WO2013098056A1 - Purification de caoutchouc nitrile éventuellement hydrogéné - Google Patents

Purification de caoutchouc nitrile éventuellement hydrogéné Download PDF

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Publication number
WO2013098056A1
WO2013098056A1 PCT/EP2012/074601 EP2012074601W WO2013098056A1 WO 2013098056 A1 WO2013098056 A1 WO 2013098056A1 EP 2012074601 W EP2012074601 W EP 2012074601W WO 2013098056 A1 WO2013098056 A1 WO 2013098056A1
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nitrile rubber
ionic liquid
alkyl
process according
aryl
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PCT/EP2012/074601
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English (en)
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Christopher Ong
Stephen Pask
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Lanxess Deutschland Gmbh
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Publication of WO2013098056A1 publication Critical patent/WO2013098056A1/fr

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    • 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
    • C08C2/02—Purification
    • C08C2/04—Removal of catalyst residues
    • 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
    • C08C2019/09—Metathese

Definitions

  • This invention provides a process for the purification of optionally hydrogenated nitrile rubber by contacting such optionally hydrogenated nitrile rubber with specific solvents.
  • Elastomers are widely used in many rubber-technology products, such as rubber tubing, transmission belts, seals, membranes, fabric coverings, shoe soles, profile sections, films, packaging materials and many other products.
  • rubber-technology products such as rubber tubing, transmission belts, seals, membranes, fabric coverings, shoe soles, profile sections, films, packaging materials and many other products.
  • the elastomers need to have the impurities removed in an elaborate way.
  • Such impurities and undesired compounds can originate from the elastomer production process, in which different additives and complex metal catalysts are used, namely during radical polymerization in an aqueous emulsion.
  • additives and catalysts are also subject to undesired degradation reactions which further results in unwanted byproducts.
  • the impurities can additionally contribute very significantly to corrosion and therefore wear of the systems needed for the hydrogenation.
  • the use of elastomers with a too high impurity level can lead to reduced surface quality of the articles due to efflorenscence as well as to mold contamination.
  • the purification of the elastomers with respect to impurities is typically carried out by expensive neutralization, coagulation, precipitation and washing - - processes in suitable organic substances, such as alcohols, ketones, ethers, water and mixtures thereof.
  • impurities are removed by contacting the reaction mixtures with ion exchange resins disposing of functional groups able to bind such impurities. Nevertheless complete purification cannot in principle be guaranteed.
  • a particular problem involves the separation of low-molecular, sometimes high-boiling (above 150°C), weakly water-soluble and/or water-insoluble impurities such as emulsifiers, fatty acids, fatty acid salts and fatty acid esters, monomers and derivatives thereof, such as dimers, oligomers or other undesired reaction products of the monomers with other components of the reaction system, organic catalyst residues and ligands, which remain in the elastomer when the elastomers have been prepared by emulsion polymerization followed by conventional purification processes.
  • weakly water-soluble and/or water-insoluble impurities such as emulsifiers, fatty acids, fatty acid salts and fatty acid esters, monomers and derivatives thereof, such as dimers, oligomers or other undesired reaction products of the monomers with other components of the reaction system, organic catalyst residues and ligands, which remain in the elastomer when the elastomers have been prepared
  • Such impurities are for example emulsifiers, fatty acids, fatty acid esters, fatty acid salts of sodium, potassium or calcium, unreacted monomers, molecular weight modifiers, catalyst components, and any reaction products thereof.
  • fractional precipitation entails high costs on the industrial scale and is ecologically disadvantageous owing to the large amounts of solvents and precipitating agents required.
  • WO 2002/34863 A teaches a process for removing mercaptans from hydrocarbon streams, for example crude oil and natural gas, by a) adding a mercaptan-containing hydrocarbon feedstream to an ionic liquid solution or dispersion of one or more basic metal salts to form mercaptides, which are then either precipitated from solution or are dissolved or dispersed in the ionic liquid and b) separating the resulting de-marcaptanized hydrocarbon feedstream from the ionic liquid.
  • the flow of hydrocarbons can either stream over/through the ionic liquid or be brought into contact in stirred tanks.
  • the basic salts can be virtually any base capable of reacting with mercaptans to form mercaptides.
  • US 2004/0133058 A discloses a process for separating close-boiling or azeotropic mixtures by using ionic liquids as selective additives in rectification.
  • the process allows to separate liquids or condensable gases in the condensed state wherein an entrainer is used which is an ionic liquid and - - which brings a change in the separation factor of the components to be separated divergent from one.
  • the ionic liquid is present at a total concentration of 5 to 90 mol %. This process is told to be superior to conventional extractive rectification regarding costs and energy. It is mentioned as particularly suitable for the following applications, eg.
  • azeotropes amines/water, THF/water, formic acid/water, alcohols/water, acetone/methanol, acetate/water, acrylate/water or close-boiling mixtures like acetic acid/water, C4 hydrocarbons, C4 hydrocarbons, and alkanes/alkenes.
  • US 2005/0010076 A discloses a process for the purification of hydrocarbons or mixtures of hydrocarbons through the removal of polarisable impurities with ionic liquids.
  • polarisable impurities Of specific importance is the removal of sulfur-containing impurities from diesel fuels or other petrol fractions to a content below a level of 50 ppm, which process is told to be significantly superior to the removal by hydrogenation methods.
  • the process also allows a dehalogenation which avoids the classical drawbacks of dehalogenation by hydrogenation (as high pressure and temperature, release of corrosive HC1 gas).
  • US 2003/0085156 A also discloses a process for the removal of organosulfur compounds from a hydrocarbon material (diesel fuel, gasoline, jet fuel etc.) by contacting the hydrocarbon material with an ionic liquid, resulting in the extraction of the sulphur compound into the ionic liquid.
  • the process can be conducted either batch-wise or continuously. It is described that a counter-current contactor can be utilized which allows for the hydrocarbon material to flow into the bottom of the contactor and rise through the ionic liquid (which enters through the top and exits through the bottom) and exit through the top.
  • a process for the regeneration of the ionic liquid is described through the removal of the organosulfur compounds from the ionic liquid by means of vapourization or solvent extraction.
  • US 2005/0090704 A relates to a process for the liquid-liquid extraction or liquid-gas extraction of olefins from a mixture of organic compounds of olefins and aliphatics, wherein the olefins are extracted by means of a phase comprising at least one ionic liquid with the extraction being carried out in countercurrent and the phase comprising the ionic liquid.
  • ruthenium-containing catalysts are e.g. known to be particularly suitable for the selective metathesis of nitrile rubber which encompasses the cleavage of the carbon-carbon double bonds without concomitant reduction of the carbon-nitrogen triple bonds present in the nitrile rubber.
  • US 2004/0132891 A teaches the use of l,2-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene) (tricyclohexylphosphine)-ruthenium (phenyl methylene) dichloride for the metathesis of nitrile rubber, however, in the absence of a co-olefin.
  • the disclosure in prior art regarding a potential separation of the metathesis catalyst from the polymer is relatively limited. Additionally there is no disclosure or teaching given at all which pays attention to the removal of any undesired by-products or impurities.
  • US 6,376,690 Bl relates to the removal of metal complexes from reaction mixtures and teaches the use of a separation process in which a solution containing a solubility-enhancing compound is added to the original reaction mixture containing the metal complexes wherein the added solution is immiscible with the original reaction mixture.
  • a solution containing a solubility-enhancing compound is added to the original reaction mixture containing the metal complexes wherein the added solution is immiscible with the original reaction mixture.
  • the second solution is just the opposite and the solubility enhancing compound is chosen in a way that it enhances the metal catalysts solubility in said second solution.
  • the solubility-enhancing compounds comprise e.g.
  • phosphines sulfonated phosphines, phosphites, phosphinites, phosphonites, arsines, stibines, ethers, amines, amides, imines, sulfoxides, carboxyls, nitrosyls, pyridines, and thioethers.
  • the metal catalyst on the basis of e.g.
  • disadvantageous ⁇ involves the addition of additives which - if not fully removed - can lateron interfere with the hydrogenation catalyst which is typically used in a subsequent step to hydrogenate the nitrile rubber.
  • the separation of two immiscible solutions while relatively easy on small scale is quite a complex process on a commercial scale of grand scale.
  • WO-A-2006/047105 discloses a process for separating a homogeneous metathesis catalyst and, optionally, one or more homogeneous metathesis degradation products from a metathesis reaction mixture containing in addition to said metathesis catalyst and said metathesis degradation product(s) one or more olefin metathesis products, one or more unconverted reactant olefins, and optionally a solvent. Said process comprises contacting the metathesis reaction mixture with a - - nanofiltration membrane, e.g.
  • the metathesis reaction mixture used may be obtained by homo- metathesis, cross-metathesis, ring-closing metathesis, or ring-opening metathesis polymerisation.
  • Polymer hydrogenation is a well known operation, as disclosed, for example, in US-A- 4,396,761, US-A-4,510,293, US-A-5,258,467 and US-A-4,595,749.
  • the subsequent separation of the hydrogenation catalyst or degradation products thereof from the polymer is not always described in detail or even at all.
  • certain rhodium containing catalysts are known to be particularly suitable for the selective hydrogenation of nitrile rubber, namely the reduction of the carbon-carbon double bonds without concomitant reduction of the carbon-nitrogen triple bonds present in nitrile rubber.
  • Such hydrogenated nitrile rubber is less susceptible to heat-induced degradation in comparison to unsaturated nitrile rubber.
  • US-A-4,464,515 teaches the use of hydrido rhodium tetrakis (triphenylphosphine) catalyst, i.e. HRh(PPh 3 ) 4 , in a process to selectively hydrogenate unsaturated nitrile rubber. There is no further disclosure about removing the hydrogenation catalyst after the hydrogenation.
  • GB-A-1,558,491 teaches the use of chloro rhodium tris(triphenylphosphine) (RhCl(PPh 3 ) 3 ) as catalyst in a similar process to hydrogenate unsaturated nitrile rubber.
  • the hydrogenation product is separated off from the reaction solution by treatment with steam or by pouring into methanol and is subsequently dried at elevated temperature and reduced pressure. Once more no teaching is provided how the hydrogenation catalyst might be removed.
  • ruthenium containing catalysts are known to be particularly suitable for either the selective metathesis or hydrogenation of nitrile rubber.
  • the process of utilizing ruthenium - - containing catalysts for the homogeneous hydrogenation of nitrile rubber is also well known.
  • US 5,075,388 it is disclosed to hydrogenate nitrile rubber in the presence of an NH 2 containing compound selected from ammonia and a C 1 . 20 primary amine.
  • US-A-6,084,033 teaches the use of a rhodium-ruthenium bimetallic complex catalyst for the hydrogenation of nitrile rubber.
  • US-A-4,631,315 teaches the hydrogenation of a nitrile rubber dissolved in a low molecular weight ketone solvent using a ruthenium-based catalyst. After hydrogenation, the polymer is separated from the solution by conventional methods, for example by (vacuum) evaporation, by blowing in water vapour or by addition of a non-solvent. A drying treatment is then carried out to remove remaining solvent or water.
  • the unsaturated nitrile rubber is first dissolved in a suitable solvent to provide a viscous rubber solution.
  • the catalyst is then dissolved in the rubber solution.
  • These hydrogenation processes are said to be homogeneous because the substrate and catalyst are contained in the same phase.
  • An advantage of the above homogeneous hydrogenation processes is that they require minimal amounts of catalyst to effect the hydrogenation.
  • a major disadvantage of such processes is that it is difficult to remove the catalyst from the reaction mixture once the reaction is complete.
  • the catalyst may be readily removed by filtration or centrifugation.
  • iron residues may also be present in the hydrogenated nitrile polymer.
  • Iron-containing residues can occur due to minimum corrosion or degradation which might happen in any metal vessel or pipes or alternatively due to the fact that iron-containing compounds might have been used as activators in the polymerisation of the nitrile rubber.
  • Iron, ruthenium and rhodium are active catalytic metals and therefore, it is desirable to remove them from the nitrile rubber as well as the hydrogenated rubber in order to improve the overall quality of the product.
  • the high price of rhodium provides an economic incentive for its recovery.
  • US-A-4,985,540 discloses a process for removing rhodium-containing catalyst residues from hydrogenated nitrile rubber by contacting a functionalized ion exchange resin with a hydrocarbon phase, which contains the hydrogenated nitrile rubber, the rhodium-containing catalyst residues and - - a hydrocarbon solvent. It is said that such process is capable of removing rhodium from viscous solutions containing less than 10 ppm rhodium (weight rhodium/weight solution).
  • the ion- exchange resins utilized are characterized as being macroreticular and modified with functional groups selected from amine, thiol, carbodithioate, thiourea, and dithiocarbamate functional groups.
  • US-A-5,208,194 further teaches the use of a sulfonic acid functionalized ion exchange resin for the recovery of Group VIII metal complexes from dilute organic solutions.
  • US 2004/0026329 A teaches of the recovery of transition metals through binding of the metal to functionalized polymer fibres.
  • the polymer fibre is suitably a polyolefin, a fluorinated polyethylene, cellulose or viscose which is functionalised by radiation grafting of at least one monomer.
  • the present invention relates to a process for the purification of an optionally hydrogenated nitrile rubber comprising contacting the optionally hydrogenated nitrile rubber with at least one ionic liquid.
  • radicals, parameters or explanations given above or below in general terms or in preferred ranges can be combined with one another in any way, i.e. including combinations of the respective ranges and preferred ranges.
  • substituted used for the purposes of the present patent application in respect of the metathesis catalyst or the salt of the general formula (I) means that a hydrogen atom on an indicated radical or atom has been replaced by one of the groups indicated in each case, with the - - proviso that the valence of the atom indicated is not exceeded and the substitution leads to a stable compound.
  • the optionally hydrogenated nitrile rubber is contacted with at least one ionic liquid.
  • Ionic liquids to be used in the process of the invention are salts or salt mixtures which are liquid in a temperature range from -20°C to 300°C, preferably from 0°C to 150°C, and particularly preferably from 20°C to 100°C.
  • Ionic liquids are typically defined through both, their cationic and their anionic portions.
  • the ionic liquid can represent, but is not restricted to compounds on the basis of quaternary ammonium cations, quaternary phosphonium cations, optionally substituted pyridinium cations, optionally substituted imidazolium cations, optionally substituted pyrazolium cations, and optionally substituted pyrimidinium cations.
  • the process according to the present invention is performed using at least one ionic liquid which is selected from the group consisting of the ionic liquids having the general formulae
  • a 1 shall mean an anion selected from the group consisting of hexafluorophosphate (PF 6 " ), nitrate (NO 3 ) " , halides, preferably fluoride, chloride, bromide or iodide, sulfates, sulfonates, aluminates, carboxylates, - - phosphates and borates, with n meaning 1, 2 or 3 depending on the negative charge of the aforementioned anions and (1/n) therefore representing 1 for a one time negatively charged anion, 1/2 for a two times negatively charged anion and 1/3 for a three times negatively charged anion,
  • X is nitrogen or phosphorous
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different and represent hydrogen, halide, alkoxy, alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, and
  • Z 1 , Z 2 , Z 3 are identical or different and represent carbon (C) or nitrogen (N), under the first proviso, that at least one of Z 1 , Z 2 , and Z 3 is nitrogen and under the second proviso that when any of Z 1 , Z 2 , Z 3 are nitrogen the attached R 1 , R 2 , or R 3 group is null.
  • the process according to the present invention is performed in the presence of at least one ionic liquid pursuant to one of the aforementioned general formulae (l)-(5) wherein n is 1 and A- represents PF 6 " , N0 3 " , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, more preferably phenyl, substituted aryl, or alkoxy.
  • the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (1) wherein n is 1 and
  • A- represents PF 6 " , N0 3 , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,
  • X is nitrogen or phosphorus
  • R 1 , R 2 , R 3 , and R 4 are identical or different and shall mean alkoxy, alkyl or aryl each having 1 -25 carbon atoms.
  • the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (2) wherein n is 1 and
  • A- represents PF 6 " , N0 3 , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different and shall mean alkoxy, alkyl or aryl each having
  • the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (3) wherein n is 1 and _ -
  • A- represents PF 6 ⁇ N0 3 " , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,
  • R 1 , R 2 , R 3 , R 4 , and R 5 are identical or different and shall mean alkoxy, alkyl or aryl each having 1 - 25 carbon atoms.
  • the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (4) wherein n is 1 and
  • A- represents PF 6 " , N0 3 , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, or alkoxy,
  • R 1 , R 2 , R 3 , R 4 , and R 5 are identical or different and shall mean alkoxy, alkyl or aryl each having
  • the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (5) wherein n is 1 and
  • A- represents PF 6 " , N0 3 , F ⁇ CI “ , Br , ⁇ , R 7 S0 3 “ , R 7 OS0 3 “ , R 7 C0 3 “ , BF 4 " , and B(R 7 ) 4 " , where R 7 is identical or different and represents alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, or alkoxy,
  • Z 1 , Z 2 , Z 3 are identical or different and represent carbon (C) or nitrogen (N), under the first proviso, that at least one of Z 1 , Z 2 , and Z 3 is nitrogen and under the second proviso that when any of Z 1 , Z2 , Z 3 are nitrogen the attached R 1 , R2 , or R 3 group is null, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different alkoxy, alkyl or aryl radicals each having 1 -25 carbon atoms.
  • the process of the present invention is performed using at least one ionic liquid selected from the group consisting of l-ethyl-3-methyl-pyridinium ethylsulfate, l-ethyl-3- methyl-imidazolium ethylsulfate, l-methyl-3-butylimidazolium chloride, l-methyl-3-ethylimidazo- lium chloride, N-butylpyridinium chloride, tetrabutylphosphonium chloride, ammonium hexa- fluorophosphate, ammonium tetrafluoroborate, ammonium tosylate, ammonium hydrogen sulphate, pyridinium hexafluorophosphate, l-methyl-3 -butyl imidazolium hexafluorophosphate, pyridinium tetrafluoroborate, pyridinium hydrogen sulphate, N-butyl
  • nitrile rubbers also referred to as "NBR” for short, are rubbers which are copolymers or terpolymers containing repeating units of at least one ⁇ , ⁇ - unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers.
  • NBR nitrile rubbers
  • nitrile rubbers and processes for producing such nitrile rubbers are well known, see, for example, W. Hofmann, Rubber Chem. Technol. 36 (1963) 1 and Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, pp. 255-261.
  • the conjugated diene in the nitrile rubber may be of any kind. It is preferred to use (C4-C6) conjugated dienes. Particular preference is given to 1 ,2-butadiene, 1,3-butadiene, isoprene, 2,3- dimethylbutadiene, piperylene or mixtures thereof. More particular preference is given to 1,3- butadiene and isoprene or mixtures thereof. 1,3 -Butadiene is especially preferred.
  • ⁇ , ⁇ -unsaturated nitrile it is possible to use any known ⁇ , ⁇ -unsaturated nitrile, preference being given to (C3-C5) ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Acrylonitrile is particularly preferred.
  • One particularly preferred nitrile rubber is a copolymer of acrylonitrile and 1,3-butadiene.
  • copolymerizable termonomers it is possible to make use, for example, of aromatic vinylmonomers, preferably styrene, a-methylstyrene and vinylpyridine, fluorine-containing vinylmonomers, preferably fluoroethyl vinyl ether, fluoropropyl vinyl ether, 0- fluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or else copolymerizable anti-ageing monomers, preferably N-(4-anilinophenyl)acrylamide, N-(4- anilinophenyl)methacrylamide, N-(4-anilinophenyl)cinnamides, N-(4-anilinophenyl)crotonamide, N-phenyl-4-(3-vinylbenzyloxy)aniline and N-phenyl-4-(4-vinylbenzyloxy)aniline, and also non
  • copolymerizable termonomers containing carboxyl groups, examples being ⁇ , ⁇ -unsaturated monocarboxylic acids, their esters, their amides, ⁇ , ⁇ -unsaturated dicarboxylic acids, their monoesters or diesters, or their corresponding anhydrides or amides.
  • ⁇ , ⁇ -unsaturated monocarboxylic acids it is possible with preference to use acrylic acid and methacrylic acid.
  • esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids preferably their alkyl esters and alkoxyalkyl esters. Preference is given to the alkyl esters, especially CpCig alkyl esters, of the ⁇ , ⁇ -unsaturated monocarboxylic acids.
  • alkyl esters especially CpCig alkyl esters, of acrylic acid or of methacrylic acid, more particularly 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 the ⁇ , ⁇ -unsaturated monocarboxylic acids more preferably alkoxyalkyl esters of acrylic acid or of methacrylic acid, more particular C2-C12 alkoxyalkyl esters of acrylic acid or of methacrylic acid, very preferably methoxymethyl acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxymethyl (meth)acrylate.
  • Use may also be made of mixtures of alkyl esters, such as those mentioned above, for example, with alkoxyalkyl esters, in the form of those mentioned above, for example.
  • cyanoalkyl acrylates and cyanoalkyl methacrylates in which the C atom number of the cyanoalkyl group is 2-12, preferably a-cyanoethyl acrylate, ⁇ -cyanoethyl acrylate and cyanobutyl methacrylate.
  • Use may also be made of hydroxyalkyl acrylates and hydroxyalkyl methacrylate in which the C atom number of the hydroxyalkyl groups is 1-12, preferably 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate and 3-hydroxypropyl acrylate; use may also be made of fluorine- substituted benzyl-group-containing acrylates or methacrylates, preferably fluorobenzyl acrylates, and fluorobenzyl methacrylate. Use may also be made of acrylates and methacrylates containing fluoroalkyl groups, preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate. Use may also be made of ⁇ , ⁇ -unsaturated carboxylic esters containing amino groups, such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.
  • ⁇ , ⁇ -unsaturated dicarboxylic acids preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.
  • Use may be made, furthermore, of ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
  • ⁇ , ⁇ -unsaturated dicarboxylic anhydrides preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
  • ⁇ , ⁇ -unsaturated dicarboxylic monoesters or diesters may be, for example, alkyl esters, preferably C1-C10 alkyl, more particularly ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or n-hexyl esters, alkoxyalkyl esters, preferably C2-C12 alkoxyalkyl, more preferably C3-C8- alkoxyalkyl, hydroxyalkyl, preferably C1-C12 hydroxyalkyl, more preferably C2-C8 hydroxyalkyl, cycloalkyl esters, preferably C5-C12 cycloalkyl, more preferably Ce-Cn cycloalkyl, alkylcycloalkyl esters, preferably Ce-Cn alkylcycloalkyl, more preferably C7-C10 alkylcycloalkyl, aryl esters,
  • 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-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-propyl- heptyl acrylate and lauryl (meth)acrylate. More particularly, n-butyl acrylate is used.
  • alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are methoxyethyl (meth)acrylate, ethoxyethyl (meth) acrylate and methoxymethyl (meth)acrylate. More particularly, methoxyethyl acrylate is used.
  • Particularly preferred hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate.
  • esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are additionally, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, epoxy (meth)acrylate, N-(2-hydroxyethyl)acrylamides, N-(2-hydroxy- methyl)acrylamides and urethane (meth)acrylate.
  • maleic acid monoalkyl esters preferably monomethyl maleate, monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;
  • maleic acid monocycloalkyl esters preferably monocyclopentyl maleate, monocyclohexyl maleate and monocycloheptyl maleate;
  • maleic acid monoalkyl cycloalkyl esters preferably monomethyl cyclopentyl maleate and monoethyl cyclohexyl maleate;
  • maleic acid monoaryl esters preferably monophenyl maleate
  • maleic acid monobenzyl esters preferably monobenzyl maleate
  • fumaric acid monoalkyl esters preferably monomethyl fumarate, monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate;
  • fumaric acid monocycloalkyl esters preferably monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate;
  • fumaric acid monoalkyl cycloalkyl esters preferably monomethyl cyclopentyl fumarate and monoethyl cyclohexyl fumarate;
  • fumaric acid monoaryl esters preferably monophenyl fumarate
  • citraconic acid monoalkyl esters preferably monomethyl citraconate, monoethyl citraconate, monopropyl citraconate and mono-n-butyl citraconate;
  • citraconic acid monocycloalkyl esters preferably monocyclopentyl citraconate, monocyclohexyl citraconate and monocycloheptyl citraconate;
  • citraconic acid monoalkyl cycloalkyl esters preferably monomethyl cyclopentyl citraconate - - and monoethyl cyclohexyl citraconate;
  • citraconic acid monoaryl esters preferably monophenyl citraconate
  • citraconic acid monobenzyl esters preferably monobenzyl citraconate
  • itaconic acid monoalkyl esters preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;
  • itaconic acid monocycloalkyl esters preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate;
  • ⁇ itaconic acid monoaryl esters preferably monophenyl itaconate
  • ester groups may also be chemically different groups.
  • di- or polyunsaturated compounds are di- or polyunsaturated acrylates, methacrylates or itaconates of polyols, such as, for example, 1,6-hexanediol diacrylate (HDODA), 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate, triethylene glycol diacrylate, butane- 1,4-diol diacrylate, propane- 1,2-diol diacrylate, butane-l,3-diol dimethacrylate, neopentylglycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate,
  • 1,6-bisacrylamide diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane or 2- acrylamidoethyl acrylate.
  • polyunsaturated vinyl compounds 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 NBR polymers may vary within wide ranges.
  • the proportion of or the sum of the conjugated dienes is typically in the range from 40 to 90% preferably in the range from 50 to 85%, by weight, based on the overall polymer.
  • the proportion of or the sum of the ⁇ , ⁇ -unsaturated nitriles is typically 10 to 60%, preferably 15 to 50%), by weight, based on the overall polymer.
  • the proportions of the monomers add up in each case to 100%> by weight.
  • the additional monomers, depending on the nature of the termonomer or termonomers may be present in amounts of 0%> to 40%> by weight, based on the overall polymer.
  • esters of (meth)acrylic acid are used as additional monomers, they are usually used in amounts of from 1 to 25% by weight.
  • ⁇ , ⁇ -unsaturated monocarboxylic or dicarboxylic acids are used as additional monomers, they are usually used in amounts of less than 10% by weight.
  • the nitrogen content of the nitrile rubbers of the invention is determined by the Kjeldahl method in accordance with DIN 53 625. Owing to the content of polar comonomers, the nitrile rubbers are usually soluble in methyl ethyl ketone to an extent of > 85% by weight at 20°C.
  • the nitrile rubbers have Mooney viscosities (ML (1+4 @100°C)) of from 10 to 150, preferably from 20 to 100, Mooney units.
  • the Mooney viscosity (ML (1+4 @100°C)) is determined at 100°C by means of a shear disc viscometer in accordance with DIN 53523/3 or ASTM D 1646.
  • the glass transition temperatures of the optionally hydrogenated nitrile rubbers of the invention are situated in the range from -70°C to +20°C, preferably in the -60°C to 10° range.
  • nitrile rubbers according to the invention which comprise repeating units of acrylonitrile, 1,3-butadiene and optionally of one or more further copolymerizable monomers.
  • Preference is likewise given to nitrile rubbers having repeating units of acrylonitrile, 1,3-butadiene and one or more ⁇ , ⁇ -unsaturated monocarboxylic or dicarboxylic acids, their esters or amides, and in particular repeating units of an alkylester of an ⁇ , ⁇ -unsaturated carboxylic acid, very particularly preferably of 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)
  • Nitrile rubbers which can be used for the purposes of the invention are also commercially available, e.g. as products from the product range of the trade names Perbunan® and Krynac® from Lanxess GmbH.
  • nitrile rubbers Prior to being subjected to the process of the present invention the nitrile rubbers can also be subjected to a metathesis reaction to lower the molecular weight which is well-known in the art and described in scientific literature and patents (e.g. US 2003/0088035 A and US 2004/0132891 A).
  • Nitrile rubbers to be subjected to the present process which have not undergone a methathesis reaction typically have a Mooney viscosity (ML 1+4 at 100°C) in the range from 30 to 70, preferably from 30 to 50. This corresponds to a weight average molecular weight Mw in the range 200,000 - 500,000, preferably in the range 200,000 - 400,000.
  • Nitrile rubbers to be subjected to the present process which have previously undergone a methathesis reaction typically have a Mooney viscosity (ML 1+4 at 100°C) in the range from 1 to 50, preferably from 1 to 30. This corresponds to a weight average molecular weight Mw in the range 25,000 - 250,000, preferably in the range 50,000 - 150,000.
  • hydrogenated nitrile butadiene rubbers for short is intended to mean all aforementioned nitrile rubbers which have been subjected to hydrogenation.
  • the nitrile rubber obtained from emulsion polymerization is converted into a solid rubber.
  • the conversion of the nitrile rubber latex into a solid rubber is carried out by the methods known to the person skilled in the art.
  • the nitrile rubber, from which impurities have been - - removed is subsequently either dissolved in an organic solvent, if the impurities were removed from it by the purification methods known to the person skilled in the art, such as precipitation or coagulation and subsequent washing, or the retentate solution obtained by the method according to the present invention, which contains the dissolved and purified nitrile butadiene rubber, directly has a transition metal catalyst suitable for the hydrogenation added to it, and is hydrogenated.
  • the inventive process allows at the same time the purification of nitrile rubbers as well as hydrogenated nitrile rubber in various aspects. It is possible to remove the following types of components (1) to (3) simultaneously:
  • ruthenium, osmium and rhodium catalysts used for catalysing the metathesis and/or hydrogenation reaction(s) and any degradation products.
  • an ionic liquid allows a facilitated separation between the catalyst, catalyst degradation products and the main product after the end of the reaction and makes it additionally possible to reuse the catalytic system.
  • the elastomers obtained by the method according to the invention are distinguished by many advantages. They exhibit less mould contamination in injection-molding applications, and the purified elastomers may be used in contact with food and in the medical field owing to the low incidence of contamination.
  • the purified elastomers can be used for insulation in the electronics field, since only reduced amounts of ionic impurities which can conduct current remain, and environmentally unfriendly substances are not left behind in the event of burning. Owing to these properties, because of the low impurity level, these elastomers are suitable for use in the cosmetic and medical fields, the food-contact and electronics sectors and in the rubber industry.
  • ruthenium, osmium and rhodium catalysts as well as the respective degradation products thereof are either used during the emulsion polymerization of the nitrile rubber, the optional metathesis reaction and/or the optional subsequent hydrogenation reaction.
  • One preferred catalyst used during hydrogenation of nitrile rubber is a rhodium- or ruthenium- containing catalyst, more preferably a catalyst of the general formula
  • M is ruthenium or rhodium
  • the radicals R 10 are identical or different and are each a CpCg- alkyl group, a C pCg-cycloalkyl group, a C6-Ci 5 -aryl group or a C 7 -Ci 5 -aralkyl group.
  • X is hydrogen or an anion, preferably halogen and particularly preferably chlorine or bromine
  • 1 is 2, 3 or 4
  • m is 2 or 3 and n is 1 , 2 or 3, preferably 1 or 3.
  • Preferred catalysts are tris(triphenylphosphine)rhodium(I) chloride, tris(tri- phenylphosphine)rhodium(III) chloride and tris(dimethyl sulphoxide)rhodium(III) chloride and also tetrakis(triphenylphosphine)rhodium hydride of the formula (C6H 5 )3P) 4 RhH and the corresponding compounds in which the triphenylphosphine has been completely or partly replaced by tricyclohexylphosphine.
  • M is osmium or ruthenium
  • X 1 and X 2 are identical or different and are two ligands, preferably anionic ligands,
  • L are identical or different ligands, preferably uncharged electron donors
  • R are identical or different and are each hydrogen, alkyl, preferably Ci-C3o-alkyl, cycloalkyl, preferably C3-C2o-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, alkynyl, preferably C2-C2o-alkynyl, aryl, preferably C6-C24-aryl, carboxylate, preferably C1-C20- carboxylate, alkoxy, preferably Ci-C2o-alkoxy, alkenyloxy, preferably C2-C20- alkenyloxy, alkynyloxy, preferably C2-C2o-alkynyloxy, aryloxy, preferably C6-C24- aryloxy, alkoxycarbonyl, preferably C2-C2o-alkoxycarbonyl, alkylamino, preferably Ci-C3o-alkylamino, alkylthio, preferably Ci-C3o-alkylthio,
  • one group R is hydrogen and the other group R is Ci-C 2 o-alkyl, C3-Cio-cycloalkyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl, C6-C24-aryl, Ci-C 2 o-carboxylate, Ci-C 2 o-alkoxy, C 2 -C 2 o-alkenyloxy, C 2 -C 2 o-alkynyloxy, C6-C24-aryloxy, C 2 -C 2 o-alkoxycarbonyl, Ci-C3o-alkylamino, Ci-C3o-alkylthio, C6-C24-arylthio, Ci-C 2 o-alkylsulphonyl or C 1 -C 20 - alkylsulphinyl, where these moiety may in each case be substituted by one or more alkyl, halogen,
  • X 1 and X 2 are identical or different and are two ligands, preferably anionic ligands.
  • X 1 and X 2 can be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C 2 o-alkoxy, C6-C24-aryloxy, C3-C 2 o-alkyldiketonate C6-C24- aryldiketonate, Ci-C 2 o-carboxylate, Ci-C 2 o-alkylsulphonate, C6-C24-arylsulphonate, C 1 -C 20 - alkylthiol, C6-C24-arylthiol, Ci-C 2 o-alkylsulphonyl or Ci-C 2 o-alkylsulphinyl.
  • X 1 and X 2 can also be substituted by one or more further groups, for example by halogen, preferably fluorine, Ci-Cio-alkyl, Ci-Cio-alkoxy or C6-C24-aryl, where these groups, too, may once again be substituted by one or more substituents selected from the group consisting of 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, Ci-C 5 -carboxylate, Ci-C 5 -alkyl, phenoxy, C 1 -C5- alkoxy, Ci-C 5 -alkylthiol, C6-C24-arylthiol, C6-C24-aryl or Ci-C 5 -alkylsulphonate.
  • X 1 and X 2 are identical and are each halogen, in particular 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-CH3-C 6 H4-S0 3 ), mesylate (CH3-SO3) or CF 3 S O 3 (trifluoromethanesulphonate) .
  • the symbols L represent identical or different ligands and are preferably uncharged electron donating ligand.
  • the two ligands L can, for example, be, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine (the latter two also being jointly referred to as "Im" ligand(s)).
  • phosphinite includes, for example, phenyl diphenylphosphinite, cyclohexyl dicyclohexylphosphinite, isopropyl diisopropylphosphinite and methyl diphenylphosphinite.
  • phosphite includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert- butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.
  • stibine includes, for example, triphenylstibine, tricyclohexylstibine and trimethylstibine.
  • sulfonate includes, for example, trifluoromethanesulphonate, 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 used as a collective term for all nitrogen-containing ligands as are mentioned by, for example, Grubbs in WO-A-03/011455.
  • examples are: pyridine, picolines (including ⁇ -, ⁇ - and ⁇ -picoline), lutidines (including 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.
  • catalysts of general formula (A) are used in which one or both of ligands L represent an imidazoline or imidazolidine ligand (also jointly referred to as "Im"- ligand in this application unless indicated otherwise), having a structure of general formulae (Ila) or (lib), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (Ila) or
  • R 8 , R 9 , R 10 , and R 11 can independently of one another, be substituted by one or more substituents, preferably straight-chain or branched Ci-Cio-alkyl, C 3 -Cg-cycloalkyl, CpCio-alkoxy or C6-C 2 4-aryl, C 2 -C 2 o heteroaryl, C 2 -C 2 o heterocyclic, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, where these abovementioned substituents, to the extent chemically possible, may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine
  • R 8 and R 9 are each identical or different and represent hydrogen, C6-C 2 4-aryl, straight-chain or branched Ci-Cio-alkyl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound.
  • R 8 and R 9 are identical and are selected from the group consisting of hydrogen, methyl, propyl, butyl and phenyl. _ -
  • R 8 and R 9 may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched Ci-Cio-alkyl or Cp Cio-alkoxy, C3-Cg-cycloalkyl, C6-C24-aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C1-C5- alkyl, Ci-C 5 -alkoxy and phenyl.
  • substituents preferably selected from the group consisting of halogen, in particular chlorine or bromine, C1
  • R 10 and R 11 are identical or different and preferably represent straight-chain or branched C1-C10- alkyl, C3-Cio-cycloalkyl, C6-C24-aryl, particularly preferably phenyl, Ci-Cur alkylsulfonate, C6-Cio-arylsulfonate.
  • R 10 and R 11 are identical and are selected from the group consisting of i-propyl, neopentyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, or 2,4,6- trimethylphenyl.
  • R 10 and R 11 may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched Ci-Cio-alkyl or Ci-Cio-alkoxy, C3- Cg-cycloalkyl, C6-C24-aryl, and a functional group selected from the group consisting of OH, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherin all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C 5 -alkyl, Ci-C 5 -alkoxy and phenyl.
  • substituents preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci
  • catalysts of general formula (A) in which one or both of ligands L represent imidazoline and imidazolidine ligands having the structures (Ilia) to (IIIu), where "Ph” means in each case phenyl, “Bu” means butyl, “Mes” represents in each case 2,4,6-trimethylphenyl, “Dipp” means in all cases 2,6-diisopropylphenyl and "Dimp” means 2,6-dimethylphenyl, and wherein the meaning of L can be identical or different in case both ligands L in general formula (A) have a structure according to (Ilia) to (IIIu), - -
  • one or both of the ligands L may have the meaning of general formulae (lie) or (lid), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (lie) or (lid),
  • R 8 , R 9 and R 10 may have all general, preferred, more preferred and most preferred meanings as defined above in relation to general formulae (Ila) and (lib), and - -
  • R , R and R are identical or different and may represent alkyl, cycloalkyl, alkoxy, aryl, aryloxy, or a heterocyclic group.
  • R 8 , R 9 , R 10 , R 15 , R 16 and R 17 may also be substituted by one or more further, identical or different substituents selected from the group consisting of straight-chain or branched Ci-C 5 -alkyl, in particular methyl, Ci-C 5 -alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.
  • substituents selected from the group consisting of straight-chain or branched Ci-C 5 -alkyl, in particular methyl, Ci-C 5 -alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester
  • the ligands L has the general formula (lid) wherein
  • R 15 , R 16 and R 17 are identical or different, even more preferably identical, and can represent d-
  • the ligand L has the general formula (lid) wherein
  • R 15 , R 16 and R 17 are identical and each selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2- methylbutyl, 3 -methylbutyl, neopentyl, 1 -ethylpropyl, n-hexyl, neophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, tolyl, 2,6-dimethylphenyl, and trifluoromethyl.
  • the ligand L possess general formula (lid) it most preferably represents 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 -S0 3 Na) 3 , P(CH 2 C 6 H 4 -S0 3 Na) 3 , P(isopropyl) 3 , P(CHCH 3 (CH 2 CH 3 )) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 or P(neophenyl) 3 .
  • X 1 , X 2 and L can have the same general, preferred and particularly preferred meanings as in the general formula (A),
  • n 0, 1 or 2
  • n 0, 1 , 2, 3 or 4 and
  • R' are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals which may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl.
  • a further catalyst of general formula (Al) is the catalyst of the formula (VI) below, where Mes is in each case 2,4,6-
  • This catalyst which is also referred to in the literature as "Nolan catalyst” is known, for example, from WO-A-2004/112951.
  • catalysts to be covered by component (1) are the catalysts of the general formula (B),
  • M is ruthenium or osmium
  • X 1 and X 2 are identical or different and are anionic ligands
  • R are identical or different and are organic moieties
  • Im is a substituted or unsubstituted imidazoline or imidazolidine ligand
  • An is an anion. - -
  • the catalysts of the general formula (B) are known in principle (see, for example, Angew. Chem. Int. Ed. 2004, 43, 6161-6165).
  • X 1 and X 2 in the general formula (B) can have the same general, preferred and particularly preferred meanings as in the formula (A).
  • the imidazoline or imidazolidine ligand usually has a structure of the general formulae (Ila) or (lib) which have been mentioned above for the catalyst of general formula (A) and can have all the structures mentioned there as preferred, in particular those of the formulae (Illa)-(IIIu).
  • R" are identical or different and are each a straight-chain or branched Cp C3o-alkyl, C 5 -C3o-cycloalkyl or aryl, where the Ci-C3o-alkyl moiety may be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
  • Aryl is an aromatic radical having from 6 to 24 skeletal carbon atoms.
  • monocyclic, bicyclic or tricyclic carbocyclic aromatic moieties having from 6 to 10 skeletal carbon atoms mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.
  • R" in the general formula (B) being identical and each being phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.
  • catalysts to be covered by component (1) are the catalysts of the general formula (C),
  • M is ruthenium or osmium
  • R 1J and R are each, independently of one another, hydrogen, Ci-C2o-alkyl, C2-C2o-alkenyl,
  • X is an anionic ligand
  • L is an uncharged ⁇ -bonded ligand which may either be monocyclic or polycyclic
  • - - is a ligand selected from the group consisting of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines,
  • catalysts to be covered by component (1) are the catalysts of the general formula (D),
  • M is ruthenium or osmium
  • X 1 and X 2 are identical or different and are anionic ligands which can have all meanings of
  • R 19 and R 20 are identical or different and are each hydrogen or substituted or unsubstituted alkyl.
  • catalysts to be covered by component (1) are the catalysts of the general formula (E), (F) and (G)
  • ligands are identical or different and are two ligands, preferably anionic ligands, is a ligand, preferably an uncharged electron donor,
  • the catalysts of the general formulae (E), (F), and (G) are known in principle, e.g. from WO 2003/011455 Al, 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 preparative methods indicated in the abovementioned literature references.
  • the catalysts of the general formulae (E), (F), and (G) can be used in which Z 1 and Z 2 are identical or different and are uncharged electron donors. These ligands are usually weakly coordinating. The ligands are typically optionally substituted heterocyclic groups.
  • These can be five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably CpCio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C6-C24-aryl, or heteroaryl, preferably C 5 -C23-heteroaryl, radicals which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C 5 -alkyl, Ci-C 5 -alkoxy and phenyl.
  • Z 1 and Z 2 encompass nitrogen-containing heterocycles such as pyridines, pyridazines, bipyridines, pyrimidines, pyrazines, pyrazolidines, pyrrolidines, piperazines, indazoles, quinolines, purines, acridines, bisimidazoles, picolylimines, imidazolines, imidazolidines and pyrroles.
  • nitrogen-containing heterocycles such as pyridines, pyridazines, bipyridines, pyrimidines, pyrazines, pyrazolidines, pyrrolidines, piperazines, indazoles, quinolines, purines, acridines, bisimidazoles, picolylimines, imidazolines, imidazolidines and pyrroles.
  • Z 1 and Z 2 can also be bridged to one another to form a cyclic structure.
  • Z 1 and Z 2 form a single bidentate ligand.
  • L can have the same general, preferred and particularly preferred meanings as L in the general formula (A) and (B).
  • R 21 and R 22 are identical or different and are each alkyl, preferably Ci-C3o-alkyl, particularly preferably Ci-C2o-alkyl, cycloalkyl, preferably C3-C2o-cycloalkyl, particularly preferably C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, particularly preferably C2-Ci6-alkenyl, alkynyl, preferably C2-C2o-alkynyl, particularly preferably
  • X 1 and X 2 are identical or different and can have the same general, preferred and particularly preferred meanings as indicated above for X 1 and X 2 in the general formula (A).
  • Further catalysts to be covered by component (1) are those of general formulae (E), (F), and (G) in which
  • M is ruthenium
  • X 1 and X 2 are both halogen, in particular chlorine,
  • R 1 and R 2 are identical or different and are five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case be substituted by one or more moieties selected from the group consisting of alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably Ci-Cio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably
  • Z 1 and Z 2 are identical or different and five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all these abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably CpCio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C6-C24-aryl, or heteroaryl, preferably C 5 -C23-heteroaryl, radicals which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C 5 -alkyl, Ci-C 5 -alkoxy
  • a further catalyst to be covered by component (1) has the structure (XIX),
  • R and R are identical or different and are each halogen, straight-chain or branched Cp C2o-alkyl, Ci-C2o-heteroalkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C6-C24-aryl, preferably bromine, phenyl, formyl, nitro, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, dialkylamino, trialkylsilyl or trialkoxysilyl.
  • R 23 and R 24 C r C 2 o-alkyl, C r C 2 o-heteroalkyl, C r Ci 0 -haloalkyl, Ci-Cio-alkoxy, C6-C24-aryl, preferably phenyl, formyl, nitro, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, trialkylsilyl and trialkoxysilyl may in turn each be substituted by one or more halogen, preferably fluorine, chlorine or bromine, Ci-C 5 -alkyl, Ci-C 5 -alkoxy or phenyl moities.
  • halogen preferably fluorine, chlorine or bromine
  • component (1) Further catalysts to be covered by component (1) have the structure (XIX a) or (XIX b), where R 23 and R 24 have the same meanin s as indicated in formula (XIX).
  • component (1) which come under general formulae (E), (F), and (G) have the structural formulae (XX)-(XXXII), where Mes is in each case 2,4,6-trimethylphenyl. - -
  • R 25_ R 32 are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol,
  • CF 3 nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (-SO 3 ), -OSO 3 " , -PO 3 " or OPO 3 " or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where all these moieties can each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an al
  • n 0 or 1
  • R -R are identical or different and can each have the same meanings as R -R . - -
  • the carbon atom denoted by "*" is bound via one or more double bonds to the catalyst framework. If the carbon atom denoted by "*" is bound via two or more double bonds to the catalyst framework, these double bonds can be cumulated or conjugated.
  • the catalysts (N) having a structural element of the general formula (Nl) include, for example, cata
  • M is ruthenium or osmium
  • X 1 and X 2 are identical or different and are two ligands, preferably anionic ligands,
  • L 1 and L 2 are identical or different ligands, preferably uncharged electron donors, where L can alternatively also be bridged to the radical R 8 ,
  • n 0, 1, 2 or 3, preferably 0, 1 or 2
  • n' is 1 or 2, preferably 1, and
  • R -R , m and A have the same meanings as in the general formula (Nl).
  • the structural element of the general formula (Nl) is bound via conjugated double bonds to the metal of the complex catalyst. In both cases, the carbon atom denoted by "*" as a double bond in the direction of the central metal of the complex catalyst.
  • the catalysts of the general formulae (N2a) and (N2b) thus encompass catalysts in which the general structural elements (N3)-(N9) - -
  • R 25_ R 32 are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF 3 , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (-SO 3 ), -OSO 3 " , -PO 3 " or OPO 3 " or alkyl, preferably Ci-C2o-alkyl, in particular Ci-Ce-alkyl, cycloalkyl , preferably C3-C20- cycloalkyl, in particular C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, alkynyl, preferably C2-C2o-alkynyl, aryl, preferably C6-C24-aryl, in particular phenyl
  • n 0 or 1
  • Ci-C6-Alkyl in the structural element of the general formula (Nl) is, for example, methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl or n-hexyl.
  • C3-Cg-Cycloalkyl in the structural element of the general formula (Nl) is, for example, cyclopropyl, cyclobutyl, cylopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • C6-C24-Aryl in the structural element of the general formula (Nl) comprises an aromatic radical having from 6 to 24 skeletal carbon atoms.
  • aromatic radicals having from 6 to 24 skeletal carbon atoms.
  • monocyclic, bicyclic or tricyclic carbocyclic aromatic radicals having from 6 to 10 skeletal carbon atoms mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.
  • X 1 and X 2 in the structural element of the general formula (Nl) have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula A.
  • L 1 and L 2 are identical or different ligands, preferably uncharged electron donors, and can have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula A. - -
  • catalysts to be covered by component (1) are catalysts of the general formulae (N2a) or (N2b) having a general structural unit (Nl) in which
  • M is ruthenium
  • X 1 and X 2 are both halogen
  • n 0, 1 or 2 in the general formula (N2a) or
  • n' is 1 in the general formula (N2b)
  • L 1 and L 2 are identical or different and have the general or preferred meanings indicated for the general formulae (N2a) and (N2b),
  • n 0 or 1
  • A is oxygen, sulphur, C(C r Cio-alkyl) 2 , -C(Ci-Ci 0 -alkyl) 2 -C(Ci-Ci 0 -alkyl) 2 -, -C(Ci_Cio- or -N(C r Ci 0 -alkyl).
  • catalysts to be covered by component (1) are catalysts of the general formulae (N2a) or (N2b) having a general structural unit (Nl) in which
  • M is ruthenium
  • X 1 and X 2 are both chlorine
  • n 0, 1 or 2 in the general formula (N2a) or
  • n' is 1 in the general formula (N2b)
  • L 1 is an imidazoline or imidazolidine ligand of one of the formulae (Ilia) to (IIIu),
  • L 2 is a sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine radical, an imidazolidine radical of one of the formulae (Xlla) to (Xllf) or a phosphine ligand, in particular PPh 3 , P(p-
  • R 25 -R 32 have the general or preferred meanings indicated for the general formulae (N2a) and
  • n 0 or 1
  • A is oxygen, sulphur, C(C r Ci 0 -alkyl) 2 , -C(C r Cio-alkyl) 2 -C(Ci-Cio-alkyl) 2 -, -C(C r Ci 0 - or -N(C r Ci 0 -alkyl).
  • Y 1 is oxygen, sulphur, N-R 41 or P-R 41 , where R 41 has the meanings indicated below,
  • R 40 and R 41 are identical or different and are each alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl which may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,
  • p is 0 or 1
  • catalysts to be covered by component (1) are catalysts of the general formulae (Q) which can be used for hydrogenation and/or molecular weight degradation reaction of nitrile rubber during a metathesis
  • M is ruthenium or osmium
  • X 1 and X 2 are identical or different ligands
  • L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure
  • R 1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl and
  • R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen or an organic or inorganic substituent
  • n 0 or 1
  • n shall mean that Y and (E) n are linked either by a single bond or by a double bond, wherein
  • Y is oxygen (O), sulfur (S), N-R or P-R and
  • E is CH 2 or
  • Y is oxygen (O), sulfur (S), N-R or P-R and directly linked by a single bond to the phenyl moiety depicted above in formula (L)
  • R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl. - -
  • the catalysts of the general formula (Q) are known in principle. Representatives of this class of compounds are e.g. the catalysts described by Hoveyda et al. in US 2002/0107138 Al and Angew Chem. Int. Ed. 2003, 42, 4592, and the catalysts described by Grela in WO-A-2004/035596, Eur. J. Org. Chem 2003, 963-966 and Angew. Chem. Int. Ed. 2002, 41, 4038 and also in J. Org. Chem. 2004, 69, 6894-96 and Chem. Eur. J 2004, 10, 777-784. Further representatives of this class of catalysts are the catalysts described in EP-A-1 905 777.
  • Components (2) which shall be removed by the process of the present invention comprise
  • iron-containing residues and degradation products thereof can occur due to a minimum corrosion or degradation which might happen in any metal vessel or pipes or alternatively due to the fact that iron-containing compounds might have been used as activators in the polymerisation of the nitrile rubber.
  • Components (III) which shall be removed according to the present invention comprise
  • ionic alkali and earth alkali based residues in particular Ca, Na, K- based ionic residues non metallic ionic residues, in particular on the basis of phosphorus
  • Fatty acids, anti-oxidants and antidegradant stabilizers are used during the emulsion polymerisation of the nitrile rubbers and prevent destabililzation of the emulsion latex and resulting solid polymer.
  • antioxidants or antidegradent stabilizers can inhibit these radicals from prematurely 'aging' the polymer.
  • these antioxidants or antidegradent stabilizers can consist of hindered amines, diamines, phenylenediamines, monophenols and bisphenols which can include but are not reststricted to; butylated hydroxytoluene (BHTTM, octylated diphenylamine (ODPA), VulkanoxTM 3100,
  • the process of the invention can be carried out in the presence of one or more organic solvents (other than the ionic liquid), which, for example, makes it easier to separate the (H)NBR from the ionic liquid and the catalyst present therein.
  • organic solvents other than the ionic liquid
  • Contacting the (H)NBR solution with at least one ionic liquid results in a two phase system being formed. If the components (1) to (3) to be removed have an ionic character they dissolve preferentially in the ionic liquid.
  • Such ionic phase comprising the catalyst, the catalyst degradation products as well as all other compounds to be removed can easily be separated from the organic solvent and (H)NBR present therein.
  • the catalyst in the ionic liquid can be recycled and used for further metathesis or hydrogenation reactions, respectively, preferably after other impurities have been removed through distillation or washing steps.
  • Processes for recycling ionic liquids are in principle known from prior art (EP-A-1 218 890; Chem. Rev. 2002, 102, 3667-3692, US 2003/0085156 A)
  • the solvent used is an organic solvent.
  • Suitable organic solvents are, in particular, halogenated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, 1 ,2- dichloroethane or trichloroethane, aromatic compounds such as benzene, toluene, xylene, cumene or halogenobenzenes, alkanes such as pentane, hexane or cyclohexane, esters such as teri-butyl- methyl esters or acetic esters, ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, amides such as dimethylformamide, antioxidants such as hydroquinones, acetone, dimethyl carbonate or alcohols.
  • halogenated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, 1 ,2- dichlor
  • Preferred solvents for use in the process of the invention are C 5 -C2o-alkanes, ethers and halogenated hydrocarbons. Acetone, toluene or mono-chlorobenzene are very particularly preferably used in the process of the invention.
  • the process pursuant to the present invention can be carried out batch-wise, i.e. discontinuously, or continuously. If the process is performed batch-wise the optionally hydrogenated nitrile rubber, in particular dissolved in an organic solvent, is contacted with at least one ionic liquid in a vessel which may be agitated. Typically the optionally hydrogenated nitrile rubber optionally dissolved is dosed into the vessel and the ionic liquid added thereafter while stirring the vessel. In an alternative embodiment the process may be performed continuously. Particularly such continuous process is performed in countercurrent flow. In another alternative embodiment it is possible to bubble the ionic liquid through the solution of the optionally hydrogenated nitrile rubber. This may be realized for both, the batch-wise as well as continuous process.
  • the ionic liquid can be removed from the optionally hydrogenated nitrile rubber e.g. by known phase separation techniques.
  • the remaining optionally hydrogenated nitrile in the organic solvent is then coagulated using typical coagulation methods. - -
  • reaction mixture comprising the optionally hydrogenated nitrile rubber, at least one solvent and at least one ionic liquid may be fed either to an extruder or to a press and the ionic liquid as well as the solvent are removed.
  • the remaining optionally hydrogenated nitrile rubber may be subjected to one or more further washing and drying steps.
  • the process of the invention is usually carried out in a temperature range from -20°C to 200°C, preferably from 0°C to 150°C, very particularly preferably from 20°C to 100°C.
  • Perbunan ® T 3429 (Nitrile Rubber) statistical butadiene-acrylonitrile copolymer with an acrylonitrile content of 34 mol% and a Mooney- Viscosity ML (l+4)@ 100 °C of 29 MU.
  • ML Mooney- Viscosity
  • Perbunan ® T 4441 (Nitrile Rubber) statistical butadiene-acrylonitrile copolymer with an acrylonitrile content of 44 mol% and a Mooney- Viscosity ML (l+4)@ 100 °C of 41 MU.
  • Ammoeng 102 Tetralkylammoniumsulfate having the formula
  • Perbunan ® T 4441 was metathesised utilizing 4 phr of 1-hexene and 0.007 phr Grubbs (II) generation catalyst.
  • the low molecular weight nitrile rubber was then hydrogenated utilizing 0,02 phr of Wilkinson's catalyst (see Table 1).
  • To the low molecular weight hydrogenated nitrile polymer solution in monochlorobenzene (100 g) was added 50 g of the ionic liquid as shown in Table 1. It was allowed to react for a determined period at a set temperature (see Table 2) while being agitated.
  • the hydrogenated nitrile rubber was generated through the hydrogenation using 0,05 phr Wilkinson's catalyst and 1 phr triphenylphosphine of a 15 wt.-%> Perbunan ® T 3429 solution in monochlorobenzene at 138°C and 85 bar of H 2 pressure. Completion of the hydrogenation was monitored through the achievement of 99+%> hydrogenation of the carbon-carbon double bonds.
  • Rh and Fe content of the hydrogenated nitrile rubber was then performed using - - ion phase chromatography.
  • the analysis of the fatty acid and the antioxidant content and residues in the polymer was performed via gas chromatography. All results are shown in Table 4.
  • control data have been obtained using a hydrogenated nitrile rubber (Therban A 3406, abvailable from Lanxess GmbH) which is manufactured on a commercial scale by hydrogenation of Perbunan ® T 3429 also using Wilkinson's catalyst and triphenylphosphine in principally the same manner as described above for Examples 3 to 5.
  • a hydrogenated nitrile rubber Therban A 3406, abvailable from Lanxess Germany GmbH
  • Table 4 illustrates that increasing the temperature at which the reaction proceeds may improve the efficiency of the purification.
  • the efficiency of the rhodium (Rh) removal rises from 83% to 90%> respectively.
  • the temperature effect relating to the efficiency of the iron (Fe) removal is lesser with only an increase in efficiency from 97%) to 99+%> occurring when moving from 22°C to 100°C respectively.
  • the antioxidant (Vulkanox ® BKF) nor the fatty acid emulsifier content were observed to be dependent on temperature as 91%> of the fatty acid emulsifier was removed from each example, while 87% to 90% of the BKF was removed.
  • Table 6 illustrates that the purification of the nitrile rubber with ionic liquids afforded a decrease in the sodium (Na) content of more than 45% for Examples 8 and 9, a decrease in potassium (K) content of more than 70% for examples 6 and 7, a decrease in the calcium (Ca) content of more than 50% and a decrease in magnesium (Mg) ion content of more than 15%.
  • Na sodium
  • K potassium
  • Ca calcium
  • Mg magnesium

Abstract

La présente invention porte sur un nouveau processus de purification d'un caoutchouc nitrile éventuellement hydrogéné, consistant à mettre en contact ledit caoutchouc nitrile éventuellement hydrogéné avec au moins un liquide ionique afin d'éliminer une large variété d'impuretés, notamment divers catalyseurs et leurs produits de dégradation, ainsi que les composés utilisés soit au cours de la polymérisation en émulsion pour préparer le caoutchouc nitrile, soit au cours de la réaction de métathèse subséquente éventuelle et/ou de la réaction d'hydrogénation éventuelle, ou tout produit de dégradation résultant de celles-ci.
PCT/EP2012/074601 2011-12-28 2012-12-06 Purification de caoutchouc nitrile éventuellement hydrogéné WO2013098056A1 (fr)

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WO2015101602A1 (fr) * 2013-12-30 2015-07-09 Lanxess Deutschland Gmbh Caoutchouc nitrile hydrogéné contenant du sulfure de phosphane ou diphosphane
WO2015101601A1 (fr) * 2013-12-30 2015-07-09 Lanxess Deutschland Gmbh Caoutchouc nitrile hydrogéné contenant de l'oxyde de phosphane ou diphosphane
WO2020020677A1 (fr) 2018-07-23 2020-01-30 Arlanxeo Deutschland Gmbh Procédé de production de caoutchouc nitrile hydrogéné et compositions hnbr de celui-ci
US20220220289A1 (en) * 2021-01-08 2022-07-14 Zeon Chemicals L.P. Hydrogenated nitrile rubber with reduced catalyst impurity
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WO2015101601A1 (fr) * 2013-12-30 2015-07-09 Lanxess Deutschland Gmbh Caoutchouc nitrile hydrogéné contenant de l'oxyde de phosphane ou diphosphane
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WO2020020677A1 (fr) 2018-07-23 2020-01-30 Arlanxeo Deutschland Gmbh Procédé de production de caoutchouc nitrile hydrogéné et compositions hnbr de celui-ci
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US11905395B2 (en) 2020-06-26 2024-02-20 Asahi Kasei Kabushiki Kaisha Molded bale of rubber composition, method for producing molded bale, crosslinking rubber composition, and tread for tire
US20220220289A1 (en) * 2021-01-08 2022-07-14 Zeon Chemicals L.P. Hydrogenated nitrile rubber with reduced catalyst impurity

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