Catalyst compositions and their use for hydrogenation of nitrile rubber

Patent metadata

Field	Value
Publication number	US-9605088-B2
Application number	US-201214352077-A
Country	US
Kind code	B2
Filing date	Oct 19, 2012
Priority date	Oct 21, 2011
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

This invention relates to novel catalyst compositions based on Ruthenium- or Osmium-based complex catalysts and to a process for selectively hydrogenating nitrile rubbers in the presence of such catalyst compositions.

First claim

What is claimed is:

1. A process of hydrogenating a nitrile rubber, the process comprising:
a) contacting a complex catalyst with hydrogen in the absence of a nitrile rubber at a temperature 75° C. to 200° C. to form a catalyst composition; and
b) hydrogenating the nitrile rubber in the presence of the catalyst composition, 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 and
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), sulphur (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

wherein if n=0, then
Y is oxygen (O), sulphur (S), N—R or P—R and directly linked by a single bond to the phenyl moiety depicted above in formula (A), and

wherein R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

2. The process according to claim 1 , wherein in step a) 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 have the meanings mentioned for the general formula (A) in claim 1 ,

(ii) catalysts of 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 ,

(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, C6-C 2 4-arylsulfonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -aryl thiol, C 1 -C 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 5 -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,
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
 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 (A5), 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 A 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),

(v) catalysts of 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 MR 7 with R 7 being hydrogen or straight chain or branched C 1 -C 20 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, and
L, R 1 , R 2 , R 3 , R 4 , R 5 and n shall have the meanings given for general formula A,

(vi) 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 has the meanings indicated below, 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, alkoxy carbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkyl sulphonyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,
or where in the alternative R 61 and R 52 may form a cyclic structure together with the two adjacent carbon atoms to which they are bound,
L is a ligand,
R 7 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino,

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Liu Qingchun
• Wei Zhenli

Classifications

• B01J2531/825

  Osmium · CPC title

• B01J2231/645

  of C=C or C-C triple bonds · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title