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  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/08—Depolymerisation
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  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0255—Phosphorus containing compounds
  • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
  • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2269—Heterocyclic carbenes
  • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
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  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
  • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
  • B01J31/30—Halides
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/02—Hydrogenation
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  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C2019/09—Metathese

Definitions

• the present invention relates to novel catalyst systems and a method for reacting chemical compounds by subjecting such compounds to a metathesis reaction in the presence of said catalyst systems.
• Metathesis reactions are widely used for chemical syntheses, e.g. in the form of ring-closing metatheses (RCM), cross-metatheses (CM) or ring-opening metatheses (ROMP). Metathesis reactions are employed, for example, for the synthesis of olefins, for the depolymerization of unsaturated polymers and for the synthesis of telechelic polymers.
• RCM ring-closing metatheses
• CM cross-metatheses
• RMP ring-opening metatheses
• Metathesis reactions are employed, for example, for the synthesis of olefins, for the depolymerization of unsaturated polymers and for the synthesis of telechelic polymers.
• Metathesis catalysts are known, inter alia, from WO-A-96/04289 and WO-A-97/06185. They have the following in-principle structure: where M is osmium or ruthenium, the radicals R are identical or different organic radicals having a wide range of structural variation, X 1 and X 2 are anionic ligands and L are uncharged electron donors.
• M is osmium or ruthenium
• the radicals R are identical or different organic radicals having a wide range of structural variation
• X 1 and X 2 are anionic ligands
• L uncharged electron donors.
• anionic ligands is used in the literature regarding such metathesis catalysts to describe ligands which are always negatively charged with a closed electron shell when regarded separately from the metal centre.
• Nitrile rubber also referred to as “NBR” for short, is rubber which is a copolymer or terpolymer of at least one ⁇ , ⁇ -unsaturated nitrile, at least one conjugated diene and, if appropriate, one or more further copolymerizable monomers.
• Hydrogenated nitrile rubber also referred to as “HNBR” for short, is produced by hydrogenation of nitrile rubber. Accordingly, the C ⁇ C double bonds of the copolymerized diene units have been completely or partly hydrogenated in HNBR.
• the degree of hydrogenation of the copolymerized diene units is usually in the range from 50 to 100%.
• Hydrogenated nitrile rubber is a specialty rubber which has very good heat resistance, an excellent resistance to ozone and chemicals and also an excellent oil resistance.
• HNBR has found wide use in a variety of applications.
• HNBR is used, for example, for seals, hoses, belts and damping elements in the automobile sector, also for stators, oil well seals and valve seals in the field of oil extraction and also for numerous parts in the aircraft industry, the electronics industry, mechanical engineering and shipbuilding.
• HNBR grades usually have a Mooney viscosity (ML 1+4 at 100° C.) in the range from 55 to 105, which corresponds to a weight average molecular weight M w (method of determination: gel permeation chromatography (GPC) against polystyrene equivalents) in the range from about 200 000 to 500 000.
• M w weight average molecular weight
• PDI polydispersity index
• HNBR processability of HNBR is subject to severe restrictions as a result of the relatively high Mooney viscosity.
• HNBR grade which has a lower molecular weight and thus a lower Mooney viscosity. This would decisively improve the processability.
• thermomechanical treatment e.g. on a roll mill or in a screw apparatus (EP-A-0 419 952).
• this thermomechanical degradation has the disadvantage that functional groups such as hydroxyl, keto, carboxyl and ester groups, are incorporated into the molecule as a result of partial oxidation and, in addition, the microstructure of the polymer is substantially altered.
• HNBR HNBR having low molar masses corresponding to a Mooney viscosity (ML 1+4 at 100° C.) in the range below 55 or a number average molecular weight of about M n ⁇ 200 000 g/mol was for a long time not possible by means of established production processes since, firstly, a step increase in the Mooney viscosity occurs in the hydrogenation of NBR and, secondly, the molar mass of the NBR feedstock used for the hydrogenation cannot be reduced at will since otherwise the work-up can no longer be carried out in the industrial plants available because the product is too sticky.
• the lowest Mooney viscosity of an NBR feedstock which can be processed without difficulties in an established industrial plant is about 30 Mooney units (ML 1+4 at 100° C.).
• the Mooney viscosity of the hydrogenated nitrile rubber obtained using such an NBR feedstock is in the order of 55 Mooney units (ML 1+4 at 100° C.).
• the Mooney viscosity is determined in accordance with ASTM standard D 1646.
• this problem is solved by reducing the molecular weight of the nitrile rubber prior to hydrogenation by degradation to a Mooney viscosity (ML 1+4 at 100° C.) of less than 30 Mooney units or a number average molecular weight of M n ⁇ 70 000 g/mol.
• the decrease in the molecular weight is achieved by metathesis in which low molecular weight 1-olefins are usually added.
• the metathesis of nitrile rubber is described, for example, in WO-A-02/100905, WO-A-02/100941 and WO-A-03/002613.
• the metathesis reaction is advantageously carried out in the same solvent as the hydrogenation reaction (in situ) so that the degraded nitrile rubber does not have to be isolated from the solvent after the degradation reaction is complete before it is subjected to the subsequent hydrogenation.
• Metathesis catalysts which have a tolerance towards polar groups, in particular towards nitrile groups, are used for catalyzing the metathetic degradation reaction.
• WO-A-02/100905 and WO-A-02/100941 describe a process which comprises degradation of nitrile rubber starting polymers by olefin metathesis and subsequent hydrogenation to form HNBR having a low Mooney viscosity.
• a nitrile rubber is reacted in a first step in the presence of a coolefin and specific catalysts based on osmium, ruthenium, molybdenum or tungsten complexes and hydrogenated in a second step.
• Hydrogenated nitrile rubbers having a weight average molecular weight (M w ) in the range from 30 000 to 250 000, a Mooney viscosity (ML 1+4 at 100° C.) in the range from 3 to 50 and a polydispersity index PDI of less than 2.5 can be obtained by this route.
• M w weight average molecular weight
• ML 1+4 at 100° C. Mooney viscosity
• PDI polydispersity index
• the metathesis of nitrile rubber can be carried out using, for example, the catalyst bis(tricyclohexylphosphine)benzylideneruthenium dichloride shown below.
• the nitrile rubbers After metathesis and hydrogenation, the nitrile rubbers have a lower molecular weight and also a narrower molecular weight distribution than the hydrogenated nitrile rubbers which have hitherto been able to be prepared according to the prior art.
• WO-A-00/71554 discloses a group of catalysts which are known in the technical field as “Grubbs (II) catalysts”.
• the hydrogenated nitrile rubber has lower molecular weights and a narrower molecular weight distribution (PDI) than when using catalysts of the Grubbs (I) type.
• PDI molecular weight distribution
• the metathetic degradation thus proceeds more efficiently when using catalysts of the Grubbs II type than when using catalysts of the Grubbs I type.
• the amounts of ruthenium necessary for this efficient metathetic degradation are still relatively high. Long reaction times are also still required for carrying out the metathesis using the Grubbs II catalyst.
• the activity of the catalysts used is also of critical importance in other types of metathesis reactions.
• the invention therefore provides a catalyst system comprising a metathesis catalyst and one or more salts of the general formula (I) K n+ A z ⁇ (I) where K is a cation with the exception of copper and A is an anion, where n is 1, 2 or 3 and z is 1, 2 or 3.
• 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.
• Suitable cations are based on elements from the Periodic Table (main groups and transition elements) which can form cations bearing one, two or three positive charges, with the exception of copper.
• Suitable cations are, for example, lithium, sodium, potassium rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, mercury and also all elements of the group of the rare earths, in particular cerium, praseodynium and neodymium, and the elements of the actinides.
• Suitable cations are complex cations based on nitrogen, phosphorus or sulphur. It is possible to use, for example, tetralkylammonium, tetraarylammonium, hydroxylammonium, tetraalkylphosphonium, tetraarylphosphonium, sulphonium, anilinium, pyridinium, imidazolium, guanidinium and hydrazinium cations and also cationic ethylenediamine derivatives.
• alkyl radicals in all the abovementioned complex cations can be identical or different and are usually each a straight-chain or branched C 1 -C 30 -alkyl radical, preferably a C 1 -C 20 -alkyl radical, particularly preferably a C 1 -C 18 -alkyl radical. These alkyl radicals can also be substituted by aryl radicals.
• C 1 -C 18 -Alkyl encompasses, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-eth
• the aryl radicals in all the abovementioned complex cations can likewise be identical or different and are usually each a C 6 -C 24 -aryl radical, preferably a C 6 -C 14 -aryl radical, particularly preferably a C 6 -C 10 -aryl radical.
• Examples of C 6 -C 24 -aryl are phenyl, o-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl and fluorenyl.
• the sulphonium cations of the [R 3 S] + type bear three identical or different radicals which can be aliphatic or aromatic in nature. These radicals can be alkyl or aryl radicals having the abovementioned general, preferred and particularly preferred meanings.
• Particularly preferred complex cations are benzyldodecyldimethylammonium, didecyldimethylammonium, dimethylanilinium, N-alkyl-N,N-bis-(2-hydroxyalkyl)-N-benzylammonium, N,N,N-triethylbenzolmethanaminium, O-methyluronium, S-methylthiuronium, pyridinium, tetrabutylammonium, tetramethyluronium, tetracetylammonium, tetrabutylphosphonium, tetraphenylphosphonium, diphenylguanidinium, di-o-tolylguanidinium, butyldiphenylsulphonium, tributylsulphonium.
• A is a singly, doubly, or triply charged anion, preferably from the group consisting of halides, pseudohalides, complex anions, anions of organic acids, aliphatic or aromatic sulphonates, aliphatic or aromatic sulphates, phosphonates, phosphates, thiophosphates, xanthogenates, dithiocarbamates and noncoordinating anions.
• Preferred halides are fluoride, chloride, bromide, iodide.
• Preferred pseudohalides are, for example triiodide, azide, cyamide, thiocyamide, thiocyanate and interhalides.
• Suitable complex anions are, for example, sulphite, sulphate, dithionite, thiosulphate, carbonate, hydrogencarbonate, perthiocarbonate, nitrite, nitrate, perchlorate, tetrafluoroborate, tetrafluoroaluminate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and hexachloroantimonate.
• Preferred singly, doubly or triply charged anions of organic acids are singly, doubly or triply charged anions of organic carboxylic acids having from 1 to 20 carbon atoms.
• the organic carboxylic acids can be saturated or monounsaturated or polyunsaturated. Selected examples are formate, acetate, propionate, butyrate, oleate, palmitate, stearate, versatate, acrylate, methacrylate, crotonate, benzoate, naphthalenecarbonate, oxalate, salicylate, terephthalate, fumarate, maleate, itaconate and abietate.
• Suitable aliphatic or aromatic sulphonates are anthraquinone-2-sulphonate, benzenesulphonate, benzene-1,3-disulphonate, decane-1-sulphonate, hexadecane-1-sulphonate, hydroquinonemono-sulphonate, methyl-4-toluenesulphonate, naphthalene-1-sulphonate, naphthalene-1,5-disulphonate, tosylate and mesylate.
• Suitable aliphatic or aromatic sulphates are, for example, dodecylsulphate and alkylbenzenesulphates.
• Suitable phosphonates, phosphates and thiophosphates are vinylphosphonate, ethylphosphonate, butylphosphonate, cetylphosphonate, dibutylphosphate, dioctylphosphate, dibutyldithiophosphate and dioctylthiophosphate.
• Suitable aliphatic or aromatic xanthogenates are ethylxanthogenate, butylxanthogenate, phenylxanthogenate, benzylxanthogenate, etc.
• Suitable aliphatic or aromatic dithiocarbamates are dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate and dibenzyldithiocarbamate.
• Noncoordinating anions are, for example, tetrakis[pentafluorophenyl]borate, pentakis-[pentafluorophenyl]phosphate, tetrakis[3,5-trifluoromethylphenyl]borate, pentakis[3,5-trifluoro-methylphenyl]phosphate and pentakis[pentafluorophenyl]cyclohexadienyl anion.
• Suitable catalysts in the catalyst systems of the invention are compounds of the general formula (A) where
• 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 C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate, C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radicals.
• radicals X 1 and X 2 can also be substituted by one or more further radicals, for example by halogen, preferably fluorine, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl, where these radicals may also in turn be substituted by one or more substitutents selected from the group consisting of halogen, preferably fluorine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy and phenyl.
• halogen preferably fluorine, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl
• X 1 and X 2 are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C 1 -C 5 -carboxylate, C 1 -C 5 -alkyl, phenoxy, C 1 -C 5 -alkoxy, C 1 -C 5 -alkylthiol, C 6 -C 24 -arylthiol, C 6 -C 24 -aryl or C 1 -C 5 -alkylsulphonate.
• halogen in particular fluorine, chlorine, bromine or iodine
• 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-CH 3 —C 6 H 4 —SO 3 ), mesylate (2,4,6-trimethylphenyl) or CF 3 SO 3 (trifluoromethanesulphonate).
• L represents identical or different ligands, preferably uncharged electron donors.
• the two ligands L can, for example, each be, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine, thioether or imidazolidine (“Im”) ligand.
• the two ligands L each being, independently of one another, a C 6 -C 24 -arylphosphine, C 1 -C 5 -alkylphosphine or C 3 -C 20 -cycloalkylphosphine ligand, a sulphonated C 6 -C 24 -arylphosphine or C 1 -C 10 -alkylphosphine ligand, a C 6 -C 24 -aryl phosphinite or C 1 -C 10 -alkyl phosphinite ligand, a C 6 -C 24 -aryl phosphonite or C 1 -C 10 -alkyl phosphonite ligand, a C 6 -C 24 -aryl phosphite or C 1 -C 10 -alkylphosphite ligand, a C 6 -C 24 -arylarsine or C 1 -C 10 -alkylars
• phosphine includes, for example, PPh 3 , P(p-Tol) 3 , P(o-Tol) 3 , PPh(CH 3 ) 2 , P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , P(p-CF 3 C 6 H 4 ) 3 , P(C 6 H 4 —SO 3 Na) 3 , P(CH 2 C 6 H 4 —SO 3 Na) 3 , P(iso-Pr) 3 , P(CHCH 3 (CH 2 CH 3 )) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 and P(neophenyl) 3 .
• Phosphinite includes, for example, triphenyl phosphinite, tricyclohexyl phosphinite, triisopropyl phosphinite and methyl diphenylphosphinite.
• Phosphite includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphate.
• Stibine includes, for example, triphenylstibine, tricyclohexylstibine and trimethylstibene.
• Sulphonate includes, for example, trifluoromethanesulphonate, tosylate and mesylate.
• Sulphoxide includes, for example, CH 3 S( ⁇ O)CH 3 and (C 6 H 5 ) 2 SO.
• Thioether includes, for example, CH 3 SCH 3 , C 6 H 5 SCH 3 , CH 3 OCH 2 CH 2 SCH 3 and tetrahydrothiophene.
• the imidazolidine radical (Im) usually has a structure of the general formula (IIa) or (IIb), where
• one or more of the radicals R 8 , R 9 , R 10 , R 11 can, independently of one another, be substituted by one or more substitutents, preferably straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl, with these abovementioned substitutents in turn being able to be substituted by one or more radicals, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy and phenyl.
• substitutents preferably straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl, with these abovementioned substitutents in turn being able
• R 8 and R 9 are each, independently of one another, hydrogen, C 6 -C 24 -aryl, particularly preferably phenyl, straight-chain or branched C 1 -C 10 -alkyl, particularly preferably propyl or butyl, or together form, with inclusion of the carbon atoms to which they are bound, a cycloalkyl or aryl radical, where all the abovementioned radicals may in turn be substituted by one or more further radicals selected from the group consisting of straight-chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 6 -C 24 -aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxyl, disulphide, carbonate, isocyanate, carbodiimi
• the radicals R 10 and R 11 are identical or different and are each straight-chain or branched C 1 -C 10 -alkyl, particularly preferably i-propyl or neopentyl, C 3 -C 10 -cycloalkyl, preferably adamantyl, C 6 -C 24 -aryl, particularly preferably phenyl, C 1 -C 10 -alkylsulphonate, particularly preferably methanesulphonate, C 6 -C 10 -arylsulphonate, particularly preferably p-toluenesulphonate.
• Radicals R 10 and R 11 of the abovementioned type may optionally be substituted by one or more further radicals selected from the group consisting of straight-chain or branched C 1 -C 5 -alkyl, in particular methyl, C 1 -C 5 -alkoxy, aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxyl, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.
• further radicals selected from the group consisting of straight-chain or branched C 1 -C 5 -alkyl, in particular methyl, C 1 -C 5 -alkoxy, aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine
• radicals R 10 and R 11 may be identical or different and are each i-propyl, neopentyl, adamantyl or mesityl.
• both ligands L in the general formula (A) being identical or different trialkylphosphine ligands in which at least one of the alkyl groups is a secondary alkyl group or a cycloalkyl group, preferably isopropyl, isobutyl, sec-butyl, neopentyl, cyclopentyl or cyclohexyl.
• one ligand L in the general formula (A) being a trialkylphosphine ligand in which at least one of the alkyl groups is a secondary alkyl group or a cycloalkyl group, preferably isopropyl, isobutyl, sec-butyl, neopentyl, cyclopentyl or cyclohexyl.
• Two catalysts which are preferred for the catalyst system of the invention and come under the general formula (A) have the structures (III) (Grubbs (I) catalyst) and (IV) (Grubbs (II) catalyst), where Cy is cyclohexyl.
• the catalysts of the general formula (B) are known in principle. Representatives of this class of compounds are the catalysts described by Hoveyda et al. in US 2002/0107138 A1 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 in J. Org. Chem. 2004, 69, 6894-96 and Chem. Eur. J 2004, 10, 777-784.
• the catalysts are commercially available or can be prepared as described in the references cited.
• L is a ligand which usually has an electron donor function and can have the same general, preferred and particularly preferred meanings as L in the general formula (A).
• L in the general formula (B) is preferably a P(R 7 ) 3 radical, where the radicals R 7 are each, independently of one another, C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl or aryl or else a substituted or unsubstituted imidazolidine radical (“Im”).
• C 1 -C 6 -Alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl or n-hexyl.
• C 3 -C 8 -Cycloalkyl encompasses cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• Aryl encompasses an aromatic radical having from 6 to 24 skeletal carbon atoms.
• Preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic radicals having from 6 to 10 skeletal carbon atoms are, for example, phenyl, biphenyl, naphthyl, phenanthrenyl and anthracenyl.
• the imidazolidine radical (Im) usually has a structure of the general formula (IIa) or (IIb), where
• One or more of the radicals R 8 , R 9 , R 10 , R 11 may, independently of one another, optionally be substituted by one or more substitutents, preferably straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl, where these abovementioned substitutents may in turn be substituted by one or more radicals, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy and phenyl.
• substitutents preferably straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl, where these abovementioned substitutents may in turn be substituted
• R 8 and R 9 are each, independently of one another, hydrogen, C 6 -C 24 -aryl, particularly preferably phenyl, straight-chain or branched C 1 -C 10 -alkyl, particularly preferably propyl or butyl, or together form, with inclusion of the carbon atoms to which they are bound, a cycloalkyl or aryl radical, where all the abovementioned radicals may in turn be substituted by one or more further radicals selected from the group consisting of straight-chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 6 -C 24 -aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxyl, disulphide, carbonate, isocyanate, carbodiimi
• the radicals R 10 and R 11 are identical or different and are each straight-chain or branched C 1 -C 10 -alkyl, particularly preferably i-propyl or neopentyl, C 3 -C 10 -cycloalkyl, preferably adamantyl, C 6 -C 24 -aryl, particularly preferably phenyl, C 1 -C 10 -alkylsulphonate, particularly preferably methanesulphonate, C 6 -C 10 -arylsulphonate, particularly preferably p-toluenesulphonate.
• Radicals R 10 and R 11 of the abovementioned type may optionally be substituted by one or more further radicals selected from the group consisting of straight-chain or branched C 1 -C 5 -alkyl, in particular methyl, C 1 -C 5 -alkoxy, aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxyl, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.
• further radicals selected from the group consisting of straight-chain or branched C 1 -C 5 -alkyl, in particular methyl, C 1 -C 5 -alkoxy, aryl and functional groups selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine
• radicals R 10 and R 11 may be identical or different and are each i-propyl, neopentyl, adamantyl or mesityl.
• Particularly preferred imidazolidine radicals (Im) have the following structures (Va-f), where Mes is in each case a 2,4,6-trimethylphenyl radical.
• X 1 and X 2 are identical or different and can be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate, C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl.
• radicals X 1 and X 2 can also be substituted by one or more further radicals, for example by halogen, preferably fluorine, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl radicals, where the latter radicals may also in turn be substituted by one or more substitutents selected from the group consisting of halogen, preferably fluorine, C 1 -C 5 -alkyl, C 1 -C 8 -alkoxy and phenyl.
• halogen preferably fluorine, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C 24 -aryl radicals
• X 1 and X 2 are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C 1 -C 5 -carboxylate, C 1 -C 5 -alkyl, phenoxy, C 1 -C 5 -alkoxy, C 1 -C 5 -alkylthiol, C 6 -C 24 -arylthiol, C 6 -C 24 -aryl or C 1 -C 5 -alkylsulphonate.
• halogen in particular fluorine, chlorine, bromine or iodine
• 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-CH 3 —C 6 H 4 —SO 3 ), mesylate (2,4,6-trimethylphenyl) or CF 3 SO 3 (trifluoromethanesulphonate).
• the radical R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.
• the radical R 1 is usually a C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylamino, C 1 -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.
• R 1 is preferably a C 3 -C 20 -cylcoalkyl radical, a C 6 -C 24 -aryl radical or a straight-chain or branched C 1 -C 30 -alkyl radical, with the latter optionally being able to be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
• R 1 is particularly preferably a straight-chain or branched C 1 -C 12 -alkyl radical.
• the C 3 -C 20 -cycloalkyl radical encompasses, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• the C 1 -C 12 -alkyl radical can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-dodecyl.
• R 1 is methyl or isopropyl.
• the C 6 -C 24 -aryl radical is an aromatic radical having from 56 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.
• radicals R 2 , R 3 , R 4 and R 5 are identical or different and can be hydrogen, organic or inorganic radicals.
• R 2 , R 3 , R 4 , R 5 are identical or different and are each hydrogen, halogen, nitro, CF 3 or an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl radicals.
• R 2 , R 3 , R 4 , R 5 are usually identical or different and are each hydrogen, halogen, preferably chlorine or bromine, nitro, CF 3 or a C 1 -C 30 -alkyl, C 3 -C 20 -cylcoalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylamino, C 1 -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radical,
• R 2 , R 3 , R 4 , R 5 are identical or different and are each nitro, a straight-chain or branched C 1 -C 30 -alkyl, C 5 -C 20 -cycloalkyl, straight-chain or branched C 1 -C 20 -alkoxy radical or a C 6 -C 24 -aryl radical, preferably phenyl or naphthyl.
• the C 1 -C 30 -alkyl radicals and C 1 -C 20 -alkoxy radicals may optionally be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
• two or more of the radicals R 2 , R 3 , R 4 or R 5 can also be bridged via aliphatic or aromatic structures.
• R 3 and R 4 can, with inclusion of the carbon atoms to which they are bound in the phenyl ring of the formula (B), form a fused-on phenyl ring so that overall a naphthyl structure results.
• R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical.
• R 6 is preferably hydrogen or a C 1 -C 30 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl or C 6 -C 24 -aryl radical.
• R 6 is particularly preferably hydrogen.
• catalysts for the catalyst system of the invention are catalysts of the general formula (B1) where
• M is ruthenium
• X 1 and X 2 are both halogen, in particular, both chlorine,
• R 1 is a straight-chain or branched C 1 -C 12 -alkyl radical
• R 2 , R 3 , R 4 , R 5 have the general and preferred meanings given for the general formula (B) and
• M is ruthenium
• X 1 and X 2 are both chlorine
• R 1 is an isopropyl radical
• R 2 , R 3 , R 4 , R 5 are all hydrogen and
• L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb), where
• This catalyst is also referred to in the literature as “Hoveyda catalyst”.
• M is ruthenium
• X 1 and X 2 are both halogen, in particular both chlorine,
• R 1 is a straight-chain or branched C 1 -C 12 -alkyl radical
• R 12 has the meanings given for the general formula (B),
• n 0, 1, 2 or 3
• R 6 is hydrogen
• M is ruthenium
• X 1 and X 2 are both chlorine
• R 1 is an isopropyl radical
• n 0
• L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb), where
• a particularly suitable catalyst which comes under the general formula (B2) has the structure (XIV) and is also referred to in the literature as “Grela catalyst”.
• a further suitable catalyst which comes under the general formula (B2) has the structure (XV), where Mes is in each case a 2,4,6-trimethylphenyl radical.
• dendritic catalysts of the general formula (B3) where D 1 , D 2 , D 3 and D 4 each have a structure of the general formula (XVI) below which is bound via the methylene group to the silicon of the formula (B3), where
• Such catalysts of the general formula (B3) are known from US 2002/0107138 A1 and can be prepared according to the information given there.
• the support is preferably a poly(styrene-divinylbenzene)copolymer (PS-DVB).
• PS-DVB poly(styrene-divinylbenzene)copolymer
• All the abovementioned catalysts of the type (B) can either be used as such in the reaction mixture of the NBR metathesis or can be applied to and immobilized on a solid support.
• solid phases or supports it is possible to use materials which firstly are inert towards the reaction mixture of the metathesis and secondly do not impair the activity of the catalyst. It is possible to use, for example, metals, glass, polymers, ceramic, organic polymer spheres or inorganic sol-gels for immobilizing the catalyst.
• the catalyst system of the invention can also be prepared using catalysts of the general formula (C), where M is ruthenium or osmium, X 1 and X 2 can be identical or different and are anionic ligands, the radicals R′ are identical or different and are organic radicals, Im is a substituted or unsubstituted imidazolidine radical and An is an anion.
• C general formula
• X 1 and X 2 in the general formula (C) can have the same general, preferred and particularly preferred meanings as in the formula (B).
• the imidazolidine radical (Im) usually has a structure of the general formula (IIa) or (IIb) which have already been mentioned for the catalyst type of the formulae (A) and (B) and can also have all the structures mentioned there as preferred, in particular those of the formulae (Va)-(Vf).
• the radicals R′ in the general formula (C) are identical or different and are each a straight-chain or branched C 1 -C 30 -alkyl, C 5 -C 30 -cylcoalkyl or aryl radical, with the C 1 -C 30 -alkyl radicals optionally being able to be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
• Aryl encompasses an aromatic radical having from 5 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.
• radicals R′ in the general formula (C) are preferably identical and are each phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.
• the catalyst systems of the invention thus comprise the metathesis catalyst and one or more salts of the general formula (I).
• the invention further provides for a process of reacting a chemical compound comprising subjecting said chemical compound to a metathesis reaction in the presence of the aforementioned catalyst systems.
• the metathesis reactions can be ring-closing metatheses (RCM), cross-metatheses (CM) or ring-opening metatheses (ROMP).
• RCM ring-closing metatheses
• CM cross-metatheses
• REP ring-opening metatheses
• the catalyst systems of the invention are preferably used for the metathesis of nitrile rubber. This is a cross-metathesis.
• the metathesis catalyst and the salt or salts of the general formula (I) is/are used in a weight ratio of salt(s):metathesis catalyst of from 0.01:1 to 10000:1, preferably from 0.1:1 to 1000:1, particularly preferably from 0.5:1 to 500:1.
• the salt or salts of the general formula (I) can be added in a solvent or without solvent to the metathesis catalyst or its solution in order to obtain the catalyst system of the invention.
• solvent or dispersion medium in which the salt or salts of the general formula (I) is/are added to the catalyst or its solution it is possible to use all known solvents.
• the salt for the addition of the salt to be effective, it is not absolutely necessary for the salt to have a high solubility in the solvent.
• Preferred solvents include but are not restricted to acetone, benzene, chlorobenzene, chloroform, cyclohexane, dichloromethane, dioxane, dimethylformamide, dimethylacetamide, dimethyl sulphone, dimethyl sulphoxide, methyl ethyl ketone, tetrahydrofuran, tetrahydropyran and toluene.
• the solvent is preferably inert towards the metathesis catalyst.
• the salt or salts of the general formula (I) can be added in a solvent or without solvent to a solution of the metathesis catalyst.
• the amount of metathesis catalyst based on the nitrile rubber used depends on the nature and the catalytic activity of the specific catalyst.
• the amount of catalyst used is usually from 1 to 1000 ppm of noble metal, preferably from 2 to 500 ppm, in particular from 5 to 250 ppm, based on the nitrile rubber used.
• the NBR metathesis can be carried out in the absence or presence of a coolefin.
• a coolefin This is preferably a straight-chain or branched C 2 -C 16 -olefin.
• Suitable coolefins are, for example, ethylene, propylene, isobutene, styrene, 1-hexene and 1-octene. Preference is given to using 1-hexene or 1-octene. If the coolefin is liquid (as in the case of, for example, 1-hexene), the amount of coolefin is preferably in the range 0.2-20% by weight based on the NBR used.
• the amount of coolefin is selected so that a pressure in the range 1 ⁇ 10 5 Pa-1 ⁇ 10 7 Pa, preferably a pressure in the range from 5.2 ⁇ 10 5 Pa to 4 ⁇ 10 6 Pa, is established in the reaction vessel at room temperature.
• the metathesis reaction can be carried out in a suitable solvent which does not deactivate the catalyst used and also does not adversely affect the reaction in any other way.
• suitable solvents include, but are not restricted to, dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane and cyclohexane.
• the particularly preferred solvent is chlorobenzene.
• the coolefin itself can function as solvent, e.g. in the case of 1-hexene, the addition of a further additional solvent can also be omitted.
• the concentration of the nitrile rubber used in the reaction mixture of the metathesis is not critical, but care naturally has to be taken to ensure that the reaction is not adversely affected by an excessively high viscosity of the reaction mixture and the mixing problems associated therewith.
• the concentration of NBR in the reaction mixture is preferably in the range from 1 to 20% by weight, particularly preferably in the range from 5 to 15% by weight, based on the total reaction mixture.
• the metathetic degradation is usually carried out at a temperature in the range from 10° C. to 150° C., preferably at a temperature in the range from 20 to 100° C.
• the reaction time depends on a number of factors, for example, on the type of NBR, the type of catalyst, the catalyst concentration used and the reaction temperature.
• the reaction is typically complete within three hours under normal conditions.
• the progress of the metathesis can be monitored by standard analytical methods, e.g. by GPC measurement or by determination of the viscosity.
• NBR nitrile rubbers
• the conjugated diene can be of any nature. Preference is given to using (C 4 -C 6 ) conjugated dienes. Particular preference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof. Very particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Especial preference is given to 1,3-butadiene.
• ⁇ , ⁇ -unsaturated nitrile it is possible to use any known ⁇ , ⁇ -unsaturated nitrile, preferably a (C 3 -C 5 ) ⁇ , ⁇ -unsaturated nitrile such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particular preference is given to acrylonitrile.
• a particularly preferred nitrile rubber is thus a copolymer of acrylonitrile and 1,3-butadiene.
• conjugated diene and the ⁇ , ⁇ -unsaturated nitrile it is possible to use one or more further copolymerizable monomers known to those skilled in the art, e.g. ⁇ , ⁇ -unsaturated monocarboxylic or dicarboxylic acids, their esters or amides.
• ⁇ , ⁇ -unsaturated monocarboxylic or dicarboxylic acids preference is given to fumaric acid, maleic acid, acrylic acid and methacrylic acid.
• esters of ⁇ , ⁇ -unsaturated carboxylic acids preference is given to using their alkyl esters and alkoxyalkyl esters.
• alkyl esters of ⁇ , ⁇ -unsaturated carboxylic acids are methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and octyl acrylate.
• Particularly preferred alkoxyalkyl esters of ⁇ , ⁇ -unsaturated carboxylic acids are methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxyethyl (meth)acrylate. It is also possible to use mixtures of alkyl esters, e.g. those mentioned above, with alkoxyalkyl esters, e.g. in the form of those mentioned above.
• the proportions of conjugated diene and ⁇ , ⁇ -unsaturated nitrile in the NBR polymers to be used can vary within wide ranges.
• the proportion of or of the sum of the conjugated dienes is usually in the range from 40 to 90% by weight, preferably in the range from 60 to 85% by weight, based on the total polymer.
• the proportion of or of the sum of the ⁇ , ⁇ -unsaturated nitriles is usually from 10 to 60% by weight, preferably from 15 to 40% by weight, based on the total polymer.
• the proportions of the monomers in each case add up to 100% by weight.
• the additional monomers can be present in amounts of from 0 to 40% by weight, preferably from 0.1 to 40% by weight, particularly preferably from 1 to 30% by weight, based on the total polymer.
• corresponding proportions of the conjugated diene or dienes and/or of the ⁇ , ⁇ -unsaturated nitrile or nitriles are replaced by the proportions of the additional monomers, with the proportions of all monomers in each case adding up to 100% by weight.
• 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 Lanxesstechnik GmbH.
• the nitrile rubbers used for the metathesis 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 M w in the range 200 000-500 000, preferably in the range 200 000-400 000.
• the determination of the Mooney viscosity is carried out in accordance with ASTM standard D 1646.
• the nitrile rubbers obtained by the metathesis process according to the invention have a Mooney viscosity (ML 1+4 at 100° C.) in the range 5-30, preferably 5-20. This corresponds to a weight average molecular weight M w in the range 10 000-200 000, preferably in the range 10 000-150 000.
• the metathetic degradation in the presence of the catalyst system of the invention can be followed by a hydrogenation of the degraded nitrile rubbers obtained. This can be carried out in the manner known to those skilled in the art.
• the catalysts used are usually based on rhodium, ruthenium or titanium, but it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper either as metal or preferably in the form of metal compounds (cf., for example, U.S. Pat. No. 3,700,637, DE-A-25 39 132, EP-A-0 134 023, DE-A-35 41 689, DE-A-35 40 918, EP-A-0 298 386, DE-A-35 29 252, DE-A-34 33 392, U.S. Pat. No. 4,464,515 and U.S. Pat. No. 4,503,196).
• Suitable catalysts and solvents for a hydrogenation in the homogeneous phase are described below and are also known from DE-A-25 39 132 and EP-A-0 471 250.
• the selective hydrogenation can be achieved, for example, in the presence of a rhodium- or ruthenium-containing catalyst. It is possible to use, for example, a catalyst of the general formula (R m 1 B) 1 M X n . where M is ruthenium or rhodium, the radicals R 1 are identical or different and are each a C 1 -C 8 -alkyl group, a C 4 -C 8 -cycloalkyl group, a C 6 -C 15 -aryl group or a C 7 -C 15 -aralkyl group.
• B is phosphorus, arsenic, sulphur or a sulphoxide group S ⁇ O
• 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
• n is 1, 2 or 3, preferably 1 or 3.
• Preferred catalysts are tris(triphenylphosphine)rhodium(I) chloride, tris(triphenylphosphine)rhodium(III) chloride and tris(dimethyl sulphoxide)rhodium(III) chloride and also tetrakis(triphenylphosphine)rhodium hydride of the formula (C 6 H 5 ) 3 P) 4 RhH and the corresponding compounds in which the triphenylphosphine has been completely or partly replaced by tricyclohexylphosphine.
• the catalyst can be utilized in small amounts. An amount in the range 0.01-1% by weight, preferably in the range 0.03-0.5% by weight and particularly preferably in the range 0.1-0.3% by weight, based on the weight of the polymer, is suitable.
• cocatalyst which is a ligand of the formula R m 1 B, where R 1 , m and B have the meanings given above for the catalyst.
• R 1 , m and B have the meanings given above for the catalyst.
• cocatalysts may be found in, for example, U.S. Pat. No. 4,631,315.
• a preferred cocatalyst is triphenylphosphine.
• the cocatalyst is preferably used in amounts in the range 0.3-5% by weight, preferably in the range 0.5-4% by weight, based on the weight of the nitrile rubber to be hydrogenated.
• the weight ratio of the rhodium-containing catalyst to the cocatalyst is preferably in the range from 1:3 to 1:55, more preferably in the range from 1:5 to 1:45.
• the cocatalyst Based on 100 parts by weight of the nitrile rubber to be hydrogenated, it is appropriate to use from 0.1 to 33 parts by weight of the cocatalyst, preferably from 0.5 to 20 parts by weight and very particularly preferably from 1 to 5 parts by weight, in particular more than 2 but less than 5 parts by weight of cocatalyst, per 100 parts by weight of the nitrile rubber to be hydrogenated.
• hydrogenation is a reaction of the double bonds present in the starting nitrile rubber to an extent of at least 50%, preferably 70-100%, particularly preferably 80-100%.
• heterogeneous catalysts these are usually supported catalysts based on palladium which are, for example, supported on carbon, silica, calcium carbonate or barium sulphate.
• a hydrogenated nitrile rubber having a Mooney viscosity (ML 1+4 at 100° C.), measured in accordance with ASTM standard D 1646, in the range 10-50, preferably from 10 to 30, is obtained.
• M w Mooney viscosity
• the catalyst system of the invention can not only be used successfully for the metathetic degradation of nitrile rubbers but can also be used universally for other metathesis reactions, e.g. for ring-closing metatheses such as the ring closure of diethyl diallyl malonate.
• the amount of the metathesis catalyst and thus the amount of noble metal can be significantly reduced at comparable reaction times compared to analogous metathesis reactions in which only the catalyst, i.e. without salts, is used.
• the reaction times are substantially shortened by the salt additions.
• the catalyst systems are used for the degradation of nitrile rubbers, degraded nitrile rubbers having significantly lower molecular weights M w and M n can be obtained.
• the Grubbs II catalyst was procured from Materia (Pasadena/California).
• the Hoveyda catalyst was procured from Aldrich under the product number 569755.
• the Grela catalyst was prepared by the method published in J. Org. Chem. 2004, 69, 6894-6896.
• the Buchmeiser Nuyken catalyst was prepared as described in Chemistry European Journal 2004, 10(3), 777-785.
• NBR NBR
• the metathetic degradation was in each case carried out using 293.3 g of chlorobenzene (herein after referred to as “MCB”/from Aldrich) which had been distilled and made inert by passing argon through it at room temperature before use. 40 g of NBR were dissolved therein at room temperature over a period of 10 hours. 0.8 g (2 phr) of 1-hexene was in each case added to the NBR-containing solution and the mixture was stirred for 30 minutes to homogenize it.
• MMB chlorobenzene
• the metathesis reaction was carried out at room temperature using the amounts of starting materials indicated below in Table 1.
• the Ru catalysts were in each case dissolved in 20 g of MCB at room temperature under argon.
• the addition of the catalyst solutions to the NBR solutions in MCB was carried out immediately after the preparation of the catalyst solutions.
• the solutions were in each case filtered by means of a 0.2 ⁇ m syringe filter made of Teflon (Chromafil PTFE 0.2 ⁇ m; from Machery-Nagel).
• the GPC analysis was subsequently carried out using a Waters instrument (Mod. 510). The analysis was carried out using a combination of 4 columns from Polymer Laboratories: 1) PLgel 5 ⁇ M Mixed-C, 300 ⁇ 7.5 mm, 2) PLgel 5 ⁇ m Mixed-C, 300 ⁇ 7.5 mm, 3) PLgel 3 ⁇ m Mixed-E, 300 ⁇ 7.5 mm, and 4) PLgel 3 ⁇ m Mixed-E, 300 ⁇ 7.5 mm.
• the calibration of the GPC columns was carried out using linear poly(methyl methacrylate) from Polymer Standards Services.
• An RI detector from Waters (Waters 410) was used as detector.
• the analysis was carried out at a flow rate of 0.5 ml/min using DMAc as eluent.
• the GPC curves were evaluated using software from Millenium.
• the molecular weights M w and M n were significantly reduced compared to the comparative experiment without salt addition (trial 1.01.).
• the salt additions thus improve the efficiency of the Grubbs II catalyst.
• the degraded nitrite rubbers obtained in the trials 1.02. to 1.19. were gel-free.
• the molecular weights M w and M n were significantly reduced compared to the comparative experiments without salt addition (trial 2.01.).
• the salt addition thus improved the efficiency of the Hoveyda catalyst.
• the degraded nitrile rubbers obtained in the trial 2.02. were gel-free.

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