CATALYST COMPOSITIONS AND THEIR USE FOR HYDROGENATION OF NITRILE RUBBER
20180223005 ยท 2018-08-09
Assignee
Inventors
- Werner Obrecht (Moers, DE)
- Sarah David (Dormagen, DE)
- Qingchun LIU (Qingdao, CN)
- Zhenli Wei (Qingdao, CN)
Cpc classification
B01J31/2265
PERFORMING OPERATIONS; TRANSPORTING
B01J2540/40
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2278
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2208
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2404
PERFORMING OPERATIONS; TRANSPORTING
B01J31/183
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/641
PERFORMING OPERATIONS; TRANSPORTING
B01J31/181
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2273
PERFORMING OPERATIONS; TRANSPORTING
B01J2540/20
PERFORMING OPERATIONS; TRANSPORTING
B01J31/1805
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2295
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J31/02
PERFORMING OPERATIONS; TRANSPORTING
B01J31/24
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Catalyst compositions based on Ruthenium- or Osmium-based complex catalysts and specific co-catalysts are provided for selectively hydrogenating nitrile rubbers in the presence of such catalyst compositions.
Claims
1. A process for hydrogenating nitrile rubber, the process comprising a) preparing a catalyst composition by contacting: a complex catalyst based on ruthenium or osmium as central metal and bearing at least one ligand bound to the ruthenium or osmium central metal in a carbene-like fashion, with at least one co-catalyst in a molar ratio of the complex catalyst to the co-catalyst in the range of 1:(20-550) wherein the co-catalyst must contain at least one vinyl group, and thereafter b) hydrogenating nitrile rubber in the presence of the catalyst composition formed in step a).
2. The process for hydrogenating nitrile rubber according to claim 1, further comprising conducting step a) at a temperature of 20 C. to 160 C.
3. The process for hydrogenating nitrile rubber according to claim 1, wherein a molar ratio of the complex catalyst to the co-catalyst in step a) is 1:(20-500).
4. The process for hydrogenating nitrile rubber according to claim 3, wherein a molar ratio of the complex catalyst to the co-catalyst is 1:(20 to below 100).
5. The process for hydrogenating nitrite rubber according to claim 1, further comprising conducting the hydrogenation in step b) at a temperature of 60 C. to 200 C., and at a hydrogen pressure of 0.5 MPa to 35 MPa.
6. The process for hydrogenating nitrile rubber according to claim 1, further comprising, prior to hydrogenation, subjecting the nitrite rubber to a molecular weight degradation in a metathesis reaction comprising contacting the nitrile rubber in the absence or presence of a co-olefin with a complex catalyst based on ruthenium or osmium as central metal and bearing at least one ligand bound to the ruthenium or osmium central metal in a carbene-like fashion, then c) contacting the complex catalyst which is present in the reaction mixture obtained after the metathesis reaction with at least one co-catalyst having at least one vinyl group in a molar ratio of the complex catalyst to the co-catalyst of 1:(20-550) to form a catalyst composition, and thereafter d) hydrogenating the nitrite rubber in the presence of the catalyst composition.
7. The process for hydrogenating nitrile rubber according to claim 1, wherein the co-catalyst has the general formula (1)
CH.sub.2CRR(1) in which R and R are identical or different and shall mean hydrogen, or OR.sup.1 wherein R.sup.1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(O)(R.sup.2), C(O)N(R).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4 wherein X is identical or different and means oxygen (O) or NR.sup.2 R.sup.2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, R.sup.3 are identical or different and represent C.sub.1-C.sub.8 alkyl or (CH.sub.2).sub.nOCHCH.sub.2, R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, n is 1 to 5, m is 1 to 10, p is 0 to 5, where in the alternative, if R and R both represent a group OR.sup.1, both R.sup.1 may be linked to each other and together represent a divalent group (C(R.sup.2).sub.2).sub.q with q being 2, 3 or 4 and R.sup.2 being identical or different and having the above defined meanings, or SR.sup.5, SOR.sup.5, SO.sub.2R.sup.5 wherein R.sup.5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or N(R.sup.6R.sup.7), P(R.sup.6R) wherein R.sup.6 and R.sup.7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, C(O)(R.sup.2), or where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 7 carbon atoms in the cyclic structure wherein one, two or three of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 wherein R.sup.8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; or P(O)(OR.sup.9).sub.2 in which R.sup.9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, however, under the proviso that R and R must not both represent hydrogen in formula (I) at the same time.
8. The process for hydrogenating nitrile rubber according to claim 1, wherein the co-catalyst is selected from the group consisting of formulae (cocat-1) to (cocat-38) ##STR00037## ##STR00038##
9. The process for hydrogenating nitrile rubber according to claim 1, wherein the complex catalyst is selected from the group consisting of (i) catalysts of general formula (A), ##STR00039## where M is osmium or ruthenium, X.sup.1 and X.sup.2 are identical or different and are two ligands, L are identical or different ligands, R are identical or different and are each hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, or alkylsulphinyl, where these groups may in each case optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moities or, as an alternative, the two groups R together with the common carbon atom to which they are bound are bridged to form a cyclic structure which can be aliphatic or aromatic in nature, may be substituted and may contain one or more heteroatoms, (ii) catalysts of general formula (A1), ##STR00040## where X.sup.1, X.sup.2 and L can have the same meanings as in the general formula (A), n is 0, 1 or 2, m is 0, 1, 2, 3 or 4 and R are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals which may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl, (iii) catalysts of general formula (B), ##STR00041## where M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and are anionic ligands, R are identical or different and are organic moieties, Im is a substituted or unsubstituted imidazoline or imidazolidine ligand, and An is an anion, (iv) catalysts of general formula (C) ##STR00042## where M is ruthenium or osmium, R.sup.13 and R.sup.14 are each, independently of one another, 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 an uncharged A-bonded ligand which may either be monocyclic or polycyclic, L.sup.3 is a ligand selected from the group consisting of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines, Y.sup. is a noncoordinating anion, and n is 0, 1, 2, 3, 4 or 5, (v) catalysts of general formula (D), ##STR00043## where M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and are anionic ligands which can have all meanings of X.sup.1 and X.sup.2 mentioned in the general formulae (A) and (B), L represent identical or different ligands which can have all meanings of L mentioned in the general formulae (A) and (B), and R.sup.19 and R.sup.20 are identical or different and are each hydrogen or substituted or unsubstituted alkyl, (vi) catalysts of general formula (E), (F) or (G), ##STR00044## where M is osmium or ruthenium, X.sup.1 and X.sup.2 are identical or different and are two ligands, L is a ligand, Z.sup.1 and Z.sup.3 are identical or different and are uncharged electron donors, and R.sup.21 and R.sup.22 are each, independently of one another, hydrogen alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulphonyl or alkylsulphinyl which are in each case substituted by one or more substituents selected from among alkyl, halogen, alkoxy, aryl or heteroaryl, (vii) catalysts (N) comprising the general structural element (N1), where the carbon atom denoted by * is bound via one or more double bonds to the catalyst having a ruthenium or osmium central metal, ##STR00045## where R.sup.25-R.sup.32 are identical or different and are each 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 alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where all these moieties can each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, two directly adjacent substituents from the group consisting of R.sup.25-R.sup.32 together with the ring carbons to which they are bound form a cyclic group, by bridging or, as an alternative, R.sup.8 is optionally bridged to 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), where R.sup.33-R.sup.39 are identical or different and can each have the same meanings as R.sup.25-R.sup.32, and (viii) catalysts of general formulae (N2a) or (N2b), ##STR00046## where M is ruthenium or osmium, X.sup.1 and X.sup.2 are identical or different and are two ligands, L.sup.1 and L.sup.3 are identical or different ligands, where L.sup.2 can alternatively also be bridged to the radical R.sup.8, n is 0, 1, 2 or 3, n is 1 or 2, and R.sup.25-R.sup.32, m and A have the same meanings as given in general formula (N1).
10. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is of general formula (A) and one group R is hydrogen and the other group R is C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.34-aryl, C.sub.1-C.sub.20-carboxylate, C.sub.1-C.sub.20-alkoxy, C.sub.1-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 or C.sub.1-C.sub.2-alkylsulphinyl, where these moieties may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.
11. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is of general formula (A) and X.sup.1 and X.sup.2 are identical and are each halogen, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CHC.sub.6H.sub.4SO.sub.3), mesylate (CH.sub.3SO.sub.3) or CF.sub.3SO.sub.3 (trifluoromethanesulphonate).
12. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is of general formula (A) and one or both of the ligands L have a structure according to general formulae (IIa)-(IId), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (IIa) to (IId), ##STR00047## where R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are identical or different and represent 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.6-C.sub.24-aryl, C.sub.7-C.sub.25-alkaryl, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heterocyclyl, C.sub.1-C.sub.30-alkoxy, C.sub.2-C.sub.3-alkenyloxy, C.sub.2-C.sub.20-alkynyloxy, C.sub.6-C.sub.20-aryloxy, C.sub.2-C.sub.20-alkoxycarbonyl, C.sub.3-C.sub.20-alkylthio, C.sub.6-C.sub.20-arylthio, Si(R).sub.3, OSi(R).sub.3, OC(O)R, C(O)R, C(O)N(R).sub.2, NRC(O)N(R).sub.2, SO.sub.2N(R).sub.2S(O)R, S(O).sub.2R, OS(O).sub.2R, halogen, nitro or cyano, wherein in all above occurrences relating to the meanings of R.sup.8, R.sup.9, R.sup.10 and R.sup.11 the group R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl, and R.sup.15, R.sup.16 and R.sup.17 are identical or different and may represent alkyl, cycloalkyl, alkoxy, aryl, aryloxy, or a heterocyclic group.
13. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is of general formula (A) and one or both of the ligands L have a structure (IIIa) to (IIIu), where in all cases Ph means phenyl, Bu butyl, Mes 2,4,6-trimethylphenyl, Dipp 2,6-diisopropylphenyl, and Dimp 2,6-dimethylphenyl, and wherein the meaning of L can be identical or different in case both ligands L have a structure according to (IIIa) to (IIIu), ##STR00048## ##STR00049## ##STR00050##
14. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is of general formula (A) and is immobilized on a support material as immobilized catalyst having the general formulae (support-1), (support-2), or (support-3), ##STR00051## wherein M, Y, L, X.sup.1, X.sup.2, and R may have the meanings given for general formula (A) and wherein supp stands for the support material.
15. The process for hydrogenating nitrile rubber according to claim 9, wherein the complex catalyst is one of the general formulae (E), (F), and (G) in which M is ruthenium, X.sup.1 and X.sup.1 are both halogen, R.sup.1 and R.sup.2 are identical or different and are five- or six-membered monocyclic groups having from 1 to 4, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the above-mentioned groups may in each case be substituted by one or more moieties selected from the group consisting of alkyl, cycloalkyl, alkoxy, halogen, aryl, or heteroaryl, Z.sup.1 and Z.sup.2 are identical or different and five- or six-membered monocyclic groups having from 1 to 4, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all these abovementioned groups may in each case optionally be substituted by one or more alkyl, cycloalkyl, alkoxy, halogen, aryl, or heteroaryl, radicals which may in turn each be substituted by one or more moieties selected from the group consisting of halogen, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl, R.sup.21 and R.sup.22 are identical or different and are each 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 has a structure of the above-described general formula (IIa) or (IIb.
16. The process for hydrogenating nitrile rubber according to claim 1, wherein the complex catalyst is selected from the catalysts shown in the following formulae, wherein in each case Cy is cyclohexyl, Mes is 2,4,6-trimethylphenyl and Ph is phenyl ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056##
17. The process for hydrogenating nitrile runner according to claim 10, wherein: the molar ratio of the complex catalyst to the co-catalyst is 1:(40 to 70); X.sup.1 and X.sup.2 are identical and are each halogen, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH.sub.3C.sub.6H.sub.4SO.sub.3), mesylate (CH.sub.3SO.sub.3) or CF.sub.3SO.sub.3 (trifluoromethanesulphonate); and one or both of the ligands L have a structure according to general formulae (IIa)-(IId), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (IIa) to (IId), ##STR00057## where R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are identical or different and represent 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.7-C.sub.25-alkaryl, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heterocyclyl, 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.20-aryloxy, C.sub.2-C.sub.20-alkoxycarbonyl, C.sub.1-C.sub.20-alkylthio, C.sub.6-C.sub.20-arylthio, Si(R).sub.3, OSi(R), OC(O)R, C(O)R, C(O)N(R).sub.2, NRC(O)N(R).sub.2, SO.sub.2N(R).sub.2, S(O)R, S(O).sub.2R, OS(O)R, halogen, nitro or cyano, wherein in all above occurrences relating to the meanings of R.sup.8, R.sup.9, R.sup.10 and R.sup.11 the group R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl, and R.sup.15, R.sup.16 and R.sup.17 are identical or different and may represent alkyl, cycloalkyl, alkoxy, aryl, aryloxy, or a heterocyclic group; and the complex catalyst is Immobilized on a support material as immobilized catalyst having the general formulae (support-1), (support-2), or (support-3), ##STR00058## wherein M, Y, L, X.sup.1, X.sup.2, and R may have the meanings given for general formula (A) and wherein supp stands for a support material selected from silica gels, macromolecular material, synthetic polymers, polyethylene glycol, polystyrenes and cross-linked polystyrenes.
Description
DETAILED DESCRIPTION OF THE INVENTION
[0071] The term substituted used for the purposes of the present patent application 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 valency of the atom indicated is not exceeded and the substitution leads to a stable compound.
[0072] For the purposes of the present patent application and invention, all the definitions of moities, parameters or explanations given above or below in general terms or in preferred ranges can be combined with one another in any way, i.e. including combinations of the respective ranges and preferred ranges.
Co-Catalyst:
[0073] In a preferred embodiment the co-catalyst has the general formula (1)
CH.sub.2CRR(1)
in which R and R are identical or different and shall mean
hydrogen,
OR.sup.1 wherein R.sup.1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(O)(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4 [0074] wherein [0075] X is identical or different and means oxygen (O) or NR.sup.2 [0076] R.sup.2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, [0077] R.sup.3 are identical or different and represent C.sub.1-C.sub.8 alkyl or (CH.sub.2).sub.nOCHCH.sub.2, [0078] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, [0079] n is in the range of from 1 to 5, [0080] m is in the range of from 1 to 10. [0081] p is in the range of from 0 to 5, [0082] or where in the alternative, if R and R both represent a group OR.sup.1, both R.sup.1 may be linked to each other and together represent a divalent group (C(R.sup.2).sub.2).sub.q with q being 2, 3 [0083] or 4 and R.sup.2 being identical or different and having the above defined meanings,
SR.sup.5, SOR.sup.5, SO.sub.2R.sup.5 [0084] wherein R.sup.5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,
N(R.sup.6R.sup.7), P(R.sup.6R.sup.7) [0085] wherein R.sup.6 and R.sup.7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, C(O)(R.sup.2), or [0086] where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 7 carbon atoms in the cyclic structure wherein one, two or three of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 [0087] wherein R.sup.8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or
P(O)(OR.sup.9).sub.2 [0088] in which R.sup.9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl,
however, under the proviso that R and R must not both represent hydrogen at the same time.
[0089] In the co-catalysts according to general formula (1) all alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl moieties in R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 or R.sup.9 may optionally be further substituted by one or more alkyl, halogen, alkoxy, alkenyloxy, aryl or heteroaryl substituents. All aforementioned moities, in particular the alkyl, alkenyl and/or alkynyl moieties can be either straight chain or branched to the extent chemically plausible. Of course, the above proviso that the valency of the atom indicated is not exceeded and the substitution leads to a stable compound shall be fulfilled.
[0090] If R and R represent OR.sup.1, both such R.sup.1 can be linked to each other and together represent a divalent group (C(R.sup.2).sub.2).sub.q with q being 2, 3, 4 or 5 and R.sup.2 being identical or different and having the meanings defined regarding formula (1) above. In such case a cyclic structure is formed by the divalent group together with the two oxygen atoms to which it the divalent group is bound and the adjacent vinylic carbon atom.
[0091] In another embodiment of the present invention the catalyst composition is obtained using at least one, preferably one, co-catalyst having the general formula (1)
CH.sub.2CRR(1)
in which R is hydrogen and R shall mean, [0092] OR.sup.1 wherein R.sup.1 shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, C.sub.6-C.sub.24-heteroaryl, C(O)(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4, [0093] wherein [0094] X is identical or different and oxygen (O) or NR.sup.2, [0095] R.sup.2 are identical or different and represent H. C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.3-C.sub.20-heteroaryl, [0096] R.sup.3 are identical or different and represent C.sub.1-C.sub.4 alkyl or (CH.sub.2).sub.nOCHCH.sub.2. [0097] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2. [0098] n is in the range of from 1 to 4, [0099] m is in the range of from 1 to 5, [0100] p is in the range of from 0 to 5,
SR, SOR.sup.5, SO.sub.2R.sup.5 [0101] wherein R.sup.5 represents C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl,
N(R.sup.6R.sup.7), P(R.sup.6R.sup.7) [0102] wherein R.sup.6 and R.sup.7 are identical or different and shall mean C.sub.1-C.sub.16-alkyl. C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl, C(O)(R.sup.2), or [0103] where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 7 carbon atoms in the cyclic structure wherein one, two or three of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 wherein R.sup.8 shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl, or
P(O)(OR.sup.9).sub.2 [0104] in which R.sup.9 are identical or different and shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl.
[0105] In another embodiment of the present invention the catalyst composition is obtained using at least one, preferably one, co-catalyst having the general formula (1)
CH.sub.2CRR(1)
in which R and R are identical or different and shall mean [0106] OR.sup.1 wherein R.sup.1 shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, C.sub.6-C.sub.4-heteroaryl, C(O(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4. [0107] wherein [0108] X is identical or different and oxygen (O) or NR.sup.2, [0109] R.sup.2 are identical or different and represent H, C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.3-C.sub.20-heteroaryl, [0110] R.sup.3 are identical or different and represent C.sub.1-C.sub.4 alkyl or (CH.sub.2).sub.nOCHCH.sub.2, [0111] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, [0112] n is in the range of from 1 to 4, [0113] m is in the range of from 1 to 5, [0114] p is in the range of from 0 to 5, [0115] or where in the alternative, if R and R both represent a group OR.sup.1, both R.sup.1 may be linked to each other and together represent a divalent group (C(R.sup.2).sub.2).sub.q with q being 2, 3 [0116] or 4 and R.sup.2 being identical or different and having the above defined meanings,
SR.sup.5, SOR.sup.5, SO.sub.2R.sup.5 [0117] wherein R.sup.5 represents C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl,
N(R.sup.6R.sup.7), P(R.sup.6R.sup.7) [0118] wherein R.sup.6 and R.sup.7 are identical or different and shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl, C(O)(R.sup.2), or [0119] where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 7 carbon atoms in the cyclic structure wherein one, two or three of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 wherein R.sup.8 shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl, or
P(O)(OR.sup.9).sub.2 [0120] in which R.sup.9 are identical or different and shall mean C.sub.1-C.sub.16-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.2-C.sub.16-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.24-aryl, or C.sub.6-C.sub.24-heteroaryl.
[0121] In another preferred embodiment of the present invention the catalyst composition is obtained using at least one, preferably one, co-catalyst having the above depicted general formula (1) wherein
CH.sub.2CRR(1) [0122] in which R is hydrogen and R shall mean [0123] OR.sup.1 wherein R.sup.1 shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, C.sub.6-C.sub.14-heteroaryl, C(O)(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4, [0124] wherein [0125] X is identical or different and oxygen (O) or NR.sup.2, [0126] R.sup.2 are identical or different and represent H, C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl, [0127] R.sup.3 are identical or different and represent methyl, ethyl or (CH.sub.2).sub.nOCHCH.sub.2, [0128] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, [0129] n is 1, 2 or 3 [0130] m is 1, 2, 3, or 4, [0131] p is 0, 1, 2, 3 or 4,
SR.sup.5, SOR.sup.5, SO.sub.2R.sup.5 [0132] wherein R.sup.5 represents C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl,
N(R.sup.6R.sup.7), P(R.sup.6R.sup.7) [0133] wherein R.sup.6 and R.sup.7 are identical or different and shall mean C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.6-C.sub.14-heteroaryl, C(O)(R.sup.2), or [0134] where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 5 carbon atoms in the cyclic structure wherein one or two of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 wherein R.sup.8 shall mean C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.12cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl,
P(O)(OR.sup.9).sub.2 [0135] in which R.sup.9 are identical or different and shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.6-C.sub.14-heteroaryl.
In another preferred embodiment of the present invention the catalyst composition is obtained using at least one, preferably one, co-catalyst having the above depicted general formula (1) wherein
CH.sub.2CRR(1)
in which R and R are identical or different and shall mean
OR.sup.1 wherein R.sup.1 shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, C.sub.6-C.sub.14-heteroaryl, C(O)(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nX].sub.mR.sup.2, [(CH.sub.2).sub.nX].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4, [0136] wherein [0137] X is identical or different and oxygen (O) or NR.sup.2, [0138] R.sup.2 are identical or different and represent H, C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl, [0139] R.sup.3 are identical or different and represent methyl, ethyl or (CH.sub.2).sub.nOCHCH.sub.2, [0140] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, [0141] n is 1, 2 or 3 [0142] m is 1, 2, 3, or 4, [0143] p is 0, 1, 2, 3 or 4, [0144] or where in the alternative, if R and R both represent a group OR.sup.1, both R.sup.1 may be linked to each other and together represent a divalent group (C(R.sup.2).sub.2).sub.q with q being 2, or 3 and R.sup.2 being identical or different and representing hydrogen or C.sub.1-C.sub.4 alkyl,
SR.sup.5, SOR.sup.5, SO.sub.2R.sup.5 [0145] wherein R.sup.5 represents C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl,
N(R.sup.6R.sup.7), P(R.sup.6R.sup.7) [0146] wherein R.sup.6 and R.sup.7 are identical or different and shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.6-C.sub.14-heteroaryl, C(O)(R.sup.2), or [0147] where in the alternative R.sup.6 and R.sup.7 may form together with such N or P atom to which they both are linked at the same time a saturated, unsaturated or aromatic cyclic structure with 4 to 5 carbon atoms in the cyclic structure wherein one or two of said carbon atoms can be replaced by a moiety selected from oxygen, sulfur, nitrogen, NR.sup.8 or PR.sup.8 wherein R.sup.8 shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.3-C.sub.14-heteroaryl,
P(O)(OR.sup.9).sub.2 [0148] in which R.sup.9 are identical or different and shall mean C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.12-alkenyl, C.sub.2-C.sub.12-alkynyl, C.sub.6-C.sub.14-aryl, or C.sub.6-C.sub.14-heteroaryl.
[0149] In another more preferred embodiment of the present invention the catalyst composition is obtained using one co-catalyst having the above depicted general formulae (1) in which R is hydrogen and R represents [0150] OR.sup.1 wherein R.sup.1 shall mean C.sub.1-C.sub.6-alkyl, C.sub.5-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl, C(O)(R.sup.2), C(O)N(R.sup.2).sub.2, [(CH.sub.2).sub.nO].sub.mR.sup.2, [(CH.sub.2).sub.nO].sub.mCHCH.sub.2, or (CH.sub.2).sub.pC(R.sup.3).sub.2R.sup.4. [0151] wherein [0152] R.sup.2 are identical or different and represent H, C.sub.1-C.sub.6-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl, [0153] R.sup.3 are identical or different and represent methyl, ethyl or (CH.sub.2).sub.nOCHCH.sub.2, [0154] R.sup.4 represents (CH.sub.2).sub.pOCHCH.sub.2, [0155] n is 1, or 2, [0156] m is 1, 2, or 3, and [0157] p is 0, 1, or 3.
[0158] In all the above mentioned preferred, more preferred and most preferred embodiments of the co-catalysts according to general formula (1) the alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl moieties in R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 or R.sup.9 may optionally be further substituted by one or more C.sub.1-C.sub.6-alkyl, C.sub.5-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl moieties. All aforementioned substituents, in particular the alkyl, alkenyl and/or alkynyl moieties can be either straight chain or branched to the extent chemically plausible.
[0159] In an even more preferred embodiment of the present invention one or more co-catalysts are used for the preparation of the novel catalyst compositions which have the following formulae:
##STR00006##
[0160] In another also preferred embodiment of the present invention a co-catalyst is used for the preparation of the novel catalyst compositions in which R and R both represent OR.sup.1 where such R.sup.1 together form a divalent group as defined above, wherein such specific co-catalysts have the following formulae with R.sup.6 having the same meaning as outlined for general formula (1).
##STR00007##
Catalysts:
[0161] The catalysts to be used in the process of the invention are complex catalysts based either on ruthenium or osmium. Furtheron, these complex catalysts have the common structural feature that they possess at least one ligand which is bound to ruthenium or osmium in a carbene-like fashion. In a preferred embodiment, the complex catalyst has two carbene ligands, i.e. two ligands which are bound in a carbene-like fashion to the central metal of the complex.
[0162] The novel catalyst composition of the present invention is obtainable using for example a catalyst of the general formula (A),
##STR00008##
where
M is osmium or ruthenium, [0163] X.sup.1 and X.sup.2 are identical or different and are two ligands, preferably anionic ligands, [0164] L are identical or different ligands, preferably uncharged electron donors, [0165] R are identical or different and are each 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, where these groups may in each case optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moities or, as an alternative, the two groups R together with the common carbon atom to which they are bound are bridged to form a cyclic structure which can be aliphatic or aromatic in nature, may be substituted and may contain one or more heteroatoms.
[0166] Various representatives of the catalysts of the formula (A) are known in principle, e.g. from WO-A-96/04289 and WO-A-97/06185.
[0167] In preferred catalysts of the general formula (A), one group R is hydrogen and the other group R is C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.10-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 or C.sub.1-C.sub.20-alkylsulphinyl, where these moiety may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.
Definition of X.sup.1 and X.sup.2
[0168] in the catalysts of the general formula (A), X.sup.1 and X.sup.2 are identical or different and are two ligands, preferably anionic ligands.
X.sup.1 and X.sup.2 can be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched C.sub.1-C.sub.30-alkyl, C.sub.6-C.sub.24-aryl, C.sub.1-C.sub.20-alkoxy, C.sub.6-C.sub.74-aryloxy, C.sub.3-C.sub.20-alkyldiketonate C.sub.6-C.sub.24-aryldiketonate, C.sub.1-C.sub.20-carboxylate, C.sub.1-C.sub.20-alkylsulphonate, C.sub.6-C.sub.24-arylsulphonate, C.sub.1-C.sub.20-alkylthiol, C.sub.6-C.sub.24-arylthiol, C.sub.1-C.sub.20-alkylsulphonyl or C.sub.1-C.sub.20-alkylsulphinyl.
X.sup.1 and X.sup.2 can also be substituted by one or more further groups, for example by halogen, preferably fluorine, C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkoxy or C.sub.6-C.sub.24-aryl, where these groups, too, may once again be substituted by one or more substituents selected from the group consisting of halogen, preferably fluorine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl.
[0169] In a preferred embodiment, X.sup.1 and X.sup.2 are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C.sub.1-C.sub.5-carboxylate, C.sub.1-C.sub.5-alkyl, phenoxy, C.sub.1-C.sub.5-alkoxy, C.sub.1-C.sub.5-alkylthiol, C.sub.6-C.sub.24-arylthiol, C.sub.6-C.sub.24-aryl or C.sub.1-C.sub.5-alkylsulphonate.
[0170] In a particularly preferred embodiment, X.sup.1 and X.sup.2 are identical and are each halogen, in particular chlorine, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH.sub.3C.sub.6H.sub.4SO.sub.3), mesylate (CH.sub.3SO.sub.3) or CF.sub.3SO.sub.3 (trifluoromethanesulphonate).
Definition of L
[0171] In the general formula (A), the symbols L represent identical or different ligands and are preferably uncharged electron donating ligand.
[0172] The two ligands L can, for example, be, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine (the latter two also being jointly referred to as Im ligand(s))
[0173] The term phosphinite includes, for example, phenyl diphenylphosphinite, cyclohexyl dicyclohexylphosphinite, isopropyl diisopropylphosphinite and methyl diphenylphosphinite.
[0174] The term phosphite includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.
[0175] The term stibine includes, for example, triphenylstibine, tricyclohexylstibine and trimethylstibine.
[0176] The term sulfonate includes, for example, trifluoromethanesulphonate, tosylate and mesylate.
[0177] The term sulfoxide includes, for example, (CH.sub.3).sub.2S(O) and (C.sub.6H.sub.5).sub.2SO.
[0178] The term thioether includes, for example, CH.sub.3SCH.sub.3, C.sub.6H.sub.5SCH.sub.3, CH.sub.3OCH.sub.2CH.sub.2SCH.sub.3 and tetrahydrothiophene.
[0179] For the purposes of the present application, the term pyridine is used as a collective term for all nitrogen-containing ligands as are mentioned by, for example, Grubbs in WO-A-031011455. Examples are: pyridine, picolines (including -, - and -picoline), lutidines (including 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine), collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4-(dimethylamino)pyridine, chloropyridines, bromopyridines, nitropyridines, quinoline, pyrimidine, pyrrole, imidazole and phenylimidazole.
[0180] In a preferred embodiment catalysts of general formula (A) are used in which one or both of ligands L represent an imidazoline or imidazolidine ligand (also jointly referred to as Im-ligand in this application unless indicated otherwise), having a structure of general formulae (IIa) or (IIb), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (IIa) or (IIb),
##STR00009##
where [0181] R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are identical or different and represent 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.7-C.sub.25-alkaryl, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heterocyclyl, 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.20-aryloxy, C.sub.6-C.sub.20-alkoxycarbonyl, C.sub.1-C.sub.20-alkylthio, C.sub.6-C.sub.20-arylthio, Si(R).sub.3, OSi(R).sub.3, OC(O)R, C(O)R, C(O)N(R).sub.2, NRC(O)N(R).sub.2, SO.sub.2N(R).sub.2S(O)R, S(O).sub.2R, OS(O).sub.2R, halogen, nitro or cyano, wherein in all above occurrences relating to the meanings of R.sup.8, R.sup.9, R.sup.10 and R.sup.11 the group R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
[0182] If appropriate, one or more of R.sup.8, R.sup.9, R.sup.10, and R.sup.11 can independently of one another, be substituted 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, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heterocyclic, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, where these abovementioned substituents, to the extent chemically possible, may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl.
[0183] Merely in the interest of clarity, it may be added that the structures of the imidazoline and imidazolidine ligand depicted in the general formulae (IIa) and (IIb) in the present patent application are equivalent to the structures (IIa) and (IIb) which are frequently also found in the literature for this imidazoline and imidazolidine ligand, respectively, and emphasize the carbene character of the imidazoline and imidazolidine. This applies analogously to the associated preferred structures (IIIa)-(IIIu) depicted below.
##STR00010##
[0184] In a preferred embodiment of the catalysts of the general formula (A), [0185] R.sup.8 and R.sup.9 are each identical or different and represent hydrogen, C.sub.6-C.sub.24-aryl, straight-chain or branched C.sub.1-C.sub.10-alkyl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound.
[0186] More preferably [0187] R.sup.8 and R.sup.9 are identical and are selected from the group consisting of hydrogen, methyl, propyl, butyl and phenyl.
[0188] The preferred and more preferred meanings of R.sup.8 and R.sup.9 may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkoxy, C.sub.3-C.sub.8-cycloalkyl, C.sub.6-C.sub.24-aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl. [0189] R.sup.10 and R.sup.11 are identical or different and preferably represent straight-chain or branched C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.6-C.sub.24-aryl, particularly preferably phenyl, C.sub.1-C.sub.10-alkylsulfonate, C.sub.6-C.sub.10-arylsulfonate.
[0190] More preferably [0191] R.sup.10 and R.sup.11 are identical and are selected from the group consisting of i-propyl, neopentyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.
[0192] These preferred meanings of R.sup.10 and R.sup.11 may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkoxy, C.sub.3-C.sub.8-cycloalkyl, C.sub.6-C.sub.24-aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl.
[0193] Particularly preferred are catalysts of general formula (A) in which one or both of ligands L represent imidazoline and imidazolidine ligands having the structures (IIIa) to (IIIu), where Ph means in each case phenyl, Bu means butyl, Mes represents in each case 2,4,6-trimethylphenyl, Dipp means in all cases 2,6-diisopropylphenyl and Dimp means 2,6-dimethylphenyl, and wherein the meaning of L can be identical or different in case both ligands L in general formula (A) have a structure according to (IIIa) to (IIIu),
##STR00011## ##STR00012## ##STR00013##
[0194] In a further preferred embodiment of catalyst (A) one or both of the ligands L may have the meaning of general formulae (IIc) or (IId), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (IIc) or (IId),
##STR00014##
wherein [0195] R.sup.8, R.sup.9 and R.sup.10 may have all general, preferred, more preferred and most preferred meanings as defined above in relation to general formulae (IIa) and (IIb), and [0196] R.sup.15, R.sup.16 and R.sup.17 are identical or different and may represent alkyl, cycloalkyl, alkoxy, aryl, aryloxy, or a heterocyclic group.
[0197] In general formulae (IIc) and (IId) R.sup.8, R.sup.9, R.sup.10, R.sup.15, R.sup.16 and R.sup.17 may also be substituted by one or more further, identical or different substituents selected from the group consisting of straight-chain or branched C.sub.1-C.sub.5-alkyl, in particular methyl, C.sub.1-C.sub.5-alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.
[0198] In a more preferred embodiment the ligands L has the general formula (Id) wherein [0199] R.sup.15, R.sup.16 and R.sup.17 are identical or different, even more preferably identical, and can represent C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.20 alkoxy, C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 aryloxy, C.sub.2-C.sub.20 heteroaryl or a C.sub.2-C.sub.20 heterocyclic group.
[0200] In an even more preferred embodiment the ligand L has the general formula (IId) wherein [0201] R.sup.15, R.sup.16 and R.sup.17 are identical and each selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, neophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, tolyl, 2,6-dimethylphenyl, and trifluoromethyl.
[0202] In case one or both of the ligand L possess general formula (Id) it most preferably represents PPh.sub.3, P(p-Tol).sub.3, P(o-Tol).sub.3, PPh(CH.sub.3).sub.2, P(CF.sub.3).sub.3, P(p-FC.sub.6H.sub.4).sub.3, P(p-CF.sub.3C.sub.6H.sub.4).sub.3, P(CH.sub.4SO.sub.3Na).sub.3, P(CH.sub.2C.sub.6H.sub.4SO.sub.3Na).sub.3, P(isopropyl).sub.3, P(CHCH.sub.3(CH.sub.2CH.sub.3)).sub.3, P(cyclopentyl).sub.3, P(cyclohexyl).sub.3, P(neopentyl).sub.3 or P(neophenyl).sub.3.
[0203] Particular preference is given to catalyst systems comprising one of the two catalysts below, which fall under the general formula (A) and have the structures (IV) (Grubbs I catalyst) and (V) (Grubbs I catalyst), where Cy is cyclohexyl.
##STR00015##
[0204] In a further embodiment, use can be made of a catalyst of the general formula (A1),
##STR00016##
where [0205] X.sup.1, X.sup.2 and L can have the same general, preferred and particularly preferred meanings as in the general formula (A), [0206] n is 0, 1 or 2, [0207] m is 0, 1, 2, 3 or 4 and [0208] R are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals which may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl.
[0209] As preferred catalyst falling under the general formula (A1), it is possible to use, for example, the catalyst of the formula (VI) below, where Mes is in each case 2,4,6-trimethylphenyl and Ph is phenyl.
##STR00017##
[0210] This catalyst is referred to in literature as Nolan catalyst and known from WO-A-2004/112951.
[0211] The catalysts of general formula (A) as well as the preferred and more preferred embodiments thereof can also be used in immobilized form to prepare the novel catalyst compositions. The immobilization favourably occurs via a chemical bond of the complex catalyst to the surface of a support material. Suited are e.g. complex catalysts having the general formulae (support-1), (support-2), or (support-3), as depicted below, wherein M, Y, L, X.sup.1, X.sup.2, and R may have all general, preferred, more preferred, particularly preferred and most preferred meanings listed above in this application for general formula (A) and wherein supp stands for the support material. Preferably the support material represents a macromolecular material, or silica gels. As macromolecular material synthetic polymers or resins may be used, with polyethylene glycol, polystyrenes or cross-linked polystyrenes (e.g. poly(styrene-divinylbenzene) copolymers (PS-DVB)) being even more preferred. Such support material comprises functional groups on its surface which are able to form covalent bonds to one of the ligands or substituents of the complex catalyst, like e.g. to the ligand L or X.sup.1 or to the substituents R.sup.3 or R.sup.4 as shown in the below depicted formulae.
##STR00018##
[0212] In such immobilized catalysts of general formulae formulae (support-1), (support-2), or (support-3) supp stands more preferably for a polymeric support, a resin, polyethyleneglycole, or silica gels having one or more functional groups X.sup.3 on their surface which are able to form a covalent bond to one of the ligands, like e.g. the L, R or X.sup.1 as shown in the above formulae. Suitable functional groups X.sup.3 on the surface are hydroxyl, amino, thiol, carboxyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, Si(R).sub.3, OSi(R).sub.3, C.sub.6-C.sub.14 aryloxy, C.sub.2-C.sub.14 heterocyclic, sulfinyl, sulfonyl, C(O)R, C(O)OR, C(O)N(R).sub.2, NRC(O)N(R).sub.2, SO.sub.2N(R).sub.2, or N(SO.sub.2R).sub.2 wherein in all above occurrences of R in X.sup.3 is identical or different and shall mean H, C.sub.1-C.sub.6-alkyl, C.sub.5-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl moieties.
[0213] Polystyrene or cross-linked polystyrene is the preferred support material, even more preferably with hydroxyl groups on the surface to allow an easy coupling to the catalyst.
[0214] A further embodiment provides catalyst systems obtainable by using a catalyst of the general formula (B),
##STR00019##
where [0215] M is ruthenium or osmium, [0216] X.sup.1 and X.sup.2 are identical or different and are anionic ligands, [0217] R are identical or different and are organic moieties, [0218] Im is a substituted or unsubstituted imidazoline or imidazolidine ligand and [0219] An is an anion.
[0220] The catalysts of the general formula (B) are known in principle (see, for example, Angew. Chem. Int. Ed. 2004, 43, 6161-6165).
[0221] X.sup.1 and X.sup.2 in the general formula (B) can have the same general, preferred and particularly preferred meanings as in the formula (A).
[0222] The imidazoline or imidazolidine ligand usually has a structure of the general formulae (IIa) or (IIb) which have been mentioned above for the catalyst of general formula (A) and can have all the structures mentioned there as preferred, in particular those of the formulae (IIIa)-(IIIu).
[0223] In general formula (B) R are identical or different and are each a straight-chain or branched C.sub.1-C.sub.30-alkyl, C.sub.5-C.sub.30-cycloalkyl or aryl, where the C.sub.1-C.sub.30-alkyl moiety may be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
[0224] Aryl is an aromatic radical having from 6 to 24 skeletal carbon atoms. As preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic moieties having from 6 to 10 skeletal carbon atoms, mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.
[0225] Preference is given to R in the general formula (B) being identical and each being phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.
[0226] A further alternative embodiment provides a catalyst system obtainable by using a catalyst of the general formula (C)
##STR00020##
where [0227] M is ruthenium or osmium, [0228] R.sup.13 and R.sup.14 are each, independently of one another, 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, [0229] X.sup.3 is an anionic ligand, [0230] L.sup.2 is an uncharged -bonded ligand which may either be monocyclic or polycyclic, [0231] L.sup.3 is a ligand selected from the group consisting of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines, [0232] Y.sup. is a noncoordinating anion and [0233] n is 0, 1, 2, 3, 4 or 5.
[0234] A further alternative embodiment provides a catalyst system obtainable by using a catalyst of the general formula (D),
##STR00021##
where [0235] M is ruthenium or osmium, [0236] X.sup.1 and X.sup.2 are identical or different and are anionic ligands which can have all meanings of X.sup.1 and X.sup.2 mentioned in the general formulae (A) and (B), [0237] the symbols L represent identical or different ligands which can have all general and preferred meanings of L mentioned in the general formulae (A) and (B), [0238] R.sup.19 and R.sup.20 are identical or different and are each hydrogen or substituted or unsubstituted alkyl.
[0239] A further alternative embodiment provides a catalyst system according to the invention obtainable by using a catalyst of the general formula (E), (F) or (G),
##STR00022##
where [0240] M is osmium or ruthenium, [0241] X.sup.1 and X.sup.2 are identical or different and are two ligands, preferably anionic ligands, [0242] L is a ligand, preferably an uncharged electron donor, [0243] Z.sup.1 and Z.sup.2 are identical or different and are uncharged electron donors, [0244] R.sup.21 and R.sup.22 are each, independently of one another, hydrogen alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulphonyl or alkylsulphinyl which are in each case substituted by one or more substituents selected from among alkyl, halogen, alkoxy, aryl or heteroaryl.
[0245] The catalysts of the general formulae (E), (F), and (G) are known in principle, e.g. from WO 2003/011455 A1, WO 2003/087167 A2, Organometalics 2001, 20, 5314 and Angew. Chem. Int. Ed. 2002, 41, 4038. The catalysts are commercially available or can be synthesized by the preparative methods indicated in the abovementioned literature references.
[0246] In the catalyst systems according to the invention, catalysts of the general formulae (E), (F), and (G) can be used in which Z.sup.1 and Z.sup.2 are identical or different and are uncharged electron donors. These ligands are usually weakly coordinating. The ligands are typically optionally substituted heterocyclic groups. These can be five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably 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 which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl.
[0247] Examples of Z.sup.1 and Z.sup.2 encompass nitrogen-containing heterocycles such as pyridines, pyridazines, bipyridines, pyrimidines, pyrazines, pyrazolidines, pyrrolidines, piperazines, indazoles, quinolines, purines, acridines, bisimidazoles, picolylimines, imidazolines, imidazolidines and pyrroles.
Z.sup.1 and Z.sup.2 can also be bridged to one another to form a cyclic structure. In this case, Z.sup.1 and Z.sup.2 form a single bidentate ligand.
[0248] In the catalysts of the general formulae (E), (F), and (G) L can have the same general, preferred and particularly preferred meanings as L in the general formula (A) and (B).
[0249] In the catalysts of the general formulae (E), (F), and (G) R.sup.2 and R.sup.22 are identical or different and are each alkyl, preferably C.sub.1-C.sub.30-alkyl, particularly preferably C.sub.1-C.sub.20-alkyl, cycloalkyl, preferably C.sub.3-C.sub.20-cycloalkyl, particularly preferably C.sub.3-C.sub.8-cycloalkyl, alkenyl, preferably C.sub.2-C.sub.20-alkenyl, particularly preferably C.sub.2-C.sub.16-alkenyl, alkynyl, preferably C.sub.2-C.sub.20-alkynyl, particularly preferably C.sub.2-C.sub.16-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, where the abovementioned substituents may be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moieties.
[0250] In the catalysts of the general formulae (E), (F), and (G) X.sup.1 and X.sup.2 are identical or different and can have the same general, preferred and particularly preferred meanings as indicated above for X.sup.1 and X.sup.2 in the general formula (A).
[0251] Preference is given to using catalysts of the general formulae (E), (F), and (G) in which [0252] M is ruthenium, [0253] X.sup.1 and X.sup.2 are both halogen, in particular chlorine, [0254] R.sup.1 and R.sup.2 are identical or different and are five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case be substituted by one or more moieties selected from the group consisting of alkyl, preferably 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, [0255] Z.sup.1 and Z.sup.2 are identical or different and five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all these abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably 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 which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy and phenyl, [0256] R.sup.21 and R.sup.22 are identical or different and are each 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.2-arylthio, C.sub.1-C.sub.20-alkylsulphonyl, C.sub.1-C.sub.20-alkylsulphinyl, and [0257] L has a structure of the above-described general formula (IIa) or (IIb), in particular one of the formulae (IIIa) to (IIIu).
[0258] A particularly preferred catalyst coming under general formula (E) has the structure (XIX),
##STR00023##
where R.sup.23 and R.sup.24 are identical or different and are each 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 bromine, phenyl, formyl, nitro, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, dialkylamino, trialkylsilyl or trialkoxysilyl.
[0259] The abovementioned meanings for R.sup.23 and R.sup.24 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, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, trialkylsilyl and trialkoxysilyl may in turn each be substituted by one or more halogen, preferably fluorine, chlorine or bromine, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-alkoxy or phenyl moities.
[0260] Particularly preferred embodiments of the catalyst of formula (XIX) have the structure (XIX a) or (XIX b), where R.sup.23 and R.sup.24 have the same meanings as indicated in formula (XIX).
##STR00024##
[0261] When R.sup.3 and R.sup.24 are each bromine in formula (XIXa), the catalyst is referred to in the literature as the Grubbs III catalyst.
[0262] Further suitable catalysts which come under general formulae (E), (F), and (G) have the structural formulae (XX)-(XXXII), where Mes is in each case 2,4,6-trimethylphenyl.
##STR00025## ##STR00026##
[0263] A further embodiment relates to a catalyst system according to the invention obtainable by using a catalyst (N) which has the general structural element (N1), where the carbon atom denoted by * is bound via one or more double bonds to the catalyst framework with a ruthenium or osmium central metal,
##STR00027##
and where [0264] R.sup.15-R.sup.32 are identical or different and are each 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 alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where all these moieties can each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, two directly adjacent substituents from the group consisting of R.sup.25-R.sup.32 together with the ring carbons to which they are bound form a cyclic group, preferably an aromatic system, by bridging or, as an alternative, R.sup.8 is optionally bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst, [0265] m is 0 or 1 and [0266] 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), where R.sup.33-R.sup.39 are identical or different and can each have the same meanings as R.sup.25-R.sup.32.
[0267] In the catalysts having the structural element of the general formula (N1) the carbon atom denoted by * is bound via one or more double bonds to the catalyst framework. If the carbon atom denoted by * is bound via two or more double bonds to the catalyst framework, these double bonds can be cumulated or conjugated.
[0268] Such catalysts (N) have been described in US-A-2009/0076226, which also discloses their preparation.
[0269] The catalysts (N) having a structural element of the general formula (N1) include, for example, catalysts of the general formulae (N2a) and (N2b) below,
##STR00028##
where [0270] M is ruthenium or osmium, [0271] X.sup.1 and X.sup.2 are identical or different and are two ligands, preferably anionic ligands, [0272] L.sup.1 and L.sup.2 are identical or different ligands, preferably uncharged electron donors, where L.sup.2 can alternatively also be bridged to the radical R.sup.8, [0273] n is 0, 1, 2 or 3, preferably 0, 1 or 2, [0274] n is 1 or 2, preferably 1, and [0275] R.sup.25-R.sup.32, m and A have the same meanings as in the general formula (N1).
[0276] In the catalysts of the general formula (N2a), the structural element of the general formula (N1) is bound via a double bond (n=0) or via 2, 3 or 4 cumulated double bonds (in the case of n=1, 2 or 3) to the central metal of the complex catalyst. In the catalysts of the general formula (N2b) suitable to be used for the catalyst systems according to the invention, the structural element of the general formula (N1) is bound via conjugated double bonds to the metal of the complex catalyst. In both cases, the carbon atom denoted by * as a double bond in the direction of the central metal of the complex catalyst.
[0277] The catalysts of the general formulae (N2a) and (N2b) thus encompass catalysts in which the general structural elements (N3)-(N9)
##STR00029##
are bound via the carbon atom denoted by * via one or more double bonds to the catalyst framework of the general formula (N10a) or (N10b)
##STR00030##
where X.sup.1 and X.sup.2, L.sup.1 and L.sup.2, n, n and R.sup.25-R.sup.39 have the meanings given for the general formulae (N2a) and (N2b).
[0278] The Ru- or Os-based carbene catalysts resulting thereof typically have five-fold coordination.
[0279] In the structural element of the general formula (N1), [0280] R.sup.25-R.sup.32 are identical or different and are each 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 alkyl, preferably C.sub.1-C.sub.20alkyl, in particular C.sub.1-C.sub.6-alkyl, cycloalkyl, preferably C.sub.3-C.sub.20-cycloalkyl, in particular C.sub.3-C.sub.8-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.4-aryl, in particular phenyl, 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.1-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, alkylsulphinyl, preferably C.sub.1-C.sub.20-alkylsulphinyl, dialkylamino, preferably di(C.sub.1-C.sub.20-alkyl)amino, alkylsilyl, preferably C.sub.1-C.sub.20-alkylsilyl, or alkoxysilyl, preferably C.sub.1-C.sub.20-alkoxysilyl, where these moities can each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, in each case two directly adjacent substituents from the group consisting of R.sup.25-R.sup.32 together with the ring carbons to which they are bound may also form a cyclic group, preferably an aromatic system, by bridging or, as an alternative, R.sup.8 is optionally bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst, [0281] m is 0 or 1 and [0282] A is oxygen, sulphur, C(R.sup.33)(R.sup.3), NR.sup.35, C(R.sup.36)C(R.sup.37) or C(R.sup.36)(R.sup.38)C(R.sup.37)(R.sup.39), where R.sup.33-R.sup.39 are identical or different and can each have the same preferred meanings as the radicals R.sup.1-R.sup.8. [0283] C.sub.1-C.sub.8-Alkyl in the structural element of the general formula (N1) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, I-ethylpropyl or n-hexyl. [0284] C.sub.3-C.sub.5-Cycloalkyl in the structural element of the general formula (N1) is, for example, cyclopropyl, cyclobutyl, cylopentyl, cyclohexyl, cycloheptyl or cyclooctyl. [0285] C.sub.6-C.sub.24-Aryl in the structural element of the general formula (N1) comprises an aromatic radical having from 6 to 24 skeletal carbon atoms. As preferred 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. [0286] X.sup.1 and X.sup.2 in the structural element of the general formula (N1) have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula A.
[0287] In the general formulae (N2a) and (N2b) and analogously in the general formulae (N10a) and (N10b), L.sup.1 and L.sup.2 are identical or different ligands, preferably uncharged electron donors, and can have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula (A).
[0288] Preference is given to catalysts of the general formulae (N2a) or (N2b) having a general structural unit (N1) in which [0289] M is ruthenium, [0290] X.sup.1 and X.sup.2 are both halogen, [0291] n is 0, 1 or 2 in the general formula (N2a) or [0292] n is 1 in the general formula (N2b) [0293] L.sup.1 and L.sup.2 are identical or different and have the general or preferred meanings indicated for the general formulae (N2a) and (N2b), [0294] R.sup.25-R.sup.32 are identical or different and have the general or preferred meanings indicated for the general formulae (N2a) and (N2b), [0295] m is either 0 or 1, [0296] and, when m=1, [0297] A is oxygen, sulphur, C(C.sub.1-C.sub.10-alkyl).sub.2, C(C.sub.1-C.sub.10-alkyl).sub.2-C(C.sub.1-C.sub.10-alkyl).sub.2-, C(C.sub.1-C.sub.10-alkyl)=C(C.sub.1-C.sub.10-alkyl)- or N(C.sub.1-C.sub.10-alkyl).
[0298] Very particular preference is given to catalysts of the general formulae (N2a) or (N2b) having a general structural unit (N1) in which [0299] M is ruthenium, [0300] X.sup.1 and X.sup.2 are both chlorine, [0301] n is 0, 1 or 2 in the general formula (N2a) or [0302] n is 1 in the general formula (N2b) [0303] L.sup.1 is an imidazoline or imidazolidine ligand of one of the formulae (IIIa) to (IIIu), [0304] L.sup.2 is a sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine radical, an imidazolidine radical of one of the formulae (XIIa) to (XIIf) or a phosphine ligand, in particular PPh.sub.3, P(p-Tol).sub.3, P(o-Tol).sub.3, PPh(CH.sub.3).sub.2, P(CF.sub.3).sub.3, P(p-FC.sub.6H.sub.4).sub.3. P(p-CF.sub.3C.sub.6H.sub.4).sub.3, P(C.sub.6H.sub.4SO.sub.3Na).sub.3, P(CH.sub.2C.sub.6H.sub.4SO.sub.3Na).sub.3, P(isopropyl).sub.3, P(CHCH.sub.3(CH.sub.2CH.sub.3)).sub.3, P(cyclopentyl).sub.3, P(cyclohexyl).sub.3, P(neopentyl).sub.3 and P(neophenyl).sub.3, [0305] R.sup.25-R.sup.32 have the general or preferred meanings indicated for the general formulae (N2a) and (N2b), [0306] m is either 0 or 1 [0307] and, when m=1, [0308] A is oxygen, sulphur, C(C.sub.1-C.sub.10-alkyl).sub.2, C(C.sub.1-C.sub.10-alkyl).sub.2-C(C.sub.1-C.sub.10-alkyl).sub.2-, C(C.sub.1-C.sub.10-alkyl)C(C.sub.1-C.sub.10-alkyl)- or N(C.sub.1-C.sub.10-alkyl).
[0309] When R.sup.25 is bridged to another ligand of the catalyst of the formula N, this results, for example for the catalysts of the general formulae (N2a) and (N2b), in the following structures of the general formulae (N13a) and (N13b)
##STR00031##
where [0310] Y.sup.1 is oxygen, sulphur, NR.sup.41 or PR.sup.41, where R.sup.41 has the meanings indicated below, [0311] R.sup.40 and R.sup.41 are identical or different and are each alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl which may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, [0312] p is 0 or 1 and [0313] Y.sup.2 when p=1 is (CH.sub.2).sub.r where r=1, 2 or 3, C(O)CH.sub.2, C(O), NCH, N(H)C(O) or, as an alternative, the entire structural unit Y.sup.1 (R.sup.4)(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 have the same meanings as in general formulae (N2a) and (N2b).
[0314] As examples of catalysts of the formula (N), mention is made of the following structures:
##STR00032## ##STR00033##
Step a) of the Process According to the Present Invention:
[0315] The preparation of the novel catalyst composition in step a) of the present process is performed at an appropriate temperature. The choice of the temperature is influenced by the nature of the co-catalyst and the boiling temperature thereof. Typically this preparation step a) is performed at a temperature in the range of from 20 C. to 160 C., preferably in the range of from 20 C. to 80 C. The suitable time for the catalyst pretreatment using vinyl-containing substance ranges from about 1 minute to 48 hours.
[0316] The ratio of the transition metal catalyst to the co-catalyst is 1:(20-550), preferably 1:(20-500), more preferably 1:(25-475), even more preferably 1:(25-450) and most preferably 1:(30-450).
[0317] In a preferred embodiment the molar ratio of the complex catalyst to the co-catalyst in a range of from 1:(20 to below 100), preferably 1:(25 to 99.5), more preferably 1:(30 to 99), even more preferably 1:(35 to 98.5) and most preferably 1:(40 to 70).
[0318] The preparation of the novel catalyst composition can be carried out in the presence or absence of a suitable solvent which does not deactivate the catalyst used and also does not have an adverse effect on the hydrogenation in any other way. Preferably an organic solvent is used to dissolve the complex catalyst. More preferred solvents include, but are not restricted to, dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane, cyclohexane and chlorobenzene. The particularly preferred solvents are chlorobenzene and methyl ethyl ketone. Typically the vinyl compound is added to the solution of the complex catalyst.
[0319] The formation of the novel catalyst composition is performed before hydrogen is brought into the reaction system.
Step b) of the Process According to the Present Invention:
[0320] Thereafter the hydrogenation of the nitrile rubber is carried out by bringing the nitrile rubber into contact with hydrogen and the catalyst composition formed in step a) of the present process.
[0321] The hydrogenation is preferably carried out at a temperature in the range of from 60 C. to 200 C., preferably from 80 C. to 180 C., most preferably from 100 C. to 160 C. and at a hydrogen pressure in the range of 0.5 MPa to 35 MPa, more preferably of 3.0 MPa to 10 MPa.
[0322] Preferably, the hydrogenation time of the nitrile rubber is from 10 minutes to 24 hours, preferably from 15 minutes to 20 hours, more preferably from 30 minutes to 12 hours, even more preferably from 1 hour to 8 hours and most preferably from 1 hour to 4 hours.
[0323] The amount of the catalyst composition which is present in the hydrogenation step b) based on the nitrile rubber can be chosen in a broad range, preferably so that from 1 to 1000 ppm of ruthenium or osmium, preferably from 2 to 500 ppm, in particular from 5 to 250 ppm, are present based on the nitrile rubber used.
[0324] In an alternative embodiment of the present process it is possible to perform a metathesis reaction prior to the preparation of the novel catalyst composition and the subsequent hydrogenation. Such alternative process (hereinafter also referred to as tandem process) comprises performing a metathesis step before the above described steps a) and b).
[0325] This means that such alternative process comprises firstly subjecting a nitrile rubber to a molecular weight degradation in a metathesis reaction comprising contacting the nitrile rubber in the absence or presence of a co-olefin with a complex catalyst based on ruthenium or osmium as central metal and bearing at least one ligand which is bound to the ruthenium or osmium central metal in a carbene-like fashion, then [0326] a) contacting the complex catalyst which is present in the reaction mixture obtained after the metathesis reaction with at least one co-catalyst having at least one vinyl group in a molar ratio of the complex catalyst to the co-catalyst in the range of 1:(20-550) to form a catalyst composition and thereafter [0327] b) hydrogenating the nitrile rubber in the presence of the catalyst composition.
[0328] In a preferred embodiment of this alternative process the molar ratio of the complex catalyst to the co-catalyst in a range of from 1:(20 to below 100), preferably 1:(25 to 99.5), more preferably 1:(30 to 99), even more preferably 1:(35 to 98.5) and most preferably 1:(40 to 70).
Metathesis Step a) of the Tandem Method:
[0329] The NBR metathesis as first step of the tandem method can be carried out in the absence or presence of a co-olefin.
[0330] This co-olefin is preferably a straight-chain or branched C.sub.2-C.sub.16-olefin. Suitable co-olefins are, for example, ethylene, propylene, isobutene, styrene, 1-hexene and 1-octene. Particular preference is given to using I-hexene or 1-octene.
[0331] In the alternative the following functionalized co-olefins can be used:
##STR00034##
[0332] If the co-olefin is liquid (as in the case of, for example, 1-hexene), the amount of co-olefin is preferably in the range 0.2-20% by weight, based on the nitrile rubber used. If the co-olefin is a gas, as in the case of, for example, ethylene, the amount of co-olefin is selected so that a pressure in the range 110.sup.5 Pa-110.sup.7 Pa, preferably a pressure in the range from 5.210.sup.5 Pa to 410.sup.6 Pa, is established in the reaction vessel at room temperature.
[0333] The metathesis reaction can be carried out in a suitable solvent which does not deactivate the catalyst used and also does not have an adverse effect on the reaction in any other way. Preferred solvents include, but are not restricted to, dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane, cyclohexane and chlorobenzene. The particularly preferred solvent is chlorobenzene. In some cases when the co-olefin itself can function as solvent, e.g. in the case of 1-hexene, the addition of a further additional solvent can be dispensed with.
[0334] The amount of catalyst based on the nitrile rubber used in the metathesis step of the tandem method according to the invention depends on the nature and the catalytic activity of the specific complex 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.
[0335] The concentration of the nitrile rubber used in the reaction mixture of the metathesis is not critical, but it should naturally be ensured that the reaction is not adversely affected by an excessively high viscosity of the reaction mixture and the associated mixing problems. The concentration of NBR in the reaction mixture is preferably in the range from 1 to 25% by weight, particularly preferably in the range from 5 to 20% by weight, based on the total reaction mixture.
[0336] 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 80 C.
[0337] The metathesis reaction time depends on a number of factors, for example on the type of NBR, the type of catalyst, the catalyst concentration and co-olefin concentration used and the reaction temperature. The progress of the cross-metathesis can be monitored by standard analytical methods, e.g. by GPC measurements or by determination of the viscosity. The reaction is typically allowed to be conducted for about 15 minutes to six hours under normal conditions. It is also possible to perform the metathesis reaction until the reaction ceases by deactivation of the catalyst.
[0338] After such metathesis step, the reaction mixture containing the metathesis catalyst is taken and brought into contact with the co-catalyst having the general formula (1) or (2). Typically the co-catalyst is simply added to the reaction mixture, preferably in the same solvent in which the metathesis was performed.
[0339] The appropriate temperature for the preparation of the novel catalyst composition after the metathesis in the tandem method can also be chosen in the range of from 20 C. to 160 C., preferably in the range of from 20 C. to 80 C. The suitable time for the preparation of the catalyst composition for the subsequent hydrogenation reaction in such tandem reaction using the vinyl-group containing co-catalyst ranges from about 5 minutes to 48 hours. The preferred time ranges from 10 minutes to 12 hours.
[0340] The subsequent hydrogenation of the nitrile rubber can be carried in the same manner as described above for the hydrogenation reaction.
[0341] One major advantage of the present invention resides in the fact that the catalyst composition used is very active, so that the catalyst residue in the final HNBR products can be low enough to make the catalyst metal removal or recycle step alleviated or even unnecessary. However, to the extent desired, the catalysts used during the process of the present invention may be removed. Such removal can be performed e.g. by using ion-exchange resins as described in EP-A-2 072 532 A1 and EP-A-2 072 533 A1. The reaction mixture obtained after the completion of the hydrogenation reaction can be taken and treated with an ion-exchange resin at e.g. 100 C. for 48 hours under nitrogen and then be precipitated in cold methanol
Nitrile Rubber:
[0342] The nitrile rubber used in the process of the present invention is a copolymer or terpolymer of at least one , -unsaturated nitrile, at least one conjugated diene and, if desired, one or more further copolymerizable monomers.
[0343] The conjugated diene can be of any nature. Preference is given to using (C.sub.4-C.sub.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.
[0344] As ,-unsaturated nitrile, it is possible to use any known ,-unsaturated nitrile, preferably a (C.sub.3-C.sub.5) ,-unsaturated nitrile such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particular preference is given to acrylonitrile.
[0345] A particularly preferred nitrile rubber used in the process of this invention is thus a copolymer having repeating units derived from acrylonitrile and 1,3-butadiene.
[0346] Apart from the conjugated diene and the ,-unsaturated nitrile, the hydrogenated nitrile rubber may comprise repeating units of one or more further copolymerizable monomers known in the art, e.g. ,-unsaturated (preferably mono-unsaturated) monocarboxylic acids, their esters and amides, ,-unsaturated (preferably mono-unsaturated) dicarboxylic acids, their mono-oder diesters, as well as the respective anhydrides or amides of said ,-unsaturated dicarboxylic acids.
[0347] As ,-unsaturated monocarboxylic acids acrylic acid and methacrylic acid are preferably used.
[0348] Esters of ,-unsaturated monocarboxylic acids may also be used, in particular alkyl esters, alkoxyalkyl esters, aryl esters, cycloalkylesters, cyanoalkyl esters, hydroxyalkyl esters, and fluoroalkyl esters.
[0349] As alkyl esters C.sub.1-C.sub.18 alkyl esters of the ,-unsaturated monocarboxylic acids are preferably used, more preferably C.sub.1-C.sub.18 alkyl esters of acrylic acid or methacrylic acid, such as methylacrylate, ethylacrylate, propylacrylate, n-butylacrylate, tert.-butylacrylate, 2-ethyl-hexylacrylate, n-dodecylacrylate, methylmethacrylate, ethylmethacrylate, propylmethacrylate, n-butylmethacrylate, tert.-butylmethacrylate and 2-ethylhexyl-methacrylate.
[0350] As alkoxyalkyl esters C.sub.2-C.sub.18 alkoxyalkyl esters of ,-unsaturated monocarboxylic acids are preferably used, more preferably alkoxyalkylester of acrylic acid or methacrylic acid such as methoxy methyl(meth)acrylate, methoxy ethyl(meth)acrylate, ethoxyethyl(meth)acrylate and methoxyethyl(meth)acrylate.
[0351] It is also possible to use aryl esters, preferably C.sub.6-C.sub.14-aryl-, more preferably C.sub.6-C.sub.10-aryl esters and most preferably the aforementioned aryl esters of acrylates and methacrylates.
[0352] In another embodiment cycloalkyl esters, preferably C.sub.5-C.sub.12-, more preferably C.sub.6-C.sub.12-cyclo-alkyl and most preferably the aforementioned cycloalkyl acrylates and methacrylates are used.
[0353] It is also possible to use cyanoalkyl esters, in particular cyanoalkyl acrylates or cyanoalkyl methacrylates, with 2 to 12 C atoms in the cyanoalkyl group, preferably -cyanoethyl acrylate, -cyanoethyl acrylate or cyanobutyl methacrylate.
[0354] In another embodiment hydroxyalkyl esters are used, in particular hydroxyalkyl acrylates and hydroxyalkyl methacrylates with 1 to 12 C-atoms in the hydroxylalkyl group, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or 3-hydroxypropyl acrylate.
[0355] It is also possible to use fluorobenzyl esters, in particular fluorobenzyl acrylates or fluorobenzyl methacrylates, preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate. Substituted amino group containing acrylates and methacrylates may also be used like dimethylaminomethyl acrylate and diethylaminoethylacrylate.
[0356] Various other esters of the ,-unsaturated carboxylic acids may also be used, like e.g. poly-ethyleneglycol(meth)acrylate, polypropyleneglycole(meth)acrylate, glycidyl(meth)acrylate, epoxy(meth)acrylate, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxymethyl)acrylamide or urethane(meth)acrylate.
[0357] It is also possible to use mixture of all aforementioned esters of ,-unsaturated carboxylic acids.
[0358] Furthon ,-unsaturated dicarboxylic acids may be used, preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.
[0359] In another embodiment anhydrides of ,-unsaturated dicarboxylic acids are used, preferably maleic anhydride, itaconic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
[0360] In a further embodiment mono- or diesters of ,-unsaturated dicarboxylic acid can be used. Suitable alkyl esters are e.g. C.sub.1-C.sub.10-alkyl, preferably ethyl-, n-propyl-, iso-propyl, n-butyl-, tert.-butyl, n-pentyl-oder n-hexyl mono- or diesters. Suitable alkoxyalkyl esters are e.g. C.sub.2-C.sub.12 alkoxyalkyl-, preferably C.sub.3-C.sub.8-alkoxyalkyl mono- or diesters. Suitable hydroxyalkyl esters are e.g. C.sub.1-C.sub.12 hydroxyalkyl-, preferably C.sub.2-C.sub.8-hydroxyalkyl mono- or diesters. Suitable cycloalkyl esters are e.g. C.sub.5-C.sub.12-cycloalkyl-, preferably C.sub.6-C.sub.12-cycloalkyl mono- or diesters. Suitable alkylcycloalkyl esters are e.g. C.sub.6-C.sub.12-alkylcycloalkyl-, preferably C.sub.7-C.sub.10-alkylcycloalkyl mono- or diesters. Suitable aryl esters are e.g. C.sub.6-C.sub.14-aryl, preferably C.sub.6-C.sub.10-aryl mono- or diesters.
[0361] Explicit examples of the ,-ethylenically unsaturated dicarboxylic acid monoester monomers include [0362] maleic acid monoalkyl esters, preferably monomethyl maleate, monoethyl maleate, monopropyl maleate, and mono n-butyl maleate; [0363] maleic acid monocycloalkyl esters, preferably monocyclopentyl maleate, monocyclohexyl maleate, and monocycloheptyl maleate; [0364] maleic acid monoalkylcycloalkyl esters, preferably monomethylcyclopentyl maleate, and monoethylcyclohexyl maleate; [0365] maleic acid monoaryl ester, preferably monophenyl maleate; [0366] maleic acid mono benzyl ester, preferably monobenzyl maleate; [0367] fumaric acid monoalkyl esters, preferably monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, and mono n-butyl fumarate; [0368] fumaric acid monocycloalkyl esters, preferably monocyclopentyl fumarate, monocyclohexyl fumarate, and monocycloheptyl fumarate; [0369] fumaric acid monoalkylcycloalkyl esters, preferably monomethylcyclopentyl fumarate, and monoethylcyclohexyl fumarate; [0370] fumaric acid monoaryl ester, preferably monophenyl fumarate; [0371] fumaric acid mono benzyl ester, preferably monobenzyl fumarate; [0372] citraconic acid monoalkyl esters, preferably monomethyl citraconate, monoethyl citraconate, monopropyl citraconate, and mono n-butyl citraconate; [0373] citraconic acid monocycloalkyl esters, preferably monocyclopentyl citraconate, monocyclohexyl citraconate, and monocycloheptyl citraconate; [0374] citraconic acid monoalkylcycloalkyl esters, preferably monomethylcyclopentyl citraconate, and monoethylcyclohexyl citraconate; [0375] citraconic acid mono aryl ester, preferably monophenyl citraconate; [0376] citraconic acid mono benzyl ester, preferably monobenzyl citraconate; [0377] itaconic acid mono alkyl esters, preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate, and mono n-butyl itaconate; [0378] itaconic acid monocycloalkyl esters, preferably monocyclopentyl itaconate, monocyclohexyl itaconate, and monocycloheptyl itaconate; [0379] itaconic acid monoalkylcycloalkyl esters, preferably monomethylcyclopentyl itaconate, and monoethylcyclohexyl itaconate; [0380] itaconic acid mono aryl ester, preferably monophenyl itaconate; [0381] itaconic acid mono benzyl ester, preferably monobenzyl itaconate.
[0382] As ,-ethylenically unsaturated dicarboxylic acid diester monomers the analogous diesters based on the above explicitly mentioned mono ester monomers may be used, wherein, however, the two organic groups linked to the CO group via the oxygen atom may be identical or different.
[0383] As further termonomers vinyl aromatic monomers like sterol, -methylstyryl and vinylpyridine, as well as non-conjugated dienes like 4-cyanocyclohexene and 4-vinylcyclohexene, as well as alkines like 1- or 2-butine may be used.
[0384] Particularly preferred are termonomers chosen from the below depicted formulae:
##STR00035##
where [0385] R.sup.1 is hydrogen or methyl group, and [0386] R.sup.2, R.sup.3, R.sup.4, R.sup.5 are identical or different and may represent H, C.sub.1-C.sub.12 alkyl, cycloalkyl, alkoxyalkyl, hydroxyalkyl, expoxyalkyl, aryl, heteroaryl.
[0387] The proportions of conjugated diene and ,-unsaturated nitrile in the NBR polymers to be used can vary within wide ranges. The proportion of the conjugated diene or the sum of 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 ,-unsaturated nitrile or the sum of , -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. In this case, corresponding proportions of the conjugated diene or dienes and/or the , -unsaturated nitrile or nitriles are replaced by proportions of the additional monomers, with the proportions of all monomers in each case adding up to 100% by weight.
[0388] The preparation of the nitrite rubbers by polymerization of the abovementioned monomers is adequately known to those skilled in the art and is comprehensively described in the literature. 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 Perbunan and Krynac grades of Lanxess Deutschland GmbH.
[0389] The nitrile rubbers to be hydrogenated have a Mooney viscosity (ML1+4 at 100 C.), measured in accordance with ASTM standard D 1646, in the range from 1 to 75, and preferably from 5 to 50. The weight average molecular weight Mw is in the range 2,000-500,000 g/mol, preferably in the range 20,000-400,000. The nitrile rubbers have a polydispersity PDI=Mw/Mn, where Mw is the weight average molecular weight and Mn is the number average molecular weight, in the range 1-5. The determination of the Mooney viscosity is carried out in accordance with ASTM Standard D 1646.
[0390] As the metathesis activity of the ruthenium- or osmium-based catalyst used to prepare the catalyst composition according to this invention is not existing in the catalyst composition of the present invention the molecular weight of the hydrogenated nitrile rubber obtained after the hydrogenation is comparable to the original NBR feedstock and not further reduced during hydrogenation.
[0391] Hence, a hydrogenated nitrile rubber with a weight average molecular weight Mw in the range 2,000-500,000 g/mol, preferably in the range 20,000-400,000 is obtained. The Mooney viscosity (ML1+4 at 100 C.), measured in accordance with ASTM standard D 1646, of the hydrogenated nitrile rubbers is in the range from 1 to 150, preferably from 10 to 100. The polydispersity PDI=Mw/Mn, where Mw is the weight average molecular weight and Mn is the number average molecular weight, in the range 1-5 and preferably in the range 1.5-4.
[0392] For the purposes of the present invention, hydrogenation is a reaction of the double bonds present in the starting nitrile rubber to an extent of at least 50%, preferably 70-100%, more preferably 80-100%; even more preferably 90-100%
[0393] In the tandem method, the nitrile rubber is firstly degraded using at least one ruthenium- or osmium-based catalyst in the absence or in the presence of a co-olefin. The vinyl compound of general formula (1) is either added when the metathesis reaction has ceased or gone to completion or added before in order to stop the metathesis at a certain degree. Thereafter, the hydrogenation can be carried out to afford hydrogenated nitrile rubber by introducing hydrogen gas. In the sequence of metathesis, catalyst composition formation and hydrogenation, the metathesis degree can be fully controlled and the molecular weight of the final hydrogenated nitrile rubber is adjustable as desired. The nitrile rubbers subjected to metathesis in the tandem method may typically have a Mooney viscosity (ML1+4 at 100 C.), measured in accordance with ASTM standard D 1646, in the range from 30 to 75, and preferably from 30 to 50. The weight average molecular weight Mw is in the range 150,000-500,000 g/mol, preferably in the range 180,000-400,000. These nitrile rubbers have a polydispersity PDI=Mw/Mn, where Mw is the weight average molecular weight and Mn is the number average molecular weight, in the range 2 to 6. The determination of the Mooney viscosity is carried out in accordance with ASTM Standard D 1646.
[0394] The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Catalysts Used in the Examples:
[0395] Catalysts (1) to (3) were purchased from Sigma Aldrich or Strem Chemicals Inc. Catalyst (4) was purchased from Xian Kaili Co. (China). The structures of these catalysts are shown below, wherein Mes means mesityl (2,4,6-trimethylphenyl) and Cy means cyclohexyl:
##STR00036##
[0396] These catalysts have the following molecular weights:
TABLE-US-00001 molecular weight catalyst [g/mol] (1) 822.96 (2) 848.97 (3) 885.55 (4) 925.22
Nitrile Butadiene Rubbers Used in the Examples:
[0397] The nitrile butadiene rubbers used in the examples had the properties outlined in Table 1.
TABLE-US-00002 TABLE 1 Nitrile Butadiene Rubbers (NBR) used (ACN means acrylonitrile) Mooney viscosity ACN content ML(1 + 4) NBR % by weight 100 C. Mn Mw PDI Perbunan 34 29 77,101 255,395 3.31 3431 VP NBR-5 34 34 73,711 243,671 3.31 NBR-6 34 34 74,698 249,935 3.35 NBR-7 34 34 70,674 251,292 3.56
[0398] Vinyl ethyl ether (VEE) was purchased from Sigma-Aldrich.
Analytical Tests:
GPC Test:
[0399] The apparent molecular weight Mn and Mw were determined by a Waters GPC system equipped with a Waters 1515 high performance liquid chromatography pump, a Waters 717plus autosampler, a PL gel 10 m mixed B column and a Waters 2414 RI detector. The GPC test was carried out at 40 C. at 1 mL/min of flow rate with THF as the eluent, and the GPC column was calibrated with narrow PS standard samples.
FT-IR Test:
[0400] The spectrum of nitrile rubber before, during and after the hydrogenation reaction was recorded on a Perkin Elmer spectrum 100 FT-IR spectrometer. The solution of the nitrile butadiene rubber in MCB was cast onto a KBr disk and dried to form a film for the test. The hydrogenation conversion is determined by the FT-IR analysis according to the ASTM D 5670-95 method.
Abbreviations:
[0401] phr: per hundred rubber (weight)
[0402] rpm: revolution per minute
[0403] Mn: number-average molecular weight
[0404] Mw: weight-average molecular weight
[0405] PDI: polydispersity index, defined as Mw/Mn
[0406] PPh.sub.3: triphenylphosphine
[0407] MCB: monochlorobenzene
[0408] VEE: vinyl ethyl ether
[0409] RT: room temperature (22+/2 C.)
Example 1: (Comparison Example, Using Catalyst (4))
[0410] A solution of 18 g Perbunan 3431VP in 282 g MCB (Perbunan 3431VP concentration of 6 wt %) was bubbled with nitrogen in a 600 mL Parr autoclave for 30 minutes, and then heated to 120 C. Wilkinson's catalyst (15 mg) and PPh.sub.3 (18 mg) was dissolved in another 22 g of degassed MCB and then added into the reactor. Hydrogenation was conducted under 4.137 MPa of hydrogen pressure and 800 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. After 5 hours of hydrogenation, the hydrogenation degree reached 90.3%, the reactor was cooled to room temperature and the pressure was released. The final molecular weights and PDI were: Mn=76,286, Mw=260,572, PDI=3.42.
Examples 2: (Inventive Example; Perbunan 3431VP; Catalyst (1); VEE as Co-Catalyst)
[0411] Catalyst (1) (9 mg) was dissolved in 22 g degassed MCB in a flask. Vinyl ethyl ether (100 L) was injected into the flask and the solution was stirred for 12 hours. A solution of 18 g Perbunan 3431VP in 282 g MCB (Perbunan 3431VP concentration of 6 wt %) was bubbled with nitrogen in a 600 mL Parr autoclave for 30 minutes, and then heated to 120 C. The catalyst solution in the flask was transferred into the reactor via syringe. Hydrogenation was conducted under 4.137 Mpa of hydrogen pressure and 800 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation, degree. After 3 hours of hydrogenation, the hydrogenation degree reached 93%. The final molecular weights and the PDI were: Mn=75,844, Mw=223,863, PDI=2.95.
Example 3: (Inventive Example; Perbunan 3431VP; Catalyst (2); VEE as Co-Catalyst)
[0412] All the conditions and operation were the same as in Example 5 except that Catalyst (2) was used (18 mg). The hydrogenation degree at 1 hour was 99%. The final molecular weights and the PDI were: Mn=71,762, Mw=221,604, PDI=3.09.
Example 4: (Inventive Example; Perbunan 3431VP; Catalyst (2); VEE as Co-Catalyst)
[0413] All the conditions and operation were the same as in Example 5 except that Catalyst (2) was used (9 mg). The hydrogenation degree at 2 hours was 95%. The final molecular weights and the PDI were: Mn=71,274, Mw=208,575, PDI=2.93.
Example 5: (Inventive Example; Perbunan 3431VP; Catalyst (3); VEE as Co-Catalyst)
[0414] All the conditions and operation were the same as in Example 5 except that Catalyst (3) was used (9 mg). The hydrogenation degree at 3 hours was 98%. The final molecular weights and the PDI were: Mn=88,070, Mw=267,466, PDI=3.04.
[0415] The conditions and the results for Example 1-5 are shown in Table 2. In such Table 2 the comparative examples are marked with an asterisk. Furtheron the abbreviation P3431VP stands for Perbunan 3431VP. Only for comparison reasons the number and weight average molecular weights as well as PDI has been included at the bottom of Table 2 with regard to the starting nitrile rubber then subjected to hydrogenation in Examples 1 to 5.
TABLE-US-00003 TABLE 2 Examples 1 to 5 (for all examples: hydrogenation temperature: 120 C. and pressure: 4.137 MPa) MCB NBR (used to Molar Perbunan dissolve ratio co- Time of 3431 VP * NBR + catalyst co-catalyst catalyst pre-treat- hydrogenation amount catalyst) amount amount to ment time degree Mn Mw Ex [g] [g] no. [mg] [mmol] type [mg] [mmol] catalyst [h] [h] [%] [g/mol] [g/mol] PDI HNBR 1* 18 282 + 22 (4) 15 0.0162 PPh.sub.3 18 0 5 90.3 76,286 260,572 3.42 2 18 282 + 22 (1) 18 0.0219 VEE 75 1.04 47.5 12 3 93 75,844 223,863 2.95 3 18 282 + 22 (2) 18 0.0212 VEE 75 1.04 49.1 12 1 99 71,762 221,604 3.09 4 18 282 + 22 (2) 9 0.0106 VEE 75 1.04 98.1 12 2 95 71,274 208,575 2.93 5 18 282 + 22 (3) 9 0.0102 VEE 75 1.04 102.3 12 3 98 88,070 267,466 3.04 * Perbunan 3431 VP 77,101 255,395 3.31
Example 6; (Comparison Example: NBR-5; Catalyst (2); First Metathesis, No Additional Treatment with a Co-Catalyst, then Hydrogenation)
[0416] A solution of 270 g NBR-5 in 4,350 g MCB was bubbled with nitrogen in a 10 L Parr autoclave for 30 minutes. 11.1 g 1-hexene dissolved in 50 g degassed MCB were added into the reactor and the mixture was stirred for 1 hour. Catalyst (2) (135 mg) was dissolved in another 100 g of degassed MCB, added into the reactor and metathesis was conducted for 1 hour. Then the reactor was heated to 140C and hydrogenation was conducted under 8.4 MPa of hydrogen pressure and 600 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. After 2 hours of hydrogenation, the hydrogenation degree reached 99.5%. The final molecular weights and the PDI were: Mn=4,648, Mw=9,952, PDI=2.14.
Example 7: (Inventive; NBR-6; Catalyst (2); Treatment with VEE as Co-Catalyst; Thereafter Hydrogenation)
[0417] Catalyst (2) (135 mg) was dissolved in 100 g degassed MCB in a flask. Vinyl ethyl ether (0.75 g) was injected into the flask and the solution was stirred under nitrogen for 12 hours at room temperature. A solution of 270 g NBR-6 in 4,350 g MCB was bubbled with nitrogen in 10 L Parr autoclave for 30 minutes, and then heated to 140 C. The catalyst solution in the flask was transferred into the reactor and 11.1 g 1-hexene dissolved in 50 g degassed MCB were added into the reactor. Hydrogenation was conducted under 8.4 MPa of hydrogen pressure and 600 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. After 3 hours of hydrogenation, the hydrogenation degree reached 99.4%. The final molecular weights and the PDI were: Mn=92,462, Mw=258,405, PDI=2.79.
Examples 8-10: (Inventive, NBR-6, Catalyst (2); Metathesis, Treatment with VEE as Co-Catalyst and Subsequent Hydrogenation)
[0418] A solution of 560 g NBR-6 in 4,516 g MCB (NBR-6 concentration of 11 wt % was bubbled with nitrogen in a 10 L Parr autoclave for 30 minutes. 23.1 g 1-hexene dissolved in 50 mL degassed MCB were added into the reactor and the mixture was stirred for 1 hour. Catalyst (2) (280 mg) was dissolved in 100 g of degassed MCB at room temperature and then added into the reactor.
[0419] The metathesis was allowed to conduct for 15 min at room temperature. Then 1.55 g of VEE dissolved in 200 g degassed MCB was added into the autoclave. After stirring for 1 hour, a sample was taken from the reactor for GPC analysis. The temperature of the autoclave was elevated to 140 C. Then the hydrogen gas was introduced into the autoclave. Hydrogenation was conducted under 8.4 MPa of hydrogen pressure and 600 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. The molecular weights and the PDI after the addition of VEE are given in the following Table 4. After 2 hours of hydrogenation, the hydrogenation degree reached 99.8% and 99.7% respectively as shown in Table 4. The final molecular weights and the PDI are given in the following Table 3.
Example 11: (Comparison Example; NBR-7; Using Catalyst (2) without Pre-Treatment)
[0420] Catalyst (2) (363 mg) was dissolved in 100 g degassed MCB in a cylinder. A solution of 518 g NBR-7 dissolved in MCB (a solid concentration of 13 wt % of NBR solution) was bubbled with nitrogen in a 10 L autoclave for 30 minutes, and then heated to 140 C. The catalyst solution in the cylinder was pressured into the reactor with hydrogen gas. Hydrogenation was conducted under 8.4 MPa of hydrogen pressure and 600 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. After 4 hours of hydrogenation, the hydrogenation degree reached >99%. The final molecular weights and the PDI were: Mn=48,564, Mw=127,044, PDI=2.60.
Example 12: (Inventive Example; NBR-7; Catalyst (2); VEE as Co-Catalyst)
[0421] Catalyst (2) (259 mg) was dissolved in 100 g degassed MCB in a cylinder. Vinyl ethyl ether (1.41 g) was injected into the cylinder and the solution was stirred at room temperature for 1 hour. A solution of 518 g NBR-7 dissolved in MCB (a solid concentration of 13 wt % of NBR solution) was bubbled with nitrogen in a 10 L autoclave for 30 minutes, and then heated to 140 C. The pre-treated catalyst solution in the cylinder was pressured into the reactor with hydrogen gas. Hydrogenation was conducted under 8.4 Mpa of hydrogen pressure and 600 rpm of agitation speed. Samples were taken from the reactor at intervals for FT-IR analysis to determine the hydrogenation degree. After 4 hours of hydrogenation, the hydrogenation degree reached >99%. The final molecular weights and the PDI were: Mn=82,973, Mw=261,751, PDI=3.20.
[0422] The examples in this section show that HNBR can be prepared by hydrogenation of NBR in the presence of a catalyst composition which is obtained by contacting a metathesis catalyst with a specific co-catalyst wherein such contacting or pretreatment of the catalyst with the co-catalyst is conducted either separately (see Ex. 2-5 and Ex. 7) or following a metathesis reaction in-situ in the reaction mixture before the addition of hydrogen (see Ex. 8 to 10). The metathesis activity of the catalyst is controlled by contacting the catalyst with the co-catalyst and thereby preparing the catalyst composition according to the invention. Thus the molecular weight of the HNBR obtained by the hydrogenation using the catalyst composition according to the invention is comparable to the original NBR feedstock. This is clearly shown e.g. by Ex. 7 in which 1-hexene which is known as typical co-olefine to enhance metathesis reactions was added to the hydrogenation reaction, but nevertheless no methathesis occurred and the average molecular weights Mn and Mw of the HNBR obtained are nearly identical to the respective values of the starting NBR. Further, the non-inventive Ex. 11* and the inventive Ex. 12 show that, with the catalyst composition which is obtained by contacting a metathesis catalyst with a specific co-catalyst, the same hydrogenation rate can be achieved by using lower loading of the metathesis catalyst (Ex. 12: 259 mg Grubbs II catalyst vs. Ex 11*: 363 mg Grubbs II catalyst). Therefore, besides controlling the metathesis activity of the metathesis catalyst, it is surprisingly found that, by using such catalyst composition, the hydrogenation activity of the catalyst also be promoted/improved.
TABLE-US-00004 TABLE 3 Reaction conditions and results of Examples 6 to 10 (1-hexene as co-catalyst for metathesis: 4.0 phr, hydrogenation pressure: 8.4 MPa, hydrogenation temperature: 140 C., hydrogenation time: 2 h) MCB to solve Pre- NBR, treat- catalyst Step 1: Molar ment and co- Meta- Co-catalyst for ratio co- Cata- Hydroge- NBR catalyst Catalyst (2) thesis pretreating the catalyst catalyst lyst nation amount amount amount time amount to time Mn Mw degree Ex [g] [g] [mg] [mmol] [h] type [g] [mmol] catalyst [h] [g/mol] [g/mol] PDI [%] HNBR 6* 270 4500 135 0.1590 1 after 14,360 34,287 2.39 0 NBR-5 metathesis after 4,648 9,952 2.14 99.5 hydrogenation 7 270 4500 135 0.1590 VEE 0.75 10.34 65 12 after 74,698 258,405 2.79 99.4 NBR-6 hydrogenation 8 560 4666 280 0.3298 0.25 VEE 1.55 21.49 65 1 after 54,576 147,365 2.70 0 NBR-6 metathesis and VEE addition after 61,976 168,310 2.72 99.8 hydrogenation 9 560 4666 280 0.3298 0.25 VEE 2.38 33.01 100 1 after 56,499 138,269 2.45 0 NBR-6 metathesis and VEE addition after 62,402 155,444 2.49 99.7 hydrogenation 10 560 4666 280 0.3298 0.25 VEE 0.95 13.17 40 1 after 56,127 137,659 2.45 0 NBR-6 metathesis and VEE addition after 64,608 163,139 2.52 99.7 hydrogenation 11* 518 3567 363 0.4276 after 48,564 127,044 2.60 >99 NBR-7 hydrogenation 12 518 3567 259 0.3051 64 1 after 82,973 261,751 3.20 >99 NBR-7 hydrogenation NBR NBR-5 73,711 243,671 3.31 NBR-6 74,698 249,935 3.35 NBR-7 70,674 255,292 3.56