Catalyst compositions and their use for hydrogenation of nitrile rubber
View Patent ↗This invention relates to novel catalyst compositions based on Ruthenium- or Osmium-based complex catalysts of the Grubbs-Hoveyda, Grela or Zhan type and specific co-catalysts comprising at least one vinyl group, pref. ethyl vinyl ether, and to a process for selectively hydrogenating nitrile rubbers in the presence of such catalyst compositions, preferably with a preceding metathesis step using the same complex catalyst as in the hydrogenation step.
1. A selective hydrogenation of nitrile rubber comprising selectively hydrogenating nitrile rubber in the presence of a catalyst composition obtained by contacting a complex catalyst with at least one co-catalyst in a molar ratio of the complex catalyst to the co-catalyst of 1:30 to 1:100, wherein:
the complex catalyst has the general formula (A)
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure,
R 1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen or an organic or inorganic substituent,
R 6 is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R, —S(═O)R, or a group containing either a C═O or a C═S structural element adjacent to a carbon atom which is bound to Y,
n is 0 or 1,
wherein if n=1, then the element shall mean that Y and (E) n are linked either by a single bond or by a double bond, wherein
(i) if Y and (E) n are linked by a single bond, then
Y is oxygen (O), sulfur (S), N—R or P—R, and
E is CH 2 , or
(ii) if Y and (E) n are linked by a double bond, then
Y is N or P, and
E is CH, and
wherein if n=0, then
Y is oxygen (O), sulfur (S), N—R or P—R, and is directly linked by a single bond to the phenyl moiety depicted above in formula (A), and
wherein in all above occurrences of general formula (A), R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; and
wherein the co-catalyst must contain at least one vinyl group, and has the general formula (1)
CH 2 ═CRR′ (1)
in which R and R′ are identical or different and in the co-catalyst shall mean hydrogen, wherein R and R′ must not both represent hydrogen, or
OR 1 wherein R 1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(═O)(R 2 ), —C(═O)N(R 2 ) 2 , —[(CH 2 ) n —X] m R 2 , —[(CH 2 ) n —X] m —CH═CH 2 , or —(CH 2 ) p —C(R 3 ) 2 R 4 , wherein
X is identical or different and means oxygen (O) or NR 2
R 2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,
R 3 are identical or different and represent C 1 -C 8 alkyl or —(CH 2 ) n′ —O—CH═CH 2 ,
R 4 represents (CH 2 ) p′ —O—CH═CH 2 ,
n is 1 to 5,
m is 1 to 10,
p is 0 to 5, or
where in the alternative, if R and R′ both represent a group OR 1 , both R 1 may be linked to each other and together represent a divalent group —(C(R 2 ) 2 ) q —with q being 2, 3 or 4 and R 2 being identical or different and having the above defined meanings, or
SR 5 , SOR 5 , SO 2 R 5 wherein R 5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or
N(R 6 R 7 ), P(R 6 R 7 ) wherein R 6 and R 7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)(R 2 ), or where in the alternative R 6 and R 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, N—R 8 or P—R 8 wherein R 8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; or
P(═O)(OR 9 ) 2 in which R 9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl.
2. The selective hydrogenation according to claim 1 , wherein the complex catalyst is contacted with one co-catalyst of the general formula (1) in which R is hydrogen and R′ shall mean,
OR 1 wherein R 1 shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 6 -C 24 -heteroaryl, —C(═O)(R 2 ) 2 , —C(═O)N(R 2 ) 2 , —[(CH 2 ) n X] m R 2 , —[(CH 2 ) n X] m —CH═CH 2 , or —(CH 2 ) p —C(R 3 ) 2 R 4 1 ,
wherein
X is identical or different and is oxygen (O) or NR 2 ,
R 2 are identical or different and represent H, C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 3 -C 20 -heteroaryl,
R 3 are identical or different and represent C 1 -C 4 alkyl or —(CH 2 ) n —O—CH═CH 2 ,
R 4 represents (CH 2 ) p —O—CH═CH 2 ,
n is 1 to 4,
m is 1 to 5,
p is 0 to 5, or
SR 5 , SOR 5 , SO 2 R 5 wherein R 5 represents C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, or
N(R 6 R 7 ), P(R 6 R 7 ) wherein R 6 and R 7 are identical or different and shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, —C(═O)(R 2 ), or where in the alternative R 6 and R 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, N—R 8 or P—R 8 wherein R 8 shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, or
P(═O)(OR 9 ) 2 in which R 9 are identical or different and shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl.
3. The selective hydrogenation according to claim 1 , wherein the complex catalyst is contacted with one co-catalyst of the general formula (1) in which R and R′ are identical or different and shall mean
OR 1 wherein R 1 shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 6 -C 24 -heteroaryl, —C(═O)(R 2 ), —C(═O)N(R 2 ) 2 , —[(CH 2 ) n X] m R 2 , —[(CH 2 ) n X] m —CH═CH 2 , or —(CH 2 ) p —C(R 3 ) 2 R 4 ,
wherein
X is identical or different and oxygen (O) or NR 2 ,
R 2 are identical or different and represent H, C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 3 -C 20 -heteroaryl,
R 3 are identical or different and represent C 1 -C 4 alkyl or —(CH 2 ) n —O—CH═CH 2 ,
R 4 represents (CH 2 ) p —O—CH═CH 2 ,
n is 1 to 4,
m is 1 to 5,
p is 0 to 5,
where in the alternative, if R and R′ both represent a group OR 1 , both R 1 may be linked to each other and together represent a divalent group —(C(R 2 ) 2 ) q— with q being 2, 3 or 4, and R 2 being identical or different and having the above defined meanings, or
SR 5 , SOR 5 , SO 2 R 5 wherein R 5 represents C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, or
N(R 6 R 7 ), P(R 6 R 7 ) wherein R 6 and R 7 are identical or different and shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, —C(═O)(R 2 ), or where in the alternative R 6 and R 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, N—R 8 or P—R 8 wherein R 8 shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl, or
P(═O)(OR 9 ) 2 in which R 9 are identical or different and shall mean C 1 -C 16 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 6 -C 24 -heteroaryl.
4. The selective hydrogenation according to claim 1 , wherein the complex catalyst is contacted with one co-catalyst of the general formula (1) in which R is hydrogen and R′ represents
OR 1 wherein R 1 shall mean C 1 -C 6 -alkyl, C 5 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl, —C(═O)(R 2 ), —C(═O)N(R 2 ) 2 , —[(CH 2 ) n O] m R 2 , —[(CH 2 ) n O] m —CH═CH 2 , or —(CH 2 ) p —C(R 3 ) 2 R 4 ,
wherein
R 2 are identical or different and represent H, C 1 -C 6 -alkyl, C 5 -C 8 -cycloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl,
R 3 are identical or different and represent methyl, ethyl or —(CH 2 ) n —O—CH═CH 2 ,
R 4 represents (CH 2 ) p —O—CH═CH 2 ,
n is 1, or 2,
m is 1, 2, or 3, and
p is 0, 1, or 3.
5. The selective hydrogenation according to claim 1 , wherein the co-catalyst is selected from the group consisting of formulae (cocat-1) to (cocat-31) and (cocat-33) to (cocat-38):
6. The selective hydrogenation according to claim 1 , wherein the complex catalyst is selected from the group consisting of:
(i) catalysts of general formula (A1),
wherein M, L, X 1 , X 2 , R 2 , R 3 , R 4 , R 5 , R 6 , n and E can have the meanings mentioned for the general formula (A) in claim 1 ,
(iii) catalysts of general formula (A3)
where
X 1 and X 2 are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight-chain or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulfonate, C 6 -C 24 -arylsulfonate, C 1 - 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 - 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl,
L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure,
R 3 is chloro, fluoro, bromo, —C(═O)R, —C(═O)OR, —OC(═O)R, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R, or —S(═O)R,
R 4 is H, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, —Si(R) 3 , —O—Si(R) 3 , C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R or —S(═O)R,
R 2 and R 5 are each H, bromo (Br), iodo (I), C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, —Si(R) 3 , —O—Si(R) 3 , C 6 -C 20 aryloxy, C 6 -C 20 aryl, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)OR, —C(═O)N(R) 2 , or —SO 2 N(R) 2 ,
R 6 is H, C 1 -C 20 alkyl, C 6 -C 20 aryl, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —SO 2 N(R) 2 , or —N(SO 2 —R) 2 , —S(═O)R, or —S(═O) 2 R, and
n is 0 or 1,
wherein if n=1, then the element
shall mean that Y and (E)r, are linked either by a single bond or by a double bond, wherein
(i) if Y and (E)r, are linked by a single bond, then
Y is oxygen (O), sulfur (S), N—R or P—R and
E is CH 2 ,or
(ii) if Y and (E), are linked by a double bond, then
Y is N or P
E is CH,
wherein if n=0, then
Y is oxygen (O), sulfur (S), N—R or P—R and directly linked by a single bond to the phenyl moiety depicted above in formula (A3), and
wherein in all above occurrences in formula (A3) R is identical or different and shall mean H, C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 2 -C 24 -heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound,
(iv) catalysts of general formula (A4)
wherein M, L, Y, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and n have the meanings given for general formula (A), and
(vii) catalysts of general formula (A7)
where
X 1 and X 2 are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight-chain or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulfonate, C 6 -C 24 -arylsulfonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 - 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl,
L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure,
Y is NR or PR, preferably NR,
R 3 is chloro, fluoro, bromo, —C(═O)R, —C(═O)OR, —OC(═O)R, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R, or —S(═O)R,
R 4 is H, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, —Si(R) 3 , —O—Si(R) 3 , C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R or —S(═O)R,
R 2 and R 5 are each H, bromo (Br), iodo (I), C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, —Si(R) 3 , —O—Si(R) 3 , C 6 -C 20 aryloxy, C 6 -C 20 aryl, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)OR, —C(═O)N(R) 2 , or —SO 2 N(R) 2 ,
R 6 is H, C 1 -C 20 alkyl, C 6 -C 20 aryl, C 2 -C 20 heterocyclic, C 2 -C 20 heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —SO 2 N(R) 2 , —N(SO 2 —R) 2 , —S(═O)R, or —S(═O) 2 R, and
wherein in all above occurrences in formula (A7) R is identical or different and shall mean H, C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 2 -C 16 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, or C 2 -C 24 -heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound.
7. The selective hydrogenation according to claim 1 , wherein the complex catalyst is selected from the group consisting of the below shown formulae, wherein Mes is in each case 2,4,6-trimethylphenyl, Ph is phenyl,
8. The selective hydrogenation according to claim 1 , further comprising:
a) preparing the catalyst composition according to claim 1 by contacting the complex catalyst according to claim 1 with the at least one co-catalyst according to claim 1 in a molar ratio of the complex catalyst to the co-catalyst of 1:30 to 1:100, and thereafter
b) hydrogenating nitrile rubber in the presence of the catalyst composition formed in step a).
9. The selective hydrogenation according to claim 8 , wherein step a) is performed at a temperature of −20° C. to 160° C.
10. The selective hydrogenation according to claim 9 , wherein the hydrogenation in step b) is carried out at a temperature of 60° C. to 200° C., and at a hydrogen pressure of 0.5 MPa to 35 MPa.
11. The selective hydrogenation according to claim 8 , wherein the nitrile rubber is subjected to a molecular weight degradation in a metathesis reaction first comprising contacting the nitrile rubber in the absence or presence of a co-olefin with the complex catalyst according to claim 1 , then
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 of 1:30 to 1:100, to form a catalyst composition, and thereafter
b) hydrogenating the nitrile rubber in the presence of the catalyst composition.
12. The selective hydrogenation according to claim 1 , wherein the catalyst has the general formula (A2)
wherein M, L, X 1 , X 2 , R 1 , R 2 , R 4 , R 5 , R 6 , n and E have the meanings mentioned for the formula (A) in claim 1 .
13. The selective hydrogenation according to claim 1 , wherein the catalyst is selected from the group consisting of
catalysts of general formula (A6)
where
M is ruthenium or osmium,
Z is oxygen (O) or sulfur (S),
Y is oxygen (O), sulfur (S), N—R 7 or P—R 7 , where R 7 is 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,
X 1 and X 2 are identical or different ligands,
R 1 is H, alkyl, alkenyl, alkynyl or aryl,
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen, organic or inorganic substituents,
R 61 is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,
R 62 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, in the alternative R 61 and R 62 form a cyclic structure together with the two adjacent carbon atoms to which they are bound,
L is a ligand, and
n is 0 or 1.
14. A selective hydrogenation of nitrile rubber in the presence of a catalyst composition obtained by contacting a complex catalyst with at least one co-catalyst in a molar ratio of the complex catalyst to the co-catalyst of 1:30 to 1:100, wherein:
the complex catalyst has the general formula (A5)
where
Y is oxygen (O) or —NR, with R representing hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
W is oxygen (O) or NR 7 , with R 7 being hydrogen or straight chain or branched C 1 -C 10 alkyl,
R 15 represents straight chain or branched alkyl,
R 16 , R 17 , R 18 and R 19 are identical or different and represent hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, aryl or heteroaryl,
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure,
R 1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen or an organic or inorganic substituent; and
wherein the co-catalyst must contain at least one vinyl group and has the general formula (1)
CH 2 ═CRR′ (1)
in which R and R′ are identical or different and in the co-catalyst shall mean hydrogen, wherein R and R′ must not both represent hydrogen, or
OR 1 wherein R 1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(═O)(R 2 ), —C(═O)N(R 2 ) 2 , —[(CH 2 ) m —X] m R 2 , —[(CH 2 ) n —X] m —CH═CH 2 , or —(CH 2 ) p —C(R 3 ) 2 R 4 , wherein
X is identical or different and means oxygen (O) or NR 2
R 2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,
R 3 are identical or different and represent C 1 -C 8 alkyl or —(CH 2 ) n′ —O—CH═CH 2 ,
R 4 represents (CH 2 ) p —O—CH═CH 2 ,
n is 1 to 5,
m is 1 to 10,
p is 0 to 5, or
where in the alternative, if R and R′ both represent a group OR 1 , both R 1 may be linked to each other and together represent a divalent group —(C(R 2 ) 2 ) q —with q being 2, 3 or 4 and R 2 being identical or different and having the above defined meanings, or
SR 5 , SOR 5 , SO 2 R 5 wherein R 5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or
N(R 6 R 7 ), P(R 6 R 7 ) wherein R 6 and R 7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)(R 2 ), or where in the alternative R 6 and R 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, N—R 8 or P—R 8 wherein R 8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; or
P(═O)(OR 9 ) 2 in which R 9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl.
15. The selective hydrogenation according to claim 14 , wherein the complex catalyst is selected from the group consisting of the below shown formulae, wherein Mes is in each case 2,4,6-trimethylphenyl, Ph is phenyl,
16. A selective hydrogenation of nitrile rubber in the presence of a catalyst composition obtained by contacting a complex catalyst with at least one co-catalyst in a molar ratio of the complex catalyst to the co-catalyst of 1:30 to 1:100, wherein:
the complex catalyst has the general formula (A)
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
L is an electron donating ligand, which can be linked or not linked with X 1 to form a cyclic structure,
R 1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen or an organic or inorganic substituent,
R 6 is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)R, —C(═O)OR, —C(═O)N(R) 2 , —C(═S)R, —C(═S)SR, —C(═S)OR, —C(═S)N(R) 2 , —S(═O) 2 N(R) 2 , —S(═O) 2 R, —S(═O)R, or a group containing either a C═O or a C═S structural element adjacent to a carbon atom which is bound to Y,
n is 0 or 1,
wherein if n=1, then the element
shall mean that Y and (E) n , are linked either by a single bond or by a double bond, wherein
(i) if Y and (E) n are linked by a single bond, then
Y is oxygen (O), sulfur (S), N—R or P—R, and
E is CH 2 , or
(ii) if Y and (E) n are linked by a double bond, then
Y is N or P, and
E is CH and
wherein if n=0, then
Y is oxygen (O), sulfur (S), N—R or P—R, and is directly linked by a single bond to the phenyl moiety depicted above in formula (A), and
wherein in all above occurrences of general formula (A), R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; and
wherein the co-catalyst is of formula (cocat-32)