FUNCTIONALISED NITRILE RUBBERS AND THE PRODUCTION THEREOF

Abstract

Provided are new functionalized nitrile rubbers, which may optionally also be in partially or wholly hydrogenated form, and also a process for preparing them by metathesis of nitrile rubbers in the presence of a metathesis catalyst and at least one functionalized allyl compound. The new functionalized nitrile rubbers are suitable for producing vulcanizable mixtures and allow the production of vulcanizates having very stable networks. Also made possible, in particular, is the synthesis of block copolymers.

Claims

1. Process for preparing functionalized nitrile rubbers by contacting a nitrile rubber with a metathesis catalyst which is a complex catalyst based on a metal from transition group 6 or 8 of the Periodic Table which has at least one ligand attached carbenically to the metal, in the presence of at least one compound of the general formula (I) or (II),
H.sub.2CCHCH.sub.2X(I)
YCH.sub.2CHCHCH.sub.2Z(II) where X is OR.sup.1, in which R.sup.1 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.2, in which R.sup.2 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.3, in which R.sup.3 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, OC(O)R.sup.4, in which R.sup.4 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, C.sub.6-C.sub.18 aryl, which is substituted by at least one radical OR.sup.5, in which R.sup.5 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, or NHC(O)OR.sup.6, in which R.sup.6 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, and Y and Z are identical or different and OR.sup.7, in which R.sup.7 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.8, in which R.sup.8 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.9, in which R.sup.9 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, OC(O)R.sup.10, in which R.sup.10 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, C.sub.6-C.sub.18 aryl, which is substituted by at least one radical OR.sup.11, in which R.sup.11 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, or NHC(O)OR.sup.12, in which R.sup.12 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl.

2. Process according to claim 1, characterized in that use is made as metathesis catalyst of (i) a catalyst of the general formula (A), ##STR00075## in which M is osmium or ruthenium, X.sup.1 and X.sup.2 are identical or different and represent two ligands, preferably anionic ligands, L represents identical or different ligands, preferably neutral electron donors, R is identical or different at each occurrence and represents hydrogen, alkyl, preferably C.sub.1-C.sub.30 alkyl, cycloalkyl, preferably C.sub.3-C.sub.20 cycloalkyl, alkenyl, preferably C.sub.2-C.sub.20 alkenyl, alkynyl, preferably C.sub.2-C.sub.20 alkynyl, aryl, preferably C.sub.6-C.sub.24 aryl, carboxylate, preferably C.sub.1-C.sub.20 carboxylate, alkoxy, preferably C.sub.1-C.sub.20 alkoxy, alkenyloxy, preferably C.sub.2-C.sub.20 alkenyloxy, alkynyloxy, preferably C.sub.2-C.sub.20 alkynyloxy, aryloxy, preferably C.sub.6-C.sub.24 aryloxy, alkoxycarbonyl, preferably C.sub.2-C.sub.20 alkoxycarbonyl, alkylamino, preferably C.sub.1-C.sub.30 alkylamino, alkylthio, preferably C.sub.1-C.sub.30 alkylthio, arylthio, preferably C.sub.6-C.sub.24 arylthio, alkylsulphonyl, preferably C.sub.1-C.sub.20 alkylsulphonyl, or alkylsulphinyl, preferably C.sub.1-C.sub.20 alkylsulphinyl, it being possible for all of these radicals to be substituted in each case optionally by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively both radicals R are bridged, with incorporation of the common C atom to which they are attached, to form a cyclic group, which may be aliphatic or aromatic in nature, is optionally substituted and may contain one or more heteroatoms, (ii) a catalyst of the general formula (A1), ##STR00076## in which X.sup.1, X.sup.2 and L can have the same general or preferred definitions as in the general formula (A), n is 0, 1 or 2, m is 0, 1, 2, 3 or 4 and R is identical or different at each occurrence and denotes alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals, all of which may be substituted in each case by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, (iii) a catalyst of the general formula (B), ##STR00077## in which M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different ligands, preferably anionic ligands, Y is oxygen (O), sulphur (S), a radical NR.sup.1 or a radical PR.sup.1, where R.sup.1 possesses the definitions stated below, R.sup.1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, which may all be substituted in each case optionally by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are identical or different and represent hydrogen or organic or inorganic radicals, R.sup.6 is H or an alkyl, alkenyl, alkynyl or aryl radical, and L is a ligand which possesses the same definitions as stated for the formula (A), (iv) a catalyst of the general formula (B1), ##STR00078## in which M, L, X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can possess the definitions stated for the general formula (B), (v) a catalyst of the general formula (B2), ##STR00079## in which M, L, X.sup.1, X.sup.2, R.sup.1 and R.sup.6 have the general and preferred definitions for the formula (B), R.sup.12 is identical or different at each occurrence and possesses the definitions stated for the radicals R.sup.2, R.sup.3, R.sup.4 and R.sup.5 in the formula (B), with the exception of hydrogen, and n is 0, 1, 2 or 3, (vi) a catalyst of the general formula (B3), ##STR00080## in which D.sup.1, D.sup.2, D.sup.3 and D.sup.4 each have a structure of the general formula (XVIII) shown below, which is attached via the methylene group shown on the right to the silicon of the formula (B3), ##STR00081## in which M, L, X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 may possess the definitions stated for the general formula (B), (vii) a catalyst of the general formula (B4), in which the symbol stands for a support, ##STR00082## (viii) a catalyst of the general formula (C), ##STR00083## in which M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and represent anionic ligands, R is identical or different at each occurrence and represents organic radicals, Im represents an optionally substituted imidazolidine radical and An represents an anion, (ix) a catalyst of the general formula (D), ##STR00084## in which M is ruthenium or osmium, R.sup.13 and R.sup.14 independently of one another are hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20 alkynyloxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkylsulphonyl or C.sub.1-C.sub.20 alkylsulphinyl, X.sup.3 is an anionic ligand, L.sup.2 is a neutral -bonded ligand, irrespective of whether it is monocyclic or polycyclic, L.sup.3 is a ligand from the group of the 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, Y is a non-coordinating anion and n is 0, 1, 2, 3, 4 or 5, (x) a catalyst of the general formula (E), ##STR00085## in which M.sup.2 is molybdenum, R.sup.15 and R.sup.16 are identical or different and are hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20 alkynyloxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkylsulphonyl or C.sub.1-C.sub.20 alkylsulphinyl, R.sup.17 and R.sup.18 are identical or different and represent a substituted or a halogen-substituted C.sub.1-C.sub.20 alkyl, C.sub.6-C.sub.24 aryl or C.sub.6-C.sub.30 aralkyl radical or silicone-containing analogues thereof, (xi) a catalyst of the general formula (F), ##STR00086## in which M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and represent anionic ligands, which may adopt all of the definitions of X.sup.1 and X.sup.2 stated in the general formulae (A) and (B), L represents identical or different ligands, which may adopt all of the definitions of L stated in the general formulae (A) and (B), R.sup.19 and R.sup.20 are identical or different and are hydrogen or substituted or unsubstituted alkyl, (xii) a catalyst of the general formulae (G), (H) or (K), ##STR00087## in which M is osmium or ruthenium, X.sup.1 and X.sup.2 are identical or different and represent two ligands, preferably anionic ligands, L represents a ligand, preferably a neutral electron donor, Z.sup.1 and Z.sup.2 are identical or different and represent neutral electron donors, R.sup.21 and R.sup.22 independently of one another are hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulphonyl or alkylsulphinyl, which in each case are substituted by one or more radicals selected from alkyl, halogen, alkoxy, aryl or heteroaryl, (xiii) a catalyst (N) containing the general structural element (N1), where the carbon atom labelled with a * is attached via one or more double bonds to the parent catalyst structure, and in which ##STR00088## R.sup.25-R.sup.32 are identical or different and are hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup. or are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl dialkylamino, alkylsilyl or alkoxysilyl, it being possible for all of these radicals to be substituted in each case optionally by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively in each case two directly adjacent radicals from the group of R.sup.25-R.sup.32 form by bridging, with inclusion of the ring carbon atoms to which they are attached, a cyclic group, preferably an aromatic system, or alternatively R.sup.8 is optionally bridged with another ligand of the ruthenium- or osmium-carbene complex catalyst, m is 0 or 1 and A is oxygen, sulphur, C(R.sup.33R.sup.34), NR.sup.35, C(R.sup.36)C(R.sup.37), C(R.sup.36)(R.sup.38)C(R.sup.37)(R.sup.39), in which R.sup.33-R.sup.39 are identical or different and may each possess the same definitions as the radicals R.sup.25-R.sup.32.

3. Process according to claim 2, characterized in that use is made as metathesis catalyst of a catalyst of the formula (IV) or (V), where Cy is cyclohexyl, ##STR00089## a catalyst of the formula (VI), where Mes in each case is 2,4,6-trimethylphenyl and Ph is phenyl, ##STR00090## a catalyst of the general formula (B1), where M represents ruthenium, X.sup.1 and X.sup.2 simultaneously are halogen, more particularly simultaneously are chlorine, R.sup.1 is a straight-chain or branched C.sub.1-C.sub.12 alkyl radical, preferably an isopropyl radical, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 possess the general and preferred definitions stated for the general formula (B), and preferably are all H, and L possesses the general and preferred definitions stated for the general formula (B), and preferably represents an optionally substituted imidazolidine radical of the formula (IIa) or (IIb), ##STR00091## in which R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are identical or different and are hydrogen, straight-chain or branched C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20 alkynyloxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio, C.sub.6-C.sub.24 arylthio, C.sub.1-C.sub.20-alkylsulphonyl, C.sub.1-C.sub.20 alkylsulphonate, C.sub.6-C.sub.24 arylsulphonate or C.sub.1-C.sub.20 alkylsulphinyl, it being possible for the aforementioned radicals to be substituted in each case by one or more substituents, preferably straight-chain or branched C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.10 alkoxy or C.sub.6-C.sub.24 aryl, and these aforementioned substituents as well may be substituted in turn by one or more radicals preferably selected from the group of halogen, more particularly chlorine or bromine, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy and phenyl, or a catalyst of the formula (VII), where Mes in each case is 2,4,6-trimethylphenyl, ##STR00092## a catalyst of the formulae (VIII), (IX), (X), (XI), (XII), (XIII), (XIV) or (XV), where Mes in each case is 2,4,6-trimethylphenyl, ##STR00093## ##STR00094## a catalyst of the general formula (B2), where M represents ruthenium, X.sup.1 and X.sup.2 simultaneously are halogen, more particularly simultaneously are chlorine, R.sup.1 is a straight-chain or branched C.sub.1-C.sub.12 alkyl radical, preferably isopropyl, R.sup.12 possesses the definitions stated for the general formula (B2), n is 0, 1, 2 or 3, preferably 0, R.sup.6 is hydrogen and L possesses the definitions stated for the general formula (B), and preferably represents an optionally substituted imidazolidine radical of the formula (IIa) or (IIb), a catalyst of the formula (XVI) or (XVII), where Mes in each case is 2,4,6-trimethylphenyl, ##STR00095## a catalyst of the general formulae (G), (H) and (K), in which M is ruthenium, X.sup.1 and X.sup.2 both represent halogen, more particularly chlorine, R.sup.1 and R.sup.2 are identical or different and represent five- or six-membered monocyclic groups having 1 to 4, preferably 1 to 3 and more preferably 1 or 2 heteroatoms, or bicyclic or polycyclic structures comprising 2, 3, 4 or 5 such five- or six-membered monocyclic groups, it being possible for all groups stated above in each case to be substituted by one or more alkyl, preferably C.sub.1-C.sub.10 alkyl, cycloalkyl, preferably C.sub.3-C.sub.8 cycloalkyl, alkoxy, preferably C.sub.1-C.sub.10 alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C.sub.6-C.sub.24 aryl, or heteroaryl, preferably C.sub.5-C.sub.23 heteroaryl radicals, R.sup.21 and R.sup.22 are identical or different and represent C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20 alkynyloxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.30 alkylamino, C.sub.1-C.sub.30 alkylthio, C.sub.6-C.sub.24 arylthio, C.sub.1-C.sub.20 alkylsulphonyl, C.sub.1-C.sub.20 alkylsulphinyl, and L possesses a structure of the general formula (IIa) or (IIb) already described above, more particularly of the formulae (IIIa) to (IIIf), a catalyst of the structure (XIX), ##STR00096## in which R.sup.23 and R.sup.24 are identical or different and are halogen, straight-chain or branched C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 heteroalkyl, C.sub.1-C.sub.10 haloalkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.24 aryl, preferably phenyl, formyl, nitro, nitrogen heterocycles, preferably pyridine, piperidine and pyrazine, carboxyl, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, dialkylamino, trialkylsilyl and trialkoxysilyl, a catalyst of the formula (XIX a) or (XIX b), where R.sup.23 and R.sup.24 possess the same definitions as indicated in the formula (XIX) and preferably both are H, ##STR00097## a catalyst of the formulae (XX)-(XXXI), where Mes is 2,4,6-trimethylphenyl, ##STR00098## ##STR00099## ##STR00100## a catalyst of the formulae (N2a) and (N2b), ##STR00101## in which M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and represent two ligands, preferably anionic ligands, L.sup.1 and L.sup.2 represent identical or different ligands, preferably neutral electron donors, where L.sup.2 alternatively may also be bridged with the radical R.sup.8, n is 0, 1, 2 or 3, preferably 0, 1 or 2, n is 1 or 2, preferably i, and R.sup.25-R.sup.32, m and A possess the same definitions as in the general formula (N1), a catalyst of the formulae (N13a) or (N13b) ##STR00102## in which Y.sup.1 is oxygen, sulphur, a radical NR.sup.41 or a radical PR.sup.41, where R.sup.41 possesses the definitions identified below, R.sup.40 and R.sup.41 are identical or different and represent an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, which may all in each case be optionally substituted by one more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, p is 0 or 1 and Y.sup.2 if p is 1, is (CH.sub.2).sub.r with r=1, 2 or 3, C(O)CH.sub.2, C(O), NCH, N(H)C(O) or else alternatively the entire structural unit Y.sup.1(R.sup.40)(Y.sup.2).sub.p is (N(R.sup.40)CHCH.sub.2), (N(R.sup.40,R.sup.41)CHCH.sub.2), and where M, X.sup.1, X.sup.2, L.sup.1, R.sup.25-R.sup.32, A, m and n possess the same definitions as in the general formulae (IIa) and (IIb), or a catalyst of the following structures ##STR00103## ##STR00104## ##STR00105##

4. Process according to claim 2 or 3, characterized in that in the functionalized olefin of the general formula (I) or (II) X is OR.sup.1, in which R.sup.1 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.2, in which R.sup.2 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, and n is 1 to 20 and preferably 1 to 6, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.3, in which R.sup.3 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl and n is 1 to 20 and preferably 1 to 6, OC(O)R.sup.4, in which R.sup.4 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, C.sub.6-C.sub.12 aryl, which is substituted by at least one radical OR.sup.5, in which R.sup.5 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, or NHC(O)OR.sup.6, in which R.sup.6 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, and Y and Z are identical or different and are OR.sup.7, in which R.sup.7 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.8, in which R.sup.8 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl and n is 1 to 20 and preferably 1 to 6, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.9, in which R.sup.9 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl and n is 1 to 20 and preferably 1 to 6, OC(O)R.sup.10, in which R.sup.10 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, C.sub.6-C.sub.12 aryl, which is substituted by at least one radical OR.sup.11, in which R.sup.11 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl, or NHC(O)OR.sup.12, in which R.sup.12 is H, C.sub.1-C.sub.12 alkyl, C.sub.7-C.sub.18 aralkyl, phenyl, naphthyl or fluorenyl and preferably is H, C.sub.1-C.sub.6 alkyl, C.sub.7-C.sub.12 aralkyl or phenyl.

5. Process according to claim 2 or 3, characterized in that use is made as functionalized olefin of tert-butyl N-allylcarbamate, p-allylanisole, o-allylanisole, p-allylphenol, o-allylphenol, allyl benzoate, allyl benzyl ether, cis-1,4-bisbenzoyloxy-2-butene, cis-2-butene-1,4-diyl dibenzoate, cis-2-butene-1,4-diyl diacetate or mixtures thereof.

6. Process according to one or more of claims 1 to 5, characterized in that the compound of the general formula (I) or (II) is used in an amount of 8*10.sup.6 mol to 8*10.sup.3 mol, preferably 1*10.sup.5 mol to 5*10.sup.3 mol and more preferably 2*10.sup.5 mol to 2*10.sup.3 mol, based on 1 g of nitrile rubber.

7. Process according to one or more of claims 1 to 6, characterized in that the metathesis catalyst is used in an amount of 4*10.sup.8 mol to 4*10.sup.5 mol, preferably of 2*10.sup.7 mol to 2*10.sup.5 mol and more preferably of 5*10.sup.7 mol to 7.5*10.sup.6 mol, based on 1 g of nitrile rubber.

8. Process according to one or more of claims 1 to 7, characterized in that the metathesis catalyst is used, relative to the functionalized olefin of the general formula (I) or (II), in a molar ratio of (5*10.sup.6 to 5):1, preferably (1*10.sup.4 to 5*10.sup.1):1, more preferably of (2*10.sup.3 to 1.5*10.sup.2):1.

9. Process according to one or more of claims 1 to 8, characterized in that the nitrile rubber used comprises repeating units which derive from at least one conjugated diene and at least one ,-unsaturated nitrile and the CC double bonds from the copolymerized diene monomers are present in either unhydrogenated or partly hydrogenated form.

10. Functionalized nitrile rubbers comprising repeating units which derive from at least one conjugated diene and at least one ,-unsaturated nitrile, and also either end groups X or end groups Y and Z, where X is OR.sup.1, in which R.sup.1 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.2, in which R.sup.2 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.3, in which R.sup.3 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, OC(O)R.sup.4, in which R.sup.4 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, C.sub.6-C.sub.18 aryl, which is substituted by at least one radical OR.sup.5, in which R.sup.5 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, or NHC(O)OR.sup.6, in which R.sup.6 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, and Y and Z are identical or different and OR.sup.7, in which R.sup.7 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, O(CH.sub.2CH.sub.2O).sub.nR.sup.8, in which R.sup.8 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, O(CH.sub.2CH(CH.sub.3)O).sub.nR.sup.9, in which R.sup.9 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20, OC(O)R.sup.10, in which R.sup.10 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, C.sub.6-C.sub.18 aryl, which is substituted by at least one radical OR.sup.11, in which R.sup.11 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, or NHC(O)OR.sup.12, in which R.sup.12 is H, C.sub.1-C.sub.18 alkyl, C.sub.7-C.sub.24 aralkyl, phenyl, naphthyl or fluorenyl, where the CC double bonds from the copolymerized diene monomers are optionally present in either partially or fully hydrogenated form.

11. Functionalized nitrile rubbers according to claim 10, characterized in that they possess a Mooney viscosity (ML 1+4 at 100 C.) in the range of 5-30, preferably in the range of 5-20, and a polydispersity PDI=Mw/Mn, where Mn represents the number average of the molecular weight and Mw the weight average of the molecular weight, in the range 1.4-4.0, preferably in the range of 1.5-3.0.

12. Vulcanizable mixtures comprising (i) at least one functionalized nitrile rubber according to claim 10 or 11, (ii) at least one crosslinker or crosslinking system and optionally (iii) one or more further rubber additives.

13. Process for producing vulcanizates, characterized in that the vulcanizable mixture according to claim 12 is crosslinked by temperature increase, preferably in a shaping process, more preferably employing injection moulding.

14. Vulcanizates based on a functionalized nitrile rubber according to claim 10 or 11.

15. Block copolymers comprising one or more blocks based on the functionalized nitrile rubber according to claim 10 or 11.

Description

EXAMPLES

[0435] In the examples which follow, the metathesis catalysts I, II and I set out in Table 1, the nitrile rubbers A, B, C and D specified in Table 2 and the olefins set out in Table 3 are used.

TABLE-US-00001 TABLE 1 Catalysts used Molar mass Catalyst Identification Structural formula [g/mol] Source I Grubbs II catalyst [00045] 848.33 From Materia/ Pasadena; U.S.A. II 2,6-Diisopropyl- phenylimidoneo- phylidenemolybdenum (VI) bis(t-butoxide) [00046] 549.65 ABCR III 2,6-Diisopropyl- phenylimidoneo- phylidenemolybdenum (VI) bis(hexafluoro-t- butoxide) [00047] 765.53 ABCR

TABLE-US-00002 TABLE 2 Nitrile rubbers used Nitrile Degree of content hydrogenation MN.sub.0 MW.sub.0 Rubber [% by weight] [%] [g/mol] [g/mol] PDI.sub.0 A 34 0 60 100 174 800 2.9 B 34 0 74 100 204 000 2.8 C 34 0 77 100 223 000 2.9 D 34 65.4 57 800 190 500 3.3 MN.sub.0 Number-average molar mass before metathetic degradation MW.sub.0 Weight-average molar mass before metathetic degradation PDI.sub.0 Polydispersity index before degradation

Tables 3a and 3b: Olefins Used

[0436] Where the olefins used were not purchased, their preparation is described below.

TABLE-US-00003 TABLE 3a Non-inventive olefins Molar mass Chemical identification Structural formula [g/mol] Source 1-Hexene [00048] 84.16 Sigma- Aldrich 1-Octene [00049] 112.21 Acros Organics 1-Decene [00050] 140.27 Acros Organics trans-4-Octene [00051] 112.21 Acros Organics 5-Decene CH.sub.3(CH.sub.2).sub.3CHCH(CH.sub.2).sub.3CH.sub.3 140.27 see synthesis instructions Styrene [00052] 104.15 Sigma- Aldrich m-Nitrostyrene [00053] 149.15 ABCR -Methylstyrene [00054] 118.18 Acros Organics trans-Stilene [00055] 180.25 Fluka 1,1-Diphenylethylene [00056] 180.25 Acros Organics Allylamine [00057] 57.09 Fluka 1-Allyl-2,3,4,5,6- pentafluorobenzene [00058] 208.13 Sigma- Aldrich 3,3,4,4,5,5,6,6,6- Nonafluoro-1-hexene [00059] 246.07 Sigma- Aldrich 4-Octene-1,8-diol [00060] 144.21 see synthesis instructions 3,10-Diisopropyl-2,11- dimethyl-6-dodecene- 3,10-diol [00061] 312.35 see synthesis instructions Diethyl fumarate [00062] 172.18 see synthesis instructions

TABLE-US-00004 TABLE 3b Inventive olefins Molar mass Chemical identification Structural formula [g/mol] Source Allyl alcohol [00063] 58.08 Acros Organics Allyl benzyl ether [00064] 148.20 Sigma- Aldrich Allyl benzoate [00065] 162.19 see synthesis instructions tert-Butyl N- allylcarbamate [00066] 157.21 Sigma- Aldrich o-Allylphenol [00067] 134.18 Acros Organics p-Allylphenol [00068] 134.18 see synthesis instructions o-Allylanisole [00069] 148.20 see synthesis instructions p-Allylanisole [00070] 148.20 Acros Organics cis-2-Butene-1,4-diyl [00071] 88.11 Fluka cis-2-Butene-1,4-diyl diacetate [00072] 172.18 see synthesis instructions cis-2-Butene-1,4-diyl dibenzoate [00073] 296.32 see synthesis instructions cis-1,4-Bisbenzyloxy-2- butene [00074] 268.53 Sigma- Aldrich

A Preparation of Olefins not Purchased:

5-Decene:

[0437] Under Schlenk conditions, 5.0 g (59 mmol) of I-hexene were first introduced into 20 ml of dry dichloromethane. The reaction was commenced by addition of 50 mg (2.95*10.sup.5 mol, 0.1 mol %) of Grubbs II catalyst in 5 ml of dichloromethane. The reaction mixture was subsequently stirred at 35 C. for 6 hours. The ethene formed was driven off by a continuous stream of inert gas. Following removal of the solvent under reduced pressure, the product, after distillation under reduced pressure (20 mbar, 58 C.), was obtained as a colourless liquid.

[0438] Yield: 2.4 g (17.8 mmol, 58%, of which 84% in trans-configuration).

4-Octene-1,8-diol

[0439] Under Schlenk conditions, 2.0 g (23.5 mmol) of 4-pentene-1-ol were introduced into 10 ml of dry dichloromethane. The self-metathesis of 4-pentene-1-ol was commenced by addition of 20 mg (2.35*10.sup.5 mol, 0.1 mol %) of Grubbs II catalyst in 6 ml of dichloromethane. The reaction mixture was subsequently stirred at room temperature for 24 hours. The ethene formed was driven off by a continuous stream of inert gas. Following removal of the solvent under reduced pressure, the product, after column chromatography (silica gel, ethyl acetate), was obtained as a colourless oil.

[0440] Yield: 745 mg (5.17 mmol, 44%, of which 83% in trans-configuration).

3,10-Diisopropyl-2,11-dimethyl-6-dodecene-3,10-diol

[0441] In a baked three-necked flask with reflux condenser, dropping funnel, inert gas inlet and pressure relief valve, 2.43 g (0.1 mol, 1 eq.) of magnesium turnings were introduced into 30 ml of dry diethyl ether. Thereafter, with gentle boiling of the solvent, a solution of 13.5 g (0.1 mol, 1 eq.) of 4-bromo-1-butene in 30 ml of diethyl ether was added dropwise and the reaction mixture was then heated under reflux for an hour. When the reaction mixture had cooled, a solution of 11.4 g (0.1 mol, 1 eq.) of 2,4-dimethyl-3-pentanone in 30 ml of diethyl ether was added dropwise and the mixture was heated under reflux for five hours. The reaction was then stopped by adding 100 ml of saturated ammonium chloride solution, the organic phase was separated off and the aqueous phase was extracted with twice 70 ml of diethyl ether. After two-fold washing of the ether phase with 100 ml of water and drying over MgSO.sub.4, the drying agent was removed by filtration and the solvent was removed under reduced pressure. Subsequent vacuum distillation yielded 3-isopropyl-2-methyl-6-hepten-3-ol under a pressure of 16 mbar and a temperature of 90 C., as a colourless liquid.

[0442] Under Schlenk conditions, 2.0 g (11.7 mmol) of 3-isopropyl-2-methyl-6-hepten-3-ol were introduced into 6 ml of dry dichloromethane. The self-metathesis of 3-isopropyl-2-methyl-6-hepten-3-ol was commenced by addition of 100 mg (0.117 mmol, 1 mol %) of Grubbs II catalyst in 6 ml of dichloromethane. The reaction mixture was subsequently stirred at room temperature for 6 hours. The ethene formed was driven off by a continuous stream of inert gas. Following removal of the solvent under reduced pressure, the product, after column chromatography (silica gel, pentane/ethyl acetate=7/1), was obtained as a colourless oil.

[0443] Yield: 1.29 g (0.41 mmol, 71%, of which 80% in trans-configuration).

Diethyl Fumarate:

[0444] In a 100 ml flask with water separator and reflux condenser, 11.6 g (0.1 mol, 1 eq.) of fumaric acid, 16.1 g (0.35 mol, 3.5 eq.) of ethanol and 1 g (5.3 mmol, 0.05 eq.) of toluenesulphonic acid were introduced into 30 ml of chloroform. This mixture was then heated under reflux until water was no longer separated off. This was followed by washing with twice 100 ml of one molar sodium hydroxide solution, and once with water. After drying over MgSO.sub.4 and removal of the drying agent by filtration, the solvent was removed under reduced pressure, to give the product as a colourless liquid.

[0445] Yield: 16.8 g (97.6 mmol, 97%).

cis-2-Butene-1,4-diyl diacetate

[0446] Under Schlenk conditions, in a Schlenk flask with dropping funnel and pressure relief valve, 17.2 g (0.1 mol, 1 eq.) of cis-2-butene-1,4-diol were introduced into 10 ml of pyridine. With ice-bath cooling, a solution of 30.6 g (0.3 mol, 3 eq.) of acetic anhydride in 20 ml of pyridine was added dropwise over the course of an hour. Following removal of the ice bath, the reaction solution was stirred at room temperature for 24 hours. Then 25 ml of dichloromethane were added, the organic phase was separated off, and washing took place with once 50 ml of two molar hydrochloric acid and with twice 80 ml of saturated sodium chloride solution. Drying over MgSO.sub.4 was followed by removal of the drying agent by filtration, and by removal of the filtrate solvent under reduced pressure. Extraction gave the product as a colourless liquid.

[0447] Yield: 16.5 g (96 mmol, 96%).

cis-2-Butene-1,4-diyl dibenzoate

[0448] Under Schlenk conditions, in a Schlenk flask with dropping funnel and pressure relief valve, 4.5 g (51 mmol, 1 eq.) of cis-2-butene-1,4-diol were introduced into 5 ml of pyridine. With ice-bath cooling, a solution of 24.5 g (0.11 mol, 2.1 eq.) of benzoic anhydride in 20 ml of pyridine was added dropwise over the course of an hour. Following removal of the ice bath, the reaction solution was stirred at room temperature for 24 hours. Then 25 ml of dichloromethane were added, the organic phase was separated off, and washing took place with once 50 ml of two molar hydrochloric acid and with twice 80 ml of saturated sodium chloride solution. Drying over MgSO.sub.4 was followed by removal of the drying agent by filtration, and by removal of the filtrate solvent under reduced pressure. Subsequent column chromatography (aluminium oxide, pentane/ethyl acetate=1/1) gave the product in the form of a pale yellow solid with a sweet odour.

[0449] Yield: 12.9 g (0.43 mmol, 85%).

All Benzoate:

[0450] Under Schlenk conditions, in a Schlenk flask with dropping funnel and pressure relief valve, 2 g (34.4 mmol, 1 eq.) of allyl alcohol were introduced into 5 ml of pyridine. With ice-bath cooling, a solution of 8.6 g (37.9 mmol, 1.1 eq.) of benzoic anhydride in 10 ml of pyridine was added dropwise over the course of an hour. Following removal of the ice bath, the reaction solution was stirred at room temperature for 24 hours. Then 25 ml of dichloromethane were added, the organic phase was separated off, and washing took place with once 50 ml of two molar hydrochloric acid and with twice 80 ml of saturated sodium chloride solution. Drying over MgSO.sub.4 was followed by removal of the drying agent by filtration, and by removal of the filtrate solvent under reduced pressure. Subsequent column chromatography (silica gel, pentane/ethyl acetate=12/1) gave the product as a colourless liquid.

[0451] Yield: 2.99 g (18.4 mmol, 54%).

p-Allylphenol:

[0452] In a baked Schlenk flask with dropping funnel and pressure relief valve, 2.96 g (20 mmol, 1 eq.) of p-allylanisole were introduced into 80 ml of dry dichloromethane. Next, after cooling of the batch to 70 C., 20 ml of a one molar solution of boron tribromide in heptane (5 g, 20 mmol, 1 eq. BBr.sub.3) were added dropwise. Following warming to 15 C., over the course of two hours, the reaction was stopped by addition of 50 ml of ice-water. The organic phase was separated off and washed with twice 50 ml of 5% strength sodium hydroxide solution. The aqueous phase was extracted with three times 50 ml of diethyl ether. The combined organic phases were then dried over MgSO.sub.4 and, following removal of the drying agent by filtration, the solvent was removed under reduced pressure. Subsequent column chromatography (silica gel, dichloromethane) gave the product as a light brown oil.

[0453] Yield: 1.45 g (10.8 mmol, 54%).

o-Allylanisole:

[0454] In a three-necked flask with reflux condenser, internal thermometer and dropping funnel, 4.0 g (29.8 mmol, 1 eq.) of o-allylphenol were introduced. Following addition of 2.13 g (38 mmol, 1.3 eq.) of potassium hydroxide in the form of a 10% strength by weight solution in water, the solution turned a blue-green colour. With cooling in a water bath, 3.76 g (29.8 mmol, 1 eq.) of dimethyl sulphate were slowly added dropwise, the temperature never rising above 40 C. This was followed by stirring at 90 C. for an hour and, after the reaction mixture had been cooled, the organic phase was separated off. The aqueous phase was extracted with three times 40 ml of diethyl ether, and the combined organic phases were washed with two times 70 ml of one molar sodium hydroxide solution, and with twice 70 ml of water. After drying over MgSO.sub.4 and after removal of the drying agent by filtration, the solvent was removed under reduced pressure. Subsequent column chromatography (silica gel, pentane/dichloromethane=2/1) gave the product as a colourless liquid.

[0455] Yield: 3.55 g (23.9 mmol, 80%).

B Implementation of the metathesis reactions

[0456] All of the metathesis reactions were carried out in solution using chlorobenzene (from Sigma-Aldrich), called MCB below. Before being used, the MCB was distilled and inertized by passage of argon at room temperature. Over a period of 12 hours, the nitrile rubber or partially hydrogenated nitrile rubber (Table 2) was dissolved in MCB at room temperature with stirring. The rubber-containing solution was admixed with the additions (without dilutions) noted in the tables below, and stirred for 30 minutes for homogenization. The metathesis catalysts (see Table 1) were each dissolved in 6 ml of inertized MCB under argon, the addition of the catalyst solutions to the NBR solutions taking place immediately after the preparation of the catalyst solutions. All of the reaction batches were designed such that the rubber concentration following addition of catalyst was 12% by weight. In the case of the experiments with 2.38*10.sup.4 mol olefin/g rubber, 40 g of rubber were used. When using 7.14*10.sup.4, 1.43*10.sup.3 and 2.86*10.sup.3 mol olefin/g rubber, 10 g of rubber were used. The metathesis reactions were carried out at 23 C., using the amounts of ingredients specified in Tables 4-6. After a reaction time of 7 hours in each case, 3 g of the reaction solution were withdrawn, and reaction was stopped by addition of 0.2 ml of ethyl vinyl ether and subsequent 30-minute stirring at room temperature.

[0457] For the GPC analysis, 0.2 ml of the nitrile rubber solutions stopped with ethyl vinyl ether was removed and diluted with 3 ml of N,N-dimethylacetamide (from Acros Organics, admixed with 5 g/l LiBr). Before the GPC analysis was carried out, the solutions were each filtered using a 0.2 m syringe filter made of Teflon (Chromafil PTFE 0.2 m; from Macherey-Nagel). Following this, GPC analysis took place using an instrument from Waters, equipped with a Waters 717 Autosampler, a PSS Gram preliminary column, a PSS Gram-30 8300 mm column and two PSS Gram-1000 8300 mm columns, from Polymer Standards Service, and with a Waters 410 RI detector and Cirrus Software Multi Version 3.0. The columns were calibrated with linear polymethyl methacrylate with molar masses of 600 to 1.64*10.sup.6 g/mol, from Polymer Standards Service. Analysis was carried out at a flow rate of 1.0 ml/min at 80 C. using N,N-dimethylacetamide (with 5 g/l LiBr) as eluent.

C Results of Experimentation

C1 Determination of Amounts of Functional Groups in the Rubber

[0458] To determine the amounts of functional groups in the rubber, 750 mg of the stopped sample were diluted with 3 ml of chloroform (HPLC grade, with 7.5 mmol/1 amylene as stabilizer) and filtered using a 0.2 m syringe filter made of Teflon (Chromafil PTFE 0.2 m; from Macherey-Nagel). The polymeric fraction was then separated from low molecular mass constituents by means of gel permeation chromatography (instrument from Waters, equipped with a Waters 717 Autosampler, a preliminary column: 1PLgel preliminary column, 1 times PLgel 5 m MIXED-C 3007.5 mm column, 1 times PLgel 5 m MIXED-C 6007.5 mm column from Polymer Laboratories and a Waters 410 RI detector). The solvent of the polymeric fraction was removed under reduced pressure and then a .sup.1H-NMR spectrum was recorded. The number of functional groups per polymer chain was determined from the integral of the functional group and the integral of the proton adjacent to the nitrile group, in accordance with the following equation:

[00001]$N\left(X\right)=\frac{I\left(X\right).Math.\%.Math..Math.\left(\mathrm{ACN}\right).Math.{\mathrm{MN}}_e}{I\left(\mathrm{ACN}\right).Math.p\left(X\right).Math.M\left(\mathrm{ACN}\right)}$

N(X) number of functional groups per polymer chain
I(X) integral of the functional group
% (ACN) nitrile content of the polymer
MN.sub.e number-average molar mass after metathetic degradation
p(X) number of protons leading to the integral I(X)
M(ACN) molar mass of acrylonitrile (53.06 g/mol)
I(ACN) integral of the backbone proton on the same carbon atom as the CN group

C2 Results of Experiment

[0459] The results from three experimental series are summarized in Tables 4, 5 and 6.

[0460] Table 4 shows the non-inventive comparative experiments of the 1st experimental series, which were carried out with constant catalyst use (5.89*10.sup.7 mol per g rubber) and olefin use (2.38*10.sup.4 mol per g rubber), with determination of the final molar masses achievable under these conditions.

[0461] Apparent from Table 4 for the 1st experimental series is that low final molar masses are achieved with a ratio (Mw.sub.e/Mw.sub.0)<55% only when using the Grubbs (II) catalyst (I) in combination with non-functionalized 1-olefins known from the prior art, such as 1-hexene, 1-octene and 1-decene, or with non-functionalized olefins having an internal double bond such as trans-4-octene. In this way, however, functionalized nitrile rubbers are not obtained. The use of the molybdenum-containing catalysts (II) and (III) in the presence of 1-hexene gives achievable final molar masses that are only slightly below 100% of the initial molar mass, meaning that there is virtually no metathetic degradation. When using the olefins 5-decene, styrene, m-nitrostyrene, -methylstyrene, trans-stilbene, 1,1-diphenylethylene, 4-octene-1,8-diol, 3,10-diisopropyl-2,11-dimethyl-6-dodecene-3,10-diol, diethyl fumaric, allylamine, 1-allyl-2,3,4,5,6-pentafluorobenzene and 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene stated in Table 4, Mw.sub.e/Mw.sub.0 is markedly above 55%.

[0462] Table 5 shows the inventive experiments of the 2nd experimental series, likewise carried out with constant catalyst use (5.89*10.sup.7 mol per g rubber) and olefin use (2.38*10.sup.4 mol per g rubber), with determination of the final molar masses achievable under these conditions.

[0463] From Table 5 it is apparent for the 2nd experimental series that when using all of the functionalized olefins of the invention, low final molar masses result, with an MW.sub.e/MW.sub.0 ratio <55%.

[0464] Table 6 shows the inventive examples of the 3rd experimental series, which were carried out using different amounts of catalyst and olefin. It is shown that when using the functionalized olefins of the invention, starting both from unhydrogenated nitrile rubber and from partially hydrogenated nitrile rubber, the metathesis produces nitrile rubbers of relatively low molecular weight M, with 0.7 to 3.3 functional groups per molecule.

TABLE-US-00005 TABLE 4 1st experimental series (comparative experiments) Catalyst Olefin Experi- ment Amount Amount [00002]$\left[\frac{{\mathrm{Mw}}_e}{{\mathrm{Mw}}_o}\right]100$ No. Type [mol/g NBR] NBR Type [mol/g NBR] [%] 1.01 I 5.89 * 10.sup.7 C 1-Hexene 2.38 * 10.sup.4 28 1.02 II 5.89 * 10.sup.7 C 1-Hexene 2.38 * 10.sup.4 95 1.03 III 5.89 * 10.sup.7 C 1-Hexene 2.38 * 10.sup.4 94 1.04 I 5.89 * 10.sup.7 A 1-Octene 2.38 * 10.sup.4 19 1.05 I 5.89 * 10.sup.7 A 1-Decene 2.38 * 10.sup.4 22 1.06 I 5.89 * 10.sup.7 C trans-4-Octene 2.38 * 10.sup.4 52 1.07 I 5.89 * 10.sup.7 C 5-Decene 2.38 * 10.sup.4 60 1.08 I 5.89 * 10.sup.7 C Styrene 2.38 * 10.sup.4 57 1.09 I 5.89 * 10.sup.7 C m-Nitrostyrene 2.38 * 10.sup.4 67 1.10 I 5.89 * 10.sup.7 A -Methylstyrene 2.38 * 10.sup.4 67 1.11 I 5.89 * 10.sup.7 A trans-Stilbene 2.38 * 10.sup.4 75 1.12 I 5.89 * 10.sup.7 A 1,1-Diphenylethylene 2.38 * 10.sup.4 66 1.13 I 5.89 * 10.sup.7 C 5-Octene-1,8-diol 2.38 * 10.sup.4 58 1.14 I 5.89 * 10.sup.7 C 3,10-Diisopropyl-2,11- 2.38 * 10.sup.4 61 dimethyl-6-dodecene- 3,10-diol 1.15 I 5.89 * 10.sup.7 B Diethyl fumarate 2.38 * 10.sup.4 59 1.16 I 5.89 * 10.sup.7 C Allylamine 2.38 * 10.sup.4 92 1.17 I 5.89 * 10.sup.7 B 1-Allyl-2,3,4,5,6- 2.38 * 10.sup.4 65 pentafluorobenzene 1.18 I 5.89 * 10.sup.7 B 3,3,4,4,5,5,6,6,6- 2.38 * 10.sup.4 88 Nonafluoro-1-hexene

TABLE-US-00006 TABLE 5 2nd experimental series (inventive experiments) Catalyst Olefin Experi- ment Amount Amount [00003]$\left[\frac{{\mathrm{Mw}}_e}{{\mathrm{Mw}}_o}\right]100$ No. Type [mol/g NBR] NBR Type [mol/g NBR] [%] 2.01 I 5.89 * 10.sup.7 C Allyl alcohol 2.38 * 10.sup.4 54 2.02 I 5.89 * 10.sup.7 C Allyl benzyl ether 2.38 * 10.sup.4 44 2.03 I 5.89 * 10.sup.7 C Allyl benzoate 2.38 * 10.sup.4 49 2.04 I 5.89 * 10.sup.7 C t-Butyl N-allylcarbamate 2.38 * 10.sup.4 44 2.05 I 5.89 * 10.sup.7 B o-Allylphenol 2.38 * 10.sup.4 45 2.06 I 5.89 * 10.sup.7 B p-Allylphenol 2.38 * 10.sup.4 47 2.07 I 5.89 * 10.sup.7 B o-Allylanisole 2.38 * 10.sup.4 38 2.08 I 5.89 * 10.sup.7 B p-Allylanisole 2.38 * 10.sup.4 33 2.09 I 5.89 * 10.sup.7 B cis-2-Butene-1,4-diol 2.38 * 10.sup.4 51 2.10 I 5.89 * 10.sup.7 B cis-1,4-Bisbenzyloxy- 2.38 * 10.sup.4 46 2-butene 2.11 I 5.89 * 10.sup.7 B cis-2-Butene-1,4-diyl 2.38 * 10.sup.4 47 dibenzoate 2.12 I 5.89 * 10.sup.7 B cis-2-Butene-1,4-diyl 2.38 * 10.sup.4 47 diacetate

TABLE-US-00007 TABLE 6 3rd experimental series (inventive experiments) Metathesis catalyst Olefin Amount [mol/g Addition (based on Amount [00004]$\left[\frac{{\mathrm{Mw}}_e}{{\mathrm{Mw}}_o}\right]100$ Number of functional groups per No. Type NBR] catalyst) NBR Type [mol/g NBR] [%] NBR chain 3.01 I 1.77 * 10.sup.6 C allyl benzyl 7.14 * 10.sup.4 14 1.2 ether 3.02 I 1.77 * 10.sup.6 C allyl 7.14 * 10.sup.4 20 1.1 benzoate 3.03 I 1.77 * 10.sup.6 C t-butyl N- 7.14 * 10.sup.4 14 1.4 alltlcarb- amate 3.04 I 1.77 * 10.sup.6 C p- 7.14 * 10.sup.4 7 1.5 allylanisole 3.05 I 1.77 * 10.sup.6 C cis-2-butene- 7.14 * 10.sup.4 24 1.9 1,4-diyl dibenzoate 3.06 I 5.89 * 10.sup.7 C cis-2-butene 1.43 * 10.sup.3 44 2.2 1,4-diyl dibenzoate 3.07 I 3.53 * 10.sup.6 C cis-2-butene- 2.38 * 10.sup.4 21 1.8 1,4-diyl dibenzoate 3.08 I 3.53 * 10.sup.6 C cis-2-butene- 1.43 * 10.sup.3 13 3.3 1,4-diyl dibenzoate 3.09 I 5.89 * 10.sup.7 100 eq. C cis-2-butene- 2.38 * 10.sup.4 21 1.2 Ti(OiPr).sub.4 1,4-diyl dibenzoate 3.10 I 5.89 * 10.sup.7 100 eq. C cis-1,4- 2.38 * 10.sup.4 32 0.7 Ti(OiPr).sub.4 bisbenzyloxy- 2-butene 3.11 I 7.06 * 10.sup.6 D cis-1,4- 2.86 * 10.sup.3 15 1.9 bisbenzyloxy- 2-butene