Process for the preparation of low molecular weight hydrogenated nitrile rubber
View Patent ↗Pursuant to the invention a process for the production of hydrogenated nitrile rubber polymers having lower molecular weights and narrower molecular weight distributions than those known in the art in the is provided wherein the process is carried out in the presence of hydrogen and optionally at least one co-(olefin). The present invention further relates to the use of specific metal compounds in a process for the production of a hydrogenated nitrile rubber by simultaneous hydrogenation and metathesis of a nitrile rubber.
1. A process for the production of a hydrogenated nitrile rubber, the process comprising contacting a nitrile rubber with a compound of formula (I),
wherein:
M is ruthenium or osmium,
Y is oxygen (O), sulphur (S), an N—R 1 radical or a P—R 1 radical, where R 1 is as defined below,
X 1 and X 2 are identical or different ligands,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, CR 13 C(O)R 14 or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 13 is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals;
R 14 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals;
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen, organic or inorganic radicals,
R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical and
L is a ligand, and
the compound of formula (I) simultaneously catalyzes metathesis and hydrogenation of the nitrile rubber.
2. The process according to claim 1 , wherein the ligand L is a phosphine, a sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine, thioether, or L is a substituted or unsubstituted imidazolidine (“Im”) ligand.
3. The process according to claim 2 , wherein the imidazolidine radical (Im) has a structure of formula (IIa) or (IIb),
where
R 8 , R 9 , R 10 , R 11 are identical or different and are each 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 1 -C 20 -carboxylate, 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 1 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, or C 1 -C 20 -alkylsulphinyl.
4. The process according to any one of claims 1 to 3 , wherein X 1 and X 2 are identical or different and represent 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 1 -C 20 -alkykldiketonate, C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl.
5. The process according to any one of claims 1 to 3 , wherein the compound of formulae (I) is a compound of formula (IV)
wherein
M is ruthenium,
X 1 and X 2 are both halogen,
R 1 is a straight-chain or branched C 1 -C 12 -alkyl radical,
R 2 , R 3 , R 4 , R 5 are identical or different and are each hydrogen, organic or inorganic radicals, and
L is a ligand.
6. The process according to claim 5 , wherein in the compound of formula (IV)
M is ruthenium,
X 1 and X 1 are both chlorine,
R 1 is an isopropyl radical,
R 2 , R 3 , R 4 , R 5 are all hydrogen, and
L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb),
where
R 8 , R 9 , R 10 , R 11
are identical or different and are each 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 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 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate or C 1 -C 20 -alkylsulphinyl.
7. The process according to claim 5 , wherein the compound of the formula (IV) is selected from the compounds of formulae (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where Mes is in each case a 2,4,6-trimethylphenyl radical
8. The process according to claim 1 , wherein the compound of formula (I) is a compound of formula (XIV)
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, CR 13 C(O)R 14 or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 13 is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals;
R 14 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals;
R 2 , R 4 and R 5 are identical or different and are each hydrogen, organic or inorganic radicals,
R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical, and
L is a ligand.
9. The process according to claim 8 , wherein in the compounds of formula (XIV)
M is ruthenium,
X 1 and X 2 are both chlorine,
R 1 is an isopropyl radical,
R 2 , R 4 and R 5 are each hydrogen, and
L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb),
where
R 8 , R 9 , R 10 , R 11
are identical or different and are each hydrogen, straight-chain or branched, cyclic or acyclic C 1 -C 30 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 CO-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 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate or C 1 -C 20 -alkylsulphinyl.
10. The process according to claim 1 , wherein the compound of formula (I) has is a compound of formula (XVII)
where
M is ruthenium or osmium,
Y is oxygen (O) or an N—R 1 radical,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
X 1 and X 2 are identical or different ligands,
R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical,
R 2 , R 3 , R 4 and R 5 are Identical or different and are each hydrogen, organic or inorganic radicals,
R 14 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 13 is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals; and
L is a ligand.
11. The process according to claim 10 , wherein in the general compound of formula (XVII)
M is ruthenium,
X 1 and X 2 are both chlorine,
R 1 is hydrogen,
R 2 , R 3 , R 4 , R 5 are all hydrogen,
R 13 is methyl
R 14 is methyl and
L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb),
where
R 8 , R 9 , R 10 , R 11
are identical or different and are each hydrogen, straight-chain or branched, cyclic or acyclic C 1 -C 30 -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 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate or C 1 -C 20 -alkylsulphinyl.
12. The process according to claim 1 , wherein the process comprises contacting the nitrile rubber with a compound of formula (XIV), wherein the compound of formula (I) is a portion of the D 1 , D 2 , D 3 , and D 4 components of the compound of formula (XIV),
where
D 1 , D 2 , D 3 and D 4 each have a structure of the general formula (XV) which is bound via the methylene group to the silicon of the formula (XIV),
where
M is ruthenium or osmium,
Y is oxygen (O), sulphur (S), an N—R 1 radical or a P—R 1 radical, where R 1 is as defined below,
X 1 and X 2 are identical or different ligands,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 2 , R 3 and R 5 are identical or different and are each hydrogen, organic or inorganic radicals,
R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical and
L is a ligand.
13. The process according to claim 1 , wherein the hydrogenation reaction is carried out in a suitable solvent selected from the group consisting of dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane and cyclohexane.
14. The process according to claim 1 , wherein the amount of the compound of formula (I) is from 5 to 1000 ppm of noble metal based on the nitrile rubber used.