 0.45% by weight to less than or equal to 0.81 % By weight, in each case based on the nitrile rubber,
  • 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 not hydrogen.
  • the present invention furthermore relates to vulcanizable mixtures of these nitrile rubbers according to the invention and to processes for the preparation of vulcanizates based thereon and to the vulcanizates obtainable thereby, in particular as moldings.
  • the present invention furthermore provides a process for preparing these nitrile rubbers according to the invention containing at least one substituted phenol of the general formula (I) in an amount in the range from 0.25 to ⁇ 0.9% by weight, preferably from 0.3 to 0 , 85% by weight), particularly preferably from 0.4% by weight to 0.85% by weight, very particularly preferably from 0.4% by weight to less than or equal to 0.81% by weight, and in particular 0, 45 wt.%> To less than or equal to 0.81 wt.%>, Based on the nitrile rubber, characterized in that
  • the resulting suspension of the nitrile rubber in the aqueous medium is admixed with at least one substituted phenol of the general formula (I), preferably in an amount in the range from 0.9 to 1.6% by weight, based on the nitrile rubber
  • R 1 , R 2 , R 3 , R 4 and R 5 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 having 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, and
  • the drying is carried out at a temperature in the range of 100 to 180 ° C, preferably at 110 to 150 ° C and the content of substituted phenol of the general formula (I) to the amount in the range of 0.25 to ⁇ 0.9 wt.%, Preferably from 0.3 to 0.85 wt.%), Particularly preferably from 0.4 wt.%> To 0.85 wt.%>, Very particularly preferably from 0.4 wt.%> To less than or equal to 0.81% by weight> and in particular 0.45% by weight> less than or equal to 0.81% by weight>, based on the nitrile rubber.
  • the rubber of the invention is characterized in that vulcanizable mixtures based thereon have improved processing safety in the form of an extended scorching time ("Mooney Scorch") which is determined with the aid of a shear disk viscometer in accordance with DIN 53 523 at 120 ° C.
  • Vulcanizable mixtures of the invention based on nitrile rubber have a higher vulcanization rate (t 90 -ti 0 ) and an improved modulus value at 300% in the vulcanized state> elongation and elongation at break B -
  • the standards by which the stated properties are measured are listed in the examples of this application.
  • Nitrile rubbers according to the invention are Nitrile rubbers according to the invention:
  • the nitrile rubber according to the invention comprises at least one substituted phenol of the general formula (I),
  • R 1 , R 2 , R 3 , R 4 and R 5 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 having one, two or three heteroatoms which are preferably oxygen, where at least one of R 1 , R 2 , R 3 , R 4 and R 5 is other than hydrogen,
  • the nitrile rubber of the invention contains substituted phenols of the general formula (I) wherein
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen, hydroxy, a linear or branched Ci-Cg 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, more preferably cyclopentyl or cyclohexyl, or a phenyl radical, wherein at least one of R 1 , R 2 , R 3 , R 4 and R 5 is not equal to Is hydrogen.
  • substituted phenols of the general formula (I) in which two or three of the radicals R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen and the remaining three or two of the radicals R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydroxy, a linear or branched Ci-Cg 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, more preferably cyclopentyl or cyclohexyl, or a phenyl radical.
  • substituted phenols of the general formula (I) selected from the group consisting of the compounds mentioned below:
  • the substituted phenols present in the nitrile rubbers according to the invention are known, for example, from DE-OS 2150639 and DE 3337567 A1 and are either commercially available or can be prepared 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 their content Therefore, to the essential value in the range of 0.25 to ⁇ 0.9% by weight, preferably from 0.3 to 0.85% by weight, particularly preferably 0.4 to 0.85% by weight, very particularly preferably 0 , 4 wt.% To less than or equal to 0.81 wt.%> And in particular 0.45 wt.%> To less than or equal to 0.81 wt.%>, Based on the nitrile rubber can be adjusted. This adjustment is possible for the skilled person by known measures.
  • the 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 repeat units of the at least one conjugated diene are preferably based on (C 4 -C 6) conjugated dienes or mixtures thereof. Particular preference is given to 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene and mixtures thereof. Particularly preferred are 1,3-butadiene, isoprene and mixtures thereof. Very particular preference is given to 1,3-butadiene.
  • 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.
  • this may be e.g. aromatic vinyl monomers, preferably styrene, ⁇ -methylstyrene and vinylpyridine, fluorine-containing vinyl monomers, preferably fluoroethyl vinyl ether, fluoropropylvinylether, o-fluoromethylstyrene, vinylpentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or else copolymerizable antiageing 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 and also non-
  • hydroxyl-containing monomers may be used as copolymerizable termonomers, 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)
  • 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.
  • esters of ⁇ , ⁇ -unsaturated monocarboxylic acids preferably their alkyl esters and alkoxyalkyl esters.
  • Alkyl esters, in particular CpCig alkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are 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 particularly 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 acrylates and cyanoalkyl methacrylates in which the C atom number of the cyanoalkyl group is 2-12, preferably ⁇ -cyanoethyl acrylate, ⁇ -cyanoethyl acrylate and 5-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-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.
  • Z0 can also be used mono- or diesters of ⁇ , ⁇ -unsaturated dicarboxylic acids.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid mono- or diesters may, for example, be alkyl, preferably C 1 -C 10 -alkyl, in particular ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or n-hexyl, alkoxyalkyl, preferably C2-C12 alkoxyalkyl, more preferably C3-C 8 - alkoxy Z5 alkyl, hydroxyalkyl, preferably C1-C12 hydroxyalkyl, more preferably C 2 -C 8 - hydroxyalkyl, cycloalkyl, preferably C 5 -Ci2-cycloalkyl, most preferably C6-Ci2-cycloalkyl, alkylcycloalkyl, preferably C6-Ci2-alkylcycloalkyl, more preferably C 7 -Cio-alkylcycloalky
  • alkyl esters of ⁇ , ⁇ -unsaturated monocarboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate , 2-Ethlyhexyl (meth) acrylate, octyl (meth) acrylate, 2-propylheptyl acrylate and lauryl (meth) acrylate.
  • 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 monomethyl fumarate, monoethyl fumarate, 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 Acidmonoarylester preferably Monophenylcitraconat
  • Citraconic acid monobenzyl ester preferably monobenzyl citraconate
  • Itaconic acid monoalkyl ester preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;
  • Itaconic acid monocycloalkyl ester preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate; Itaconic acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl itaconate 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 according to the invention can vary within wide limits.
  • 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 of the invention add up to 100% by weight each.
  • the additional monomers can be present in amounts of from 0 to 40% by weight, preferably 0 to 30% by weight, particularly 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 repeating units of the ⁇ , ⁇ -unsaturated nitriles are replaced by the proportions of these additional 5 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.
  • esters of (meth) acrylic acid are used as additional monomers ⁇ , ⁇ -unsaturated mono- or 10 dicarboxylic acids, this is usually done in amounts of less than 10 wt.%>.
  • Nitrile rubbers according to the invention which have repeating units of acrylonitrile and 1,3-butadiene are preferred. Also preferred are nitrile rubbers, the repeat 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-
  • the nitrogen content is determined in the 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.%> Soluble.
  • the glass transition temperatures of the 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 nitrile rubbers have Mooney viscosities ML 1 + 4 at 100 ° C of 10 to 150 Mooney - 30 units (MU), preferably from 20 to 100 MU.
  • the Mooney viscosities of the nitrile rubbers are 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 35 nitrile rubbers or of the hydrogenated nitrile rubbers after drying and before aging are referred to below as MV 0.
  • MV The Mooney viscosities are determined.
  • the values for the Mooney viscosity determined after storage of the nitrile rubber at 100 ° C. for 48 hours are designated MV 1.
  • the storage stability (LS) is determined as the difference between the Mooney viscosity values before and after hot air storage:
  • R 1 , R 2 , R 3 , R 4 and R 5 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 having one, two or three heteroatoms which are preferably oxygen, where at least one of R 1 , R 2 , R 3 , R 4 and R 5 is other than hydrogen,
  • the resulting suspension of the nitrile rubber in the aqueous medium is admixed with at least one substituted phenol of the general formula (I), preferably in an amount in the range from 0.9 to 1.6% by weight, based on the nitrile rubber
  • the drying is carried out at a temperature in the range of 100 to 180 ° C, preferably at 1 10 to 150 ° C and the content of substituted phenol of the general formula (I) to the amount in the range of 0.25 to ⁇ 0.9 wt.%>, Preferably from 0.3 to 0.85 wt.%), Particularly preferably from 0.4 wt.%> To 0.85 wt.%>, Very particularly preferably 0.4 wt.% > to less than or equal to 0.81% by weight> and in particular 0.45% by weight> to less than or equal to 0.81% by weight>, based on the nitrile rubber.
  • Step 1
  • the preparation of the nitrile rubber is typically carried out via an emulsion polymerization to form a suspension of the nitrile rubber in an aqueous medium. This is usually referred to as the formation of a nitrile rubber latex.
  • the emulsion polymerization is well known to the skilled person and extensively described in the literature.
  • Emulsion polymerizations are carried out using emulsifiers.
  • emulsifiers for this purpose, a wide range of emulsifiers is known and accessible to the person skilled in the art.
  • emulsifiers for example, anionic emulsifiers or neutral emulsifiers can be used.
  • Anionic emulsifiers are preferably used, particularly preferably in the form of water-soluble salts.
  • Modified resin acids obtained by dimerization, disproportionation, hydrogenation and modification of resin acid mixtures containing abietic acid, neoabietic acid, palustric acid, levopimaric acid can be used as anionic emulsifiers.
  • a particularly preferred modified rosin acid is the disproportionated rosin acid (Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 31, pp. 345-355).
  • anionic emulsifiers and fatty acids can be used. These contain 6 to 22 C atoms per molecule. They can be fully saturated or contain one or more double bonds in the molecule.
  • fatty acids are caproic acid, lauric acid, myristic acid, palmitic acid. acid, stearic acid, oleic acid, linoleic acid, linolenic acid.
  • the carboxylic acids are usually based on origin-specific oils or fats such. Castoroil, cottonseed, peanut oil, linseed oil, coconut fat, palm kernel oil, olive oil, rapeseed oil, soybean oil, fish oil and beef tallow, etc. (Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 13, pp.
  • carboxylic acids are derived from coconut fatty acid and beef tallow and are partially or completely hydrogenated. Such carboxylic acids based on modified resin acids or fatty acids are used as water-soluble lithium sodium, potassium and ammonium salts. Sodium and potassium salts are preferred.
  • Suitable anionic emulsifiers are also sulfonates, sulfates and phosphates which are bonded to an organic radical.
  • Suitable organic radicals are aliphatic, aromatic, alkylated aromatics, fused aromatics, and methylene-bridged aromatics, where the methylene-bridged and fused aromatics may additionally be alkylated.
  • the length of the alkyl chains is 6 to 25 C atoms.
  • the length of the alkyl chains bonded to the aromatics is between 3 and 12 C atoms.
  • the sulfates, sulfonates and phosphates are used as lithium, sodium, potassium and ammonium salts.
  • the sodium, potassium and ammonium salts are preferred.
  • sulfonates, sulfates and phosphates are Na lauryl sulfate, Na alkyl sulfonate, Na alkylarylsulfonate, Na salts methylenverbschreibter arylsulfonates, Na salts alkylated Naphthalinsulfonate and the Na salts of methylenverbschreibter naphthalenesulfonates, which may also be oligomerized, the degree of oligomerization between 2 to 10 lies.
  • the alkylated naphthalenesulfonic acids and the methylene-bridged (and optionally alkylated) naphthalenesulfonic acids are present as mixtures of isomers, which may also contain more than 1 sulfonic acid group (2 to 3 sulfonic acid groups) in the molecule.
  • Neutral emulsifiers are derived from addition products of ethylene oxide and propylene oxide on compounds with sufficiently acidic hydrogen. These include, for example, phenol, alkylated phenol and alkylated amines. The average degrees of polymerization of the epoxides are between 2 and 20.
  • neutral emulsifiers are ethoxylated nonylphenols having 8, 10 and 12 ethylene oxide units.
  • the neutral emulsifiers are usually not used alone, but in combination with anionic emulsifiers.
  • Preferred are the Na and K salts of disproportionated abietic acid and partially hydrogenated tallow fatty acid, and mixtures thereof, sodium lauryl sulfate, Na alkyl sulfonates, sodium alkyl benzene sulfonate and alkylated and methylene-bridged naphthalenesulfonic acids.
  • the emulsifiers are in an amount of 0.2 to 15 parts by weight, preferably 0.5 to 12.5 parts by weight, more preferably 1.0 to 10 parts by weight based on 100 parts by weight of Monomermischung used.
  • the emulsion polymerization is carried out using the emulsifiers mentioned. If, after completion of the polymerization, latices are obtained which tend to premature self-coagulation owing to a certain instability, the said emulsifiers can also be added for the post-stabilization of the latexes. This may be necessary in particular before removal of unreacted monomers by treatment with water vapor and before latex storage.
  • At least one molecular weight regulator is used to control the molecular weight of the resulting nitrile rubber.
  • the regulator is usually used in an amount of from 0.01 to 3.5 parts by weight, preferably from 0.05 to 3 parts by weight, more preferably 0.1 to 2.5 parts by weight, in particular 0.1 to 1 , 5 parts by weight, based on 100 parts by weight of the monomer used.
  • Mercaptan-containing carboxylic acids mercaptan-containing alcohols, xanthogen disulfides, thiuram disulfides, halogenated hydrocarbons, branched aromatic or aliphatic hydrocarbons and also linear or branched mercaptans can be used to adjust the molecular weight.
  • These compounds usually have from 1 to 20 carbon atoms (see Z5 Rubber Chemistry and Technology (1976), 49 (3), 610-49 (Uraneck, CA): "Molecular weight control of elastomers prepared by emulsion polymerization” and DC Blackley, Emulsion Polymerization, Theory and Practice, Applied Science Publishers Ltd London, 1975, pp. 329-381).
  • Examples of mercaptan-containing alcohols and mercaptan-containing carboxylic acids are monothioethylene glycol and mercaptopropionic acid.
  • xanthogen disulphides are dimethylxanthogen disulphide, diethylxanthogen disulphide, and diisopropylxanthogen disulphide.
  • thiuram disulfides include tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide.
  • halogenated hydrocarbons are carbon tetrachloride, chloroform, methyl iodide, diiodomethane, difluorodijodomethane, 1,4-diiodobutane, 1,6-diiodohexane, ethyl bromide, ethyl iodide, 1,2-dibromotetrafluoroethane, bromotrifluoroethene, bromodifluoroethene.
  • branched hydrocarbons are those from which an H radical can easily be split off. Examples of these are toluene, ethylbenzene, cumene, pentaphenylethane, triphenylmethane, 2,4-diphenyl-4-methyl-1-pentene, dipentene and terpenes such as limonene, ⁇ -pinene, ⁇ -pinene, ⁇ -carotene and ⁇ -carotene.
  • linear or branched mercaptans examples include n-hexyl mercaptan or mercaptans containing 12-16 carbon atoms and at least three tertiary carbon atoms, wherein the sulfur is bonded to one of these tertiary carbon atoms. These mercaptans are preferred and can be used either singly or in mixtures. Suitable examples are the addition of hydrogen sulfide to oligomerized propene, in particular tetrameric propene, or to oligomerized isobutene, especially trimeric isobutene, which are often referred to in the literature as tertiary dodecyl mercaptan ("t-DDM").
  • alkylthiols or (isomeric) mixtures of alkylthiols are either commercially available or can be prepared by a process which is adequately described in the literature by a person skilled in the art (see, for example, JP 07-316126, JP 07-316127 and JP 07-316128 and US Pat GB 823,823 and GB 823,824.).
  • Another example of an alkyl thiol is 2,2,4,6,6,8,8-pentamethylheptane-4-thiol.
  • the metering of the molecular weight regulator or of the molecular weight regulator mixture takes place either at the beginning of the polymerization or else in portions during the course of the polymerization, with the portionwise addition of all or individual components of the regulator mixture during the polymerization being preferred.
  • the molecular weight regulator is due to its function to some extent in the form of end groups in the nitrile rubber again.
  • an alkylthiol or a When used as a mixture of alkylthiols, the nitrile rubber has alkylthio end groups to a certain extent.
  • Such a nitrile rubber preferably contains 2,2,4,6,6-pentamethylheptane-4-thio, 2,4,4,6,6-pentamethylheptane-2-thio, 2,3,4,6,6-pentamethylheptane -2-thio and 2,3,4,6,6-pentamethylheptane-3-thio end groups.
  • Suitable peroxo compounds are hydrogen peroxide, peroxodisulfates, peroxodiphosphates, hydroperoxides, peracids, peracid esters, peracid anhydrides and peroxides having two organic radicals.
  • Suitable salts of peroxodisulfuric acid and peroxodiphosphoric acid are the sodium, potassium and ammonium salts.
  • Suitable hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide and p-menthane hydroperoxide.
  • Suitable peroxides having two organic radicals are dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, t-butyl peracetate, etc.
  • Suitable azo compounds are azobisisobutyronitrile, azobisvaleronitrile and azobiscyclohexanenitrile.
  • Hydrogen peroxide, hydroperoxides, peracids, peracid esters, peroxodisulfate and peroxo diphosphate are also used in combination with reducing agents.
  • Suitable reducing agents are sulfenates, sulfinates, sulfoxylates, dithionite, sulfite, metabisulfite, disulfite, sugars, urea, thiourea, xanthates, thioxanthogenates, hydrazinium salts, amines and amine derivatives such as aniline, dimethylaniline, monoethanolamine, diethanolamine or triethanolamine.
  • Initiator systems consisting of an oxidizing and a reducing agent are called redox systems.
  • salts of transition metal compounds such as iron, cobalt or nickel in combination with suitable complexing agents such as sodium ethylenediamtetraacetat, sodium nitrilotriacetate and trisodium phosphate or Tetrakaliumdiphsophat.
  • Preferred redox systems are, for example: 1) potassium peroxodisulfate in combination with triethanolamine, 2) ammonium peroxodiphosphate in combination with sodium metabisulfite (Na 2 S 2 O 5 ), 3) p-menthane hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe-II sulfate (FeS0 4 ⁇ 7H 2 O), sodium ethylenediaminoacetate and trisodium phosphate; 4) cumene hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe-II sulfate (FeS 4 X 7 H 2 O), sodium ethylenediamine acetate and tetrapotassium diphosphate.
  • the amount of oxidizing agent is 0.001 to 1 part by weight based on 100 parts by weight of monomer.
  • the molar amount of reducing agent is between 50% to 500% based on the molar amount of the oxid
  • the molar amount of complexing agent refers to the amount of transition metal used and is usually equimolar with this.
  • all or individual components of the initiator system are added at the beginning of the polymerization or during the polymerization.
  • the addition in portions of all and also individual components of the activator system during the polymerization is preferred.
  • the reaction rate can be controlled.
  • the amount of water used in the emulsion polymerization is in the range of 100 to 900 parts by weight, preferably in the range of 120 to 500 parts by weight, more preferably in the range of 150 to 400 parts by weight of water based on 100 parts by weight the monomer mixture.
  • salts can be added to the aqueous phase during the emulsion polymerization.
  • Typical salts are salts of monovalent metals in the form of potassium and sodium hydroxide, sodium sulfate, sodium carbonate, sodium bicarbonate, sodium chloride and potassium chloride. Preference is given to sodium and potassium hydroxide, sodium bicarbonate and potassium chloride.
  • the amounts of these electrolytes are in the range 0 to 1 parts by weight, preferably 0 to 0.5 parts by weight based on 100 parts by weight of the monomer mixture.
  • the polymerization can be carried out either batchwise or continuously in a stirred tank cascade.
  • the polymerization time is in the range of 5 h to 15 h and depends essentially on the acrylonitrile content of the monomer mixture and on the polymerization temperature.
  • the polymerization temperature is in the range of 0 to 30 ° C, preferably in the range of 5 to 25 ° C.
  • conversions in the range of 50 to 90%, preferably in the range of 60 to 85%, are reached, the polymerization is stopped.
  • a Abstoppstoff is added to the reaction mixture.
  • hydrazine and hydroxylamine and salts derived therefrom such as hydrazinium sulfate and hydroxylammonium sulfate, diethylhydroxylamine, diisopropylhydroxylamine, hydrosoluble salts of hydroquinone, sodium dithionite, phenyl-a-naphthylamine and aromatic phenols such as tert
  • the resulting suspension of the nitrile rubber in the aqueous medium is admixed with at least one substituted phenol of the general formula (I), preferably in an amount in the range from 0.9 to 1.6% by weight, based on the nitrile rubber.
  • the addition of the substituted phenol can be carried out, for example, in combination with one of the abovementioned stopping agents and / or in combination with another non-steam-volatile aging inhibitor.
  • the addition is also possible separately from the stopping agent and can be done before or after the addition of Abstoppffens.
  • the substituted phenol of the general formula (I) has proven useful to add the substituted phenol of the general formula (I) as an aqueous dispersion.
  • concentration of this aqueous dispersion is typically in a range of 2.50-70 wt.%), Preferably 5-60 wt.%>.
  • 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).
  • a coagulation of the nitrile rubber according to the invention takes place.
  • the latex coagulation of the nitrile rubber preferably takes place according to the process generally described in EP-A-1 369 436.
  • the Nitrilkautschukkrümel obtained during coagulation are washed, separated by sieves and mechanically pre-dewatered. Subsequently, drying at temperatures of 100 to 180 ° C, preferably at 110 to 150 ° C is performed.
  • the drying is preferably carried out by means of a fluidized bed drying at temperatures of 100 to 180 ° C, preferably at 110 to 150 ° C.
  • a suitable fluidized bed dryer comprises a drying unit in which the nitrile rubber to be dried is applied to a passage-like bottom, preferably in the form of a perforated plate or a split plate, and then with air at a temperature in the range of 100 to 180 ° C, preferably is flowed through at 110 to 150 ° C.
  • the moist exhaust air is discharged from the drying unit.
  • the apertured bottom may also be vibrated so that the nitrile rubber may be dried under vibration.
  • the substituted phenol of the general formula (I) present in the nitrile rubber contains 20-90% by weight, in particular 30-80% by weight, based on the amount of the substituted phenol of the general formula (I ) is removed in nitrile rubber.
  • the final nitrile rubber according to the invention when dried, has volatile contents ⁇ 1.0% by weight, a gel fraction ⁇ 1% by weight and a phenol content of the general formula (I) in the range from 0.25 to ⁇ 0.9% by weight. %> on.
  • Vulcanisable mixtures process for their preparation, vulcanizates and their preparation:
  • the invention furthermore relates to vulcanizable mixtures comprising at least one nitrile rubber according to the invention and at least one crosslinking system.
  • These vulcanizable mixtures may preferably contain one or more further typical rubber additives.
  • These vulcanizable mixtures are prepared by mixing at least one nitrile rubber (i) according to the invention and 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 cumyl peroxide, 1,3-bis (t-butylperoxy isopropyl) 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.
  • 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
  • DPTT dipentamethylene thiuram tetrasulfide
  • TMTD tetramethyl thiuram disulfide
  • Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthogenates, guanidine derivatives, caprolactams and thiourea derivatives Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthogenates, guanidine derivatives, caprolactams and thiourea derivatives.
  • dithiocarbamates can be used, for example: ammonium dimethyldithiocarbamate, sodium diethyldithiocarbamate 10 (SDEC), sodium dibutyldithiocarbamate (SDBC), Zinkdimethyl- dithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZBEC), Zinkpenta- methylendithiocarbamat (Z5MC), tellurium diethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel dimethyldithiocarbamate and zinc diisononyl dithiocarbamate.
  • SDEC sodium diethyldithiocarbamate 10
  • SDBC sodium dibutyldithiocarbamate
  • thiurams e.g. Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Dimethyldiphenylthiuramdisulfid, Tetrabenzylthiuramdisulfid, Dipentamethylenthiuram- tetrasulfid or Tetraethylthiuramdisulfid (TETD) are used.
  • Z0 As 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-Z5 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
  • 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 for example, zinc di (C 2 -C 6) alkyl dithiophosphates copper di (C 2 - 35 Ci6) alkyl dithiophosphates and dithiophosphoryl polysulfide can be used.
  • caprolactam for example, dithio-bis-caprolactam can be used.
  • DPTU dithio-bis-caprolactam
  • 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).
  • a sulfur crosslinking it is possible in addition to the crosslinking agents and additives mentioned above to use other inorganic or organic substances, such as zinc oxide, zinc carbonate, lead oxide, magnesium oxide, saturated or unsaturated organic fatty acids and their zinc salts, polyalcohols, amino alcohols, such as Example triethanolamine and amines such as dibutylamine, dicyclohexylamine, cyclohexylethylamine and polyetheramines.
  • 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 that forms two or more amino groups.
  • 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.
  • hexamethylenediamine and hexamethylenediamine carbamate are particularly preferred.
  • 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.
  • Applicable are e.g. Tetramethylguanidine, tetraethylguanidine, diphenylguanidine, di-o-tolylguanidine (DOTG), o-tolylbiguanidine and di-o-tolylguanidine salt of dicathecolboronic acid.
  • Aldehydin crosslinking accelerators such as e.g. n-Butylaldehydanilin. At least one bi- or polycyclic aminic base is particularly preferably used as crosslinking accelerator. These are known to the person skilled in the art.
  • 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: cyclohexylthiophthalimide (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 Pat. No. 4,857,571 to delay scorching. Preference is given to sterically hindered p-dialkylaminophenols, in particular Ethanox 703 (Sartomer).
  • These 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,
  • organic silanes such as, for example, bis (triethoxy-silyl-propyl-tetrasulfide), bis (tri-ethoxy-silyl-propyl-disulfide), vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy
  • 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 0 to 10 phr based on 100 phr of the nitrile rubber.
  • mold release agents there are e.g.
  • fatty and oleic acids and their derivatives 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 mold release agents are used as a blend component in amounts of about 0 to 10 phr, preferably 0.5 to 5 phr, based on 100 phr of the nitrile rubber.
  • 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. If rolls are used as a mixing unit, it is possible to proceed in an analogous manner and in the order of metering.
  • the invention further provides a process for the preparation of vulcanizates based on the nitrile rubbers of the invention, wherein the vulcanizable mixtures containing the 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 more 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 out in presses, autoclaves, hot air installations or in so-called automatic mat vulcanization plants, with temperatures in the range from 120.degree. C. to 200.degree. C., preferably 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 on the basis of the nitrile rubbers according to the invention, preferably in the form of molded parts.
  • 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, a flat gasket, a shaft seal, a Seal, a sealing cap, a dust cap, a plug seal, a Thermoisolierschlauch (with and without PVC additive), an oil cooler hose, an air intake hose, a power steering hose, a shoe sole or parts thereof or a pump diaphragm act.
  • Capillary column HP-5, length: 30 m; Inner diameter 0.32 mm;
  • the same device settings are used to determine the response ratio of 2,6-di-tert-butyl-p-cresol to naphthalene as the basis for calculating the content of 2,6-di-tert-butyl-p-cresol.
  • the recovery rate ("WAR") of 2,6-di-tert-butyl-p-cresol in dried nitrile rubber (KB NBR ) is calculated on the basis of the amount of 2,6-di-tert.butyl- p-cresol (KB LATEX ) calculated according to the following formula:
  • Nitrile rubber The volatile contents were determined according to ISO 248: 2005 (E) (fourth edition of 15.06.2005) "Rubber, raw - Determination of volatile matter content” according to the "Oven Method” method described under point 3.2.
  • the calcium content was determined by ICP-OES (inductively coupled plasma-optical emission spectrometry) at a wavelength of 317.933 nm against calibration matrix adapted calibration solutions.
  • ICP-OES inductively coupled plasma-optical emission spectrometry
  • 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.
  • the storage stability of the unvulcanized nitrile rubber was subjected to a hot air storage (48 h) in a convection oven at 100 ° C. The after 48 hours Storage at 100 ° C determined Mooney viscosity values were designated MV 1.
  • the storage stability (LS) was determined as the difference between the values of the Mooney viscosity after hot air storage (MV 1) and before the hot air storage (MV 0):
  • nitrile rubber (LS) is sufficient as long as the Mooney viscosity does not change by more than 5 Mooney units after 48 hours of storage at 100 ° C (MV 1 - MV 0).
  • the scorching behavior (“Mooneyscorch”) is determined using a shear disk viscometer 10 according to DIN 53 523 at 120 ° C. A small rotor (S) is used for the determination. "MS 5 (120 ° C.)” denotes the time in minutes, in which the Mooney viscosity value increases by 5 Mooney units from the minimum value.
  • the vulcanization rate is determined according to DIN 53 529, part 3 at 160 ° C using a 15 rheometer from Monsanto (MDR 2000E) as the difference of t 90 - tio, where tio and t 90 are the vulcanization times, where 10% or 90% of the final vulcanization degree are reached.
  • the vulcanization behavior of the mixtures was determined in the rheometer at 160 ° C. according to DIN 53 529. In this way, the characteristic vulcanization times tio and t 90 were determined.
  • the mechanical properties of the rubbers such as tension at 300% elongation (0 300 ), tensile strength (G max ) and elongation at break ( b ) are determined on vulcanizates according to DIN 53 504.
  • Table 1 gives a tabular overview of the examples carried out.
  • Dodecylmercaptan used by the manufacturers Lanxess (Latex A) and Chevron Phillips (Latex B).
  • the latices Prior to latex coagulation, the latices were treated with varying amounts of 2,6-di-tert-butyl-p-cresol (Vulkanox® KB the
  • VTS vacuum drying cabinet
  • NBR latexes (latex A and latex B) were prepared, which differ in the type of tertiary dodecylmercaptan (Lanxess and Chevron Phillips) used for molecular weight control. All starting materials are given in parts by weight based on 100 parts by weight of the monomer mixture.
  • Table 2 Feedstocks for the preparation of NBR latexes A and B
  • the preparation of the NBR latex was carried out batchwise in a 2 m 3 autoclave with stirrer.
  • the emulsifiers Erkantol® BXG (12.85 kg), Baykanol® PQ (3.85 kg) and the potassium salt of coconut fatty acid (2.56 kg) were charged with 84 g of sodium hydroxide in an autoclave and purged with a stream of nitrogen , Thereafter, the destabilized monomers (255.5 kg of butadiene and 94.5 kg of acrylonitrile) and a portion of the regulator were added to the reactor.
  • Dodecyl mercaptan from Chevron Phillips (corresponding to 0.31 parts by weight according to Table 2) and 0.665 kg potassium peroxodisulfate (corresponding to 0.19 parts by weight according to Table 1).
  • the polymerization batches were dissolved by adding 4.165 kg of sodium dithionite (1.19 parts by weight) and 4.48 kg of potassium hydroxide (1.28 parts by weight) in 105 kg of water (30 parts by weight ) stopped. Unreacted monomers and other volatiles were removed by steam distillation under reduced pressure.
  • NBR latices A and B were mixed with different amounts of 4-methyl-2,6-tert-butylphenol (Vulkanox® KB from Lanxess GmbH) (Table 4). For this, a 50% dispersion of Vulkanox.RTM ® KB in water was used.
  • aqueous solutions of sodium or magnesium chloride were used for the coagulation of the NBR latices.
  • concentration of the salt solutions and the amounts of salt used for the precipitation were each calculated without water of crystallization and were based on the solid contained in the latex.
  • Both the sodium chloride solution and the magnesium chloride solution were each 26% by weight, with normal industrial water (not deionized and thus containing calcium ions) being used for the preparation of the aqueous solution.
  • 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 nitrile rubber, the coagulation temperature, the temperature in the wash and the duration of the wash are summarized in Table 4.
  • the workup of the NBR latexes was carried out batchwise in a stirred, open container with 200 1 capacity, which was provided with 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.
  • a latex amount was used, which was calculated so that at 100% yield each 25 kg of solid were obtained.
  • the latex was placed in the coagulation tank, heated to 60 ° C and coagulated with stirring by slow addition of the aqueous salt solution. After completion of the latex coagulation, the rubber crumbs were washed by dilution washing without prior separation of the serum.
  • normal calcium ion-containing tap water (“BW”) was used with the flow rate of wash water kept constant (200 l / h).
  • VTS vacuum drying oven
  • FB fluidized bed drying
  • the drying in a vacuum drying oven was carried out batchwise at 70 ° C., during which a slight air stream was passed through during the drying. After drying, the contents of volatile components ⁇ 1, 0 wt.%.
  • the fluid bed drying was carried out discontinuously in a laboratory dryer (rapid dryer TG 200) from Kurt Retsch (Haan / Dusseldorf). 1.2 kg of the mechanically dehydrated rubber were used in each case for the FB drying. 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 6a).
  • the unvulcanized nitrile rubbers were characterized analytically (contents of 4-methyl-2,6-tert-butylphenol, calcium, chlorine and gel) and by their storage stability (LS).
  • Table 5 summarizes the properties of the nitrile rubbers obtained by drying in a vacuum drying oven.
  • Nitrile rubbers 2.1 - 2.5 (not according to the invention)
  • the contents of 4-methyl-2,6-but-butylphenol are in the range from 0.9 to 1.58% by weight (Table 5). From this, based on the Vulkanox® KB amounts given in the latex, recovery rates for 4-methyl-2,6-but-butylphenol of 97 to 100% are calculated. The recovery rates are independent of the type of electrolyte used in latex coagulation and the conditions used in the crumb wash. Furthermore, the nitrile rubber thermally dried in the VTS has sufficient storage stability LS.
  • the Ca contents are in the range from 390 to 650 ppm, the chlorine contents in the range from 75 to 130 ppm and the gel contents in the range from 0.4 to 0.7% by weight. Table 6a summarizes the conditions for the fluid bed drying of the nitrile rubbers.
  • Table 6b summarizes the properties of the nitrile rubbers obtained after fluidized-bed drying.
  • the contents of 4-methyl-2,6-but-butylphenol are in the range from 0.49 to 0.81% by weight (Table 6b). From this, based on the Vulkanox® KB amounts given in the latex, recovery rates for 4-methyl-2,6-but-butylphenol of 49 to 54% are calculated. The recovery rates are independent of the type of electrolyte used in latex coagulation and the conditions used in the crumb wash. Furthermore, the nitrile rubber obtained by FB drying has gel contents in the range from 0.4 to 0.6% by weight and sufficient storage stability LS.
  • rubber mixtures were prepared on the basis of the nitrile rubbers obtained in Examples 2.1 to 2.5 and Inventive Examples 3.1 * to 3.5 *.
  • an internal mixer with 1.5 1 internal volume GK 1.5 from Werner & Pfleiderer, Stuttgart
  • intermeshing kneading elements PS 5A - blade geometry
  • Table 8 Properties of the nitrile rubbers from Examples 2.1 to 2.5 not according to the invention and the examples according to the invention 3.1 * -3.5 *
  • Table 8 shows that the nitrile rubbers 3.1 *, 3.2 *, 3.3 *, 3.4 * and 3.5 * according to the invention have a higher scorch safety (larger MS 5 values), a slower scorch (larger tlO values), a higher vulcanization rate (t 90 -ti 0 ) and in the vulcanized state have higher stress values at 300% elongation (0300) and comparable good elongations at break.
  • the advantages of the nitrile rubbers according to the invention are clearly visible.

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Abstract

L'invention concerne de nouveaux caoutchoucs nitriles contenant du phénol qui présentent 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 une stabilité au stockage, des modules et un allongement à la rupture particulièrement bon(ne)s.
EP14828481.3A 2013-12-30 2014-12-29 Caoutchoucs nitriles stables au stockage et procédé pour les fabriquer Withdrawn EP3090016A1 (fr)

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PCT/EP2014/079372 WO2015101600A1 (fr) 2013-12-30 2014-12-29 Caoutchoucs nitriles stables au stockage et procédé pour les fabriquer
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WO2018012906A1 (fr) * 2016-07-13 2018-01-18 정대호 Composition destinée à un revêtement de sol comportant des fibres de noix de coco et procédé de fabrication de revêtement de sol utilisant ladite composition
EP3604355B1 (fr) * 2017-03-28 2021-09-01 Zeon Corporation Procédé de production d'un caoutchouc nitrile carboxylé
WO2019011813A1 (fr) * 2017-07-12 2019-01-17 Arlanxeo Deutschland Gmbh Procédé pour la production de polymères d'isooléfine avec une préparation de système amorceur améliorée
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
US11673130B2 (en) * 2018-12-12 2023-06-13 Arlanxeo Deutschland Gmbh Catalyst system containing a metathesis catalyst and at least one phenolic compound and a process for metathesis of nitrile-butadiene rubber (NBR) using the catalyst system
CN116444702A (zh) * 2023-05-11 2023-07-18 山东非金属材料研究所 一种黏度标准物质用聚异丁烯油的制备方法

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RU2676643C2 (ru) 2019-01-09
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TW201536849A (zh) 2015-10-01
RU2016131350A3 (fr) 2018-08-07
CN105873995A (zh) 2016-08-17
TWI653271B (zh) 2019-03-11
EP2889326A1 (fr) 2015-07-01
CN105873995B (zh) 2019-06-21
MX2016008700A (es) 2016-09-06
JP6445020B2 (ja) 2018-12-26
EP2889326B1 (fr) 2016-09-14
KR102208079B1 (ko) 2021-01-27
JP2018141162A (ja) 2018-09-13
RU2016131350A (ru) 2018-02-06
US20160376422A1 (en) 2016-12-29
JP2017504690A (ja) 2017-02-09
WO2015101600A1 (fr) 2015-07-09

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