Vanadium pyridine-imine complex, catalytic system comprising said vanadium pyridine-immine complex and a (co) polymerization process of conjugated dienes

Patent metadata

Field	Value
Publication number	US-10633474-B2
Application number	US-201615765782-A
Country	US
Kind code	B2
Filing date	Nov 10, 2016
Priority date	Nov 11, 2015
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

Vanadium pyridine-imine complex having general formula (I), wherein: —R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , equal to or different from each other, represent a hydrogen atom; or are selected from linear or branched C 1 -C 20 alkyl groups, preferably C 1 -C 15 , optionally halogenated cycloalkyl groups optionally substituted, aryl groups optionally substituted; —X 1 , X 2 and X 3 , equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or are selected from linear or branched C 1 -C 20 alkyl groups, preferably C 1 -C 15 , —OCOR 7 groups or —OR 7 groups wherein R 7 is selected from linear or branched C 1 -C 20 alkyl groups, preferably C 1 -C 15 ; —Y is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); —n is 0 or 1. Said vanadium pyridine-imine complex having general formula (I) can be advantageously used in a catalytic system for the (co) polymerization of conjugated dienes.

First claim

The invention claimed is:

1. A vanadium pyridine-imine complex having a formula (I):

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an optionally halogenated linear or branched C 1 -C 15 alkyl group
X 1 , X 2 and X 3 each independently represent a halogen atom, a linear or branched C 1 -C 20 alkyl group, a —OCOR 7 group or a —OR 7 group, wherein R 7 is a linear or branched C 1 -C 20 alkyl group;
Y is diethylether, tetrahydrofuran (THF), or dimethoxyethane; and
n is 0 or 1,

with the proviso that when n is 0, R 2 is an optionally substituted cycloalkyl group.

2. The vanadium pyridine-imine complex of claim 1 , wherein:
X 1 , X 2 and X 3 , each independently represent a halogen atom;
Y is tetrahydrofuran (THF); and
n is 1.

3. A catalytic system for (co)polymerization of conjugated dienes, comprising:
(a) the vanadium pyridine-imine complex of claim 1 ; and
(b) a co-catalyst that is an aluminum organo-derivative compound.

4. The catalytic system of claim 3 , wherein the co-catalyst comprises an aluminoxane having a formula (III):
(R 12 ) 2 —Al—O—[—Al(R 13 )—O-] m -Al—(R 14 ) 2   (III)

wherein R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, or aryl group, optionally substituted with one or more silicon or germanium atoms; and m is an integer of 0 to 1000.

5. A process of (co)polymerizing conjugated dienes, comprising (co)polymerizing one or more conjugated dienes with a catalytic system comprising:
(a) a vanadium pyridine-imine complex; and
(b) a co-catalyst that is an aluminum organo-derivative compound,
wherein the vanadium pyridine-imine complex having a formula (I):

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, an optionally halogenated linear or branched C 1 -C 20 alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group;
X 1 , X 2 and X 3 each independently represent a halogen atom, a linear or branched C 1 -C 20 alkyl group, a —OCOR 7 group or a —OR 7 group, wherein R 7 is a linear or branched C 1 -C 20 alkyl group;
Y is an ether; and
n is 0 or 1.

6. The process of claim 5 , wherein the one or more conjugated dienes comprise 1,3-butadiene or isoprene.

7. The vanadium pyridine-imine complex of claim 1 , wherein X 1 , X 2 and X 3 each independently represent a linear or branched C 1 -C 15 alkyl group.

8. The vanadium pyridine-imine complex of claim 1 , wherein n is 0.

9. The vanadium pyridine-imine complex of claim 1 , wherein n is 1.

10. The catalytic system of claim 3 , wherein the co-catalyst comprises at least one selected from the group consisting of (b 1 ), (b 2 ), (b 3 ) and (b 4 ):
(b 1 ) a compound having a formula (II):
Al(R 9 )(R 10 )(R 11 )  (II)

wherein R 9 represents a hydrogen atom, a fluorine atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, aryl group, alkylaryl group, arylalkyl group, or alkoxy group; R 10 and R 11 each independently represent a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, aryl group, alkylaryl group, or arylalkyl group;
(b 2 ) an aluminoxane having a formula (III):
(R 12 ) 2 —Al—O—[—Al(R 13 )—O-] m -Al—(R 14 ) 2   (III)

wherein R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, or aryl group, optionally substituted with one or more silicon or germanium atoms; and m is an integer of 0 to 1000
(b 3 ) an aluminum organo-derivative compound that is partially hydrolyzed; and
(b 4 ) a halogen-aluminum alkyl having a formula (IV) or (V):
Al(R 15 ) p (X 3 ) 3-p   (IV)

Al 2 (R 15 ) q (X 3 ) 3-q   (V)

wherein p is 1 or 2; q is an integer of 1 to 5; each R 15 independently represents a linear or branched C 1 -C 20 alkyl group; and X 3 represents a chlorine or bromine atom.

11. The process of claim 5 , wherein:
R 1 represents a hydrogen atom or a linear or branched C 1 -C 20 alkyl group;
R 2 represents an optionally substituted cycloalkyl group or an optionally substituted amyl group;
R 3 , R 4 , R 5 and R 6 , each represent a hydrogen atom;
X 1 , X 2 and X 3 , each independently represent a halogen atom;
Y is tetrahydrofuran (THF); and
n is 1;
wherein the co-catalyst comprises an aluminoxane having a formula (III):
(R 12 ) 2 —Al—O—[—Al(R 13 )—O-] m -Al—(R 14 ) 2   (III)

wherein R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, or aryl group, optionally substituted with one or more silicon or germanium atoms; and m is an integer of 0 to 1000.

12. The process of claim 5 , wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an optionally halogenated linear or branched C 1 -C 15 alkyl group.

13. The process of claim 5 , wherein X 1 , X 2 and X 3 each independently represent a linear or branched C 1 -C 15 alkyl group.

14. The process of claim 5 , wherein n is 0.

15. The process of claim 5 , wherein n is 1.

16. The process of claim 5 , wherein R 2 is selected from the group consisting of 2,6-di-iso-propylphenyl-2-methyl-phenyl and 2,4,6-trimethylphenyl.

17. The process of claim 5 , wherein the co-catalyst comprises at least one selected from the group consisting of (b 1 ), (b 2 ), (b 3 ) and (b 4 ):
(b 1 ) a compound having a formula (II):
Al(R 9 )(R 10 )(R 11 )  (II)

wherein R 9 represents a hydrogen atom, a fluorine atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, aryl group, alkylaryl group, arylalkyl group, or alkoxy group; R 10 and R 11 each independently represent a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, aryl group, alkylaryl group, or arylalkyl group;
(b 2 ) an aluminoxane having a formula (III):
(R 12 ) 2 —Al—O—[—Al(R 13 )—O-] m -Al—(R 14 ) 2   (III)

wherein R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, or a linear or branched C 1 -C 20 alkyl group, cycloalkyl group, or aryl group, optionally substituted with one or more silicon or germanium atoms; and m is an integer of 0 to 1000
(b 3 ) an aluminum organo-derivative compound that is partially hydrolyzed; and
(b 4 ) a halogen-aluminum alkyl having a formula (IV) or (V):
Al(R 15 ) p (X 3 ) 3-p   (IV)

Al 2 (R 15 ) q (X 3 ) 3-q   (V)

wherein p is 1 or 2; q is an integer of 1 to 5; each R 15 independently represents a linear or branched C 1 -C 20 alkyl group; and X 3 represents a chlorine or bromine atom.

Assignees

• Versalis Spa

Inventors

• Ricci Giovanni
• Leone Giuseppe
• Sommazzi Anna
• Masi Francesco

Classifications

• C08F4/68034

  NN · CPC title

• C08F136/08

  Isoprene · CPC title

• C07F9/005 Primary

  Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages · CPC title

• C08F136/06

  Butadiene · CPC title

• C08F236/06

  Butadiene · CPC title