Catalyst compositions and their use for hydrogenation of nitrile rubber

Patent metadata

Field	Value
Publication number	US-10508156-B2
Application number	US-201815882145-A
Country	US
Kind code	B2
Filing date	Jan 29, 2018
Priority date	Oct 21, 2011
Publication date	Dec 17, 2019
Grant date	Dec 17, 2019

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.

First claim

What is claimed is:

1. A process of hydrogenating a nitrile rubber comprising
a) preparing the catalyst composition by contacting a complex catalyst based on ruthenium or osmium as central metal and bearing at least one carbene ligand which is bound to the ruthenium or osmium central metal with at least one co-catalyst in a molar ratio of the complex catalyst to the co-catalyst in the range of 1:(20 to below 100) wherein the co-catalyst must contain at least one vinyl group and thereafter
b) hydrogenating the nitrile rubber in the presence of the catalyst composition formed in step a) as hydrogenation catalyst,
wherein the co-catalyst has the general formula (1)
CH 2 ═CRR′  (1)

in which R and R′ are identical or different and shall mean 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═C 2 ,
R 4 represents (CH 2 ) p —O—CH═CH 2 ,
n is in the range of from 1 to 5,
m is in the range of from 1 to 10,
p is in the range of from 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 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,
however, under the proviso that R and R′ must not both represent hydrogen in formula (1) at the same time.

2. The process of hydrogenating a nitrile rubber according to claim 1 , further comprising conducting step a) at a temperature of −20° C. to 160° C.

3. The process of hydrogenating a nitrile 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 in the range of 0.5 MPa to 35 MPa.

4. The process of hydrogenating nitrile rubber according to claim 1 , further comprising, prior to hydrogenation, subjecting the 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 carbene 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, then
b) 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
c) hydrogenating the nitrile rubber in the presence of the catalyst composition.

5. The process of hydrogenating nitrile rubber according to claim 1 , wherein the co-catalyst is selected from the group consisting of formulae (cocat-1) to (cocat-38)

6. The process of hydrogenating nitrile rubber according to claim 1 , wherein the complex catalyst is selected from the group consisting of
(i) catalysts of general formula (A),

where
M is osmium or ruthenium,
X 1 and X 2 are identical or different and are two ligands, preferably anionic ligands,
L are identical or different ligands, preferably uncharged electron donors,
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),

where
X 1 , X 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),

where
M is ruthenium or osmium,
X 1 and X 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)

where
M is ruthenium or osmium,
R 13 and R 14 are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl,
X 3 is an anionic ligand,
L 2 is an uncharged π-bonded ligand which may either be monocyclic or polycyclic,
L 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 − is a noncoordinating anion and
n is 0, 1, 2, 3, 4 or 5,

(v) catalysts of general formula (D),

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Obrecht Werner
• David Sarah
• Liu Qingchun
• Wei Zhenli

Classifications

• B01J31/2286

  Alkynes, e.g. acetylides · CPC title

• B01J31/1805

  the ligands containing nitrogen · CPC title

• B01J31/2208

  Oxygen, e.g. acetylacetonates · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J2540/20

  Non-coordinating groups comprising halogens · CPC title