Hydrogenation catalyst compositions and their use for hydrogenation of nitrile rubber

Patent metadata

Field	Value
Publication number	US-11713361-B2
Application number	US-201917048370-A
Country	US
Kind code	B2
Filing date	Apr 11, 2019
Priority date	Apr 20, 2018
Publication date	Aug 1, 2023
Grant date	Aug 1, 2023

Abstract

This invention relates to novel hydrogenation catalyst compositions obtainable from reacting metal-based complex hydrogenation catalysts with specific co-catalysts and to a process for selectively hydrogenating nitrile rubbers in the presence of such novel hydrogenation catalyst compositions.

First claim

What is claimed is:

1. A process for hydrogenating a nitrile rubber comprising:
a) preparing a hydrogenation catalyst composition by contacting a complex hydrogenation catalyst of the general formula (IA) or (IB)

M is ruthenium;
z is selected from the group consisting of oxygen, sulphur, selenium, NR″″, PR″″, AsR″″ and SbR″″; R″, R′″ and R″″ are each a radical independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3-8 cycloalkyl, C 1-6 alkyl-C 1-6 alkoxysilyl, C 1-6 alkyl-aryloxysilyl, C 1-6 alkyl-C 3-10 cycloalkoxysilyl, aryl and heteroaryl, or R″ and R′″ together form an aryl or heteroaryl radical, each said radical (when different from hydrogen) being optionally substituted with one or more, preferably 1 to 3, substituents R 5 each independently selected from the group consisting of halogen atoms, C 1-6 alkyl, C 1-6 alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C 1-6 alkyl-C 1-6 alkoxysilyl, C 1-6 alkyl-aryloxysilyl, C 1-6 alkyl-C 3-10 cycloalkoxysilyl, alkylammonium and arylammonium;
R′ is either methyl, phenyl or substituted phenyl (e.g. dimethyl bromo phenyl or diisopropylphenyl) when included in a compound having the general formula (IA) or, is methylene or benzylidene when included in a compound having the general formula (IB);
R 1 is an electron donating complex ligand, which could be linked or not linked with R 2 to form a cyclic structure;
R 2 is an anionic ligand;
R 3 and R 4 are each hydrogen or a radical selected from the group consisting of C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 carboxylate, C 1-20 alkoxy, C 2-20 alkenyloxy, C 2-20 alkynyloxy, aryl, aryloxy, C 1-20 alkoxycarbonyl, C 1-8 alkylthio, C 1-20 alkylsulfonyl, C 1-20 alkylsulfinyl C 1-20 alkylsulfonate, arylsulfonate, C 1-20 alkylphosphonate, arylphosphonate, C 1-20 alkylammonium and arylammonium;
R′ and one of R 3 and R 4 may be bonded to each other to form a bidentate ligand;
R′″ and R″″ may be bonded to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorous, arsenic and antimony;
R 3 and R 4 together may form a fused aromatic ring system having the formula (VI)

and
y represents the number of sp 2 carbon atoms between M and the carbon atom bearing R 3 and R 4 and is 0 or 1,
with at least one co-catalyst of the general formula (1) in a molar ratio of the complex hydrogenation catalyst to the co-catalyst in the range of 1:(20-550)
CH 2 ═CRR′  (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 -alky, 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,
and thereafter

b) hydrogenating the nitrile rubber with hydrogen in the presence of the catalyst composition formed in step a).

2. The process of claim 1 wherein:
the co-catalyst is selected from the group consisting of formulae (cocat-1) to (cocat-7) and (cocat-10) to (cocat-12)

3. The process of claim 1 wherein the ligand R 1 of the complex hydrogenation catalyst has a structure corresponding to the general formulae (IIa) or (IIb),

where
R 8 , R 9 , R 10 and R 11 are identical or different and represent hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 7 -C 25 -alkaryl, C 2 -C 20 heteroaryl, C 2 -C 20 heterocyclyl, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 20 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 20 -arylthio, —Si(R) 3 , —O—Si(R) 3 , —O—C(═O)R, C(═O)R, —C(═O)N(R) 2 , —NR—C(═O)—N(R) 2 , —SO 2 N(R) 2 , —S(═O)R, —S(═O) 2 R, —O—S(═O) 2 R, halogen, nitro or cyano; wherein in all above occurrences relating to the meanings of R 8 , R 9 , R 10 and R 11 the group R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

4. The process of claim 1 , wherein R 2 is selected from the group consisting of 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 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl.

5. The process of claim 1 wherein y=0.

6. The process of claim 1 , wherein R 3 and R 4 together form a fused aromatic ring system having the formula (VI)

7. The process of claim 1 , wherein in step a)
(i) [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II)
or
(ii) [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]-[3-phenyl-1H-inden-1-ylidene](chloro)ruthenium(II)
is used as a complex hydrogenation catalyst.

8. The process of claim 1 , wherein step a) is performed at a temperature in the range of from −20° C. to 160° C.

9. The process of claim 1 , wherein the hydrogenation in step b) is carried out at a temperature in the range of from 60° C. to 200° C. and at a hydrogen pressure in the range of 0.5 MPa to 35 MPa.

10. The process according to of claim 1 , wherein prior to step a), 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 hydrogenation catalyst of the general formulae (IA) or (IB), and wherein in step a) the complex hydrogenation catalyst is present in the reaction mixture obtained after the metathesis reaction.

11. The process of claim 2 wherein the ligand R 1 of the complex hydrogenation catalyst has a structure corresponding to the general formulae (IIa) or (IIb),

where
R 8 , R 9 , R 10 and R 11 are identical or different and represent hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 7 -C 25 -alkaryl, C 2 -C 20 heteroaryl, C 2 -C 20 heterocyclyl, C 1 -C 20 -alkoxy, C 2 -C 20 -alke

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Liu Qingchun
• Wei Zhenli
• Gao nian

Classifications

• C08C19/00

  Chemical modification of rubber · CPC title

• C08C19/02 Primary

  Hydrogenation · CPC title

• B01J31/0204

  Ethers · CPC title

• B01J31/2217

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• B01J31/2273

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