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US 10,500,578 B2Granted
Catalyst compositions and their use for hydrogenation of nitrile rubber
AssigneeArlanxeo Deutschland GmbH
InventorsWerner Obrecht, Sarah David, Qingchun Liu, Zhenli Wei
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Abstract
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.
Claims16
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,
- X1 and X2 are identical or different ligands,
- L is an electron donating ligand, which can be linked or not linked with X1 to form a cyclic structure,
- R1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
- R2, R3, R4 and R5 are identical or different and are each hydrogen or an organic or inorganic substituent,
- R6 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)2N(R)2, —S(═O)2R, —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 CH2, 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)
- CH2═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
- OR1 wherein R1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(═O)(R2), —C(═O)N(R2)2, —[(CH2)n—X]mR2, —[(CH2)n—X]m—CH═CH2, or —(CH2)p—C(R3)2R4, wherein
- X is identical or different and means oxygen (O) or NR2
- R2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,
- R3 are identical or different and represent C1-C8 alkyl or —(CH2)n′—O—CH═CH2,
- R4 represents (CH2)p′—O—CH═CH2,
- 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 OR1, both R1 may be linked to each other and together represent a divalent group —(C(R2)2)q—with q being 2, 3 or 4 and R2 being identical or different and having the above defined meanings, or
- SR5, SOR5, SO2R5 wherein R5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or
- N(R6R7), P(R6R7) wherein R6 and R7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)(R2), or where in the alternative R6 and R7 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—R8 or P—R8 wherein R8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl;
- or
- P(═O)(OR9)2 in which R9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl.
33 more elements
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 NR7, with R7 being hydrogen or straight chain or branched C1-C10 alkyl,
- R15 represents straight chain or branched alkyl,
- R16, R17, R18 and R19 are identical or different and represent hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, aryl or heteroaryl,
- M is ruthenium or osmium,
- X1 and X2 are identical or different ligands,
- L is an electron donating ligand, which can be linked or not linked with X1 to form a cyclic structure,
- R1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
- R2, R3, R4 and R5 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)
- CH2═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
- OR1 wherein R1 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(═O)(R2), —C(═O)N(R2)2, —[(CH2)m—X]mR2, —[(CH2)n—X]m—CH═CH2, or —(CH2)p—C(R3)2R4, wherein
- X is identical or different and means oxygen (O) or NR2
- R2 are identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,
- R3 are identical or different and represent C1-C8 alkyl or —(CH2)n′—O—CH═CH2,
- R4 represents (CH2)p—O—CH═CH2,
- 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 OR1, both R1 may be linked to each other and together represent a divalent group —(C(R2)2)q—with q being 2, 3 or 4 and R2 being identical or different and having the above defined meanings, or
- SR5, SOR5, SO2R5 wherein R5 represents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or
- N(R6R7), P(R6R7) wherein R6 and R7 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, —C(═O)(R2), or where in the alternative R6 and R7 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—R8 or P—R8 wherein R8 shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl;
- or
- P(═O)(OR9)2 in which R9 are identical or different and shall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl.
25 more elements
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,
- X1 and X2 are identical or different ligands,
- L is an electron donating ligand, which can be linked or not linked with X1 to form a cyclic structure,
- R1 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,
- R2, R3, R4 and R5 are identical or different and are each hydrogen or an organic or inorganic substituent,
- R6 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)2N(R)2, —S(═O)2R, —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 CH2, 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)
19 more elements
Dependencies are inferred from the claim text.