Oxo-nitrogenated complex of cobalt, catalytic system comprising said oxo-nitrogenated complex and process for the (CO) polymerization of conjugated dienes

Patent metadata

Field	Value
Publication number	US-9493404-B2
Application number	US-201314646051-A
Country	US
Kind code	B2
Filing date	Dec 18, 2013
Priority date	Dec 20, 2012
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

The present invention relates to an oxo-nitrogenated complex of cobalt having the general formula (I) wherein the residues R 1 , R 2 , R 3 , X 1 and X 2 are as defined in the claims. Said oxo-nitrogenated complex of cobalt 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. An oxo-nitrogenated complex of cobalt having general formula (I):

wherein:
R 1 and R 2 , the same or different, represent a hydrogen atom, or they are selected from linear or branched C 1 -C 20 alkyl groups optionally halogenated, cycloalkyl groups optionally substituted; or aryl groups optionally substituted;
R 3 represents a hydrogen atom, or it is selected from linear or branched C 1 -C 20 alkyl groups optionally halogenated, or cycloalkyl groups optionally substituted; or aryl groups optionally substituted; or R 3 represents a ketoimine group having formula:

wherein R′ and R″, the same or different, represent a hydrogen atom, or they are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups optionally substituted; aryl groups optionally substituted;
X 1 and X 2 , the same or different, represent a halogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 alkyl groups.

2. The oxo-nitrogenated complex of cobalt having general formula (I) according to claim 1 , wherein:
R 1 and R 2 , the same as each other, represent a hydrogen atom, or they are selected from linear or branched C 1 -C 20 alkyl groups;
R 3 is selected from linear or branched C 1 -C 20 alkyl groups, or phenyl groups optionally substituted with linear or branched C 1 -C 20 alkyl groups; or R 3 represents a ketoimine group having formula:

wherein R′ and R″, the same as each other, represent a hydrogen atom;
X 1 and X 2 , the same as each other, represent a halogen atom.

3. A catalytic system for the (co)polymerization of conjugated dienes comprising:
(a) at least one oxo-nitrogenated complex of cobalt having general formula (I) according to claim 1 ;
(b) at least one co-catalyst selected from organic compounds of an element M′ different from carbon, said element M′ being selected from elements belonging to groups 2, 12, 13 or 14, of the Periodic Table of Elements.

4. The catalytic system for the (co)polymerization of conjugated dienes according to claim 3 , wherein said co-catalyst (b) is selected from (b 1 ) aluminium alkyls having general formula (II):
Al(X′) n (R 5 ) 3-n   (II)

wherein X′ represents a halogen atom; R 5 is selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, or aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and n is an integer ranging from 0 to 2.

5. The catalytic system for the (co)polymerization of conjugated dienes according to claim 3 , wherein said co-catalyst (b) is selected from (b 2 ) organo-oxygenated compounds of an element M′ different from carbon belonging to groups 13 or 14 of the Periodic Table of Elements.

6. The catalytic system for the (co)polymerization of conjugated dienes according to claim 3 , wherein said co-catalyst (b) is selected from (b 3 ) organometallic compounds or mixtures of organometallic compounds of an element M′ different from carbon capable of reacting with the oxo-nitrogenated complex of cobalt having general formula (I), extracting therefrom a substituent X 1 or X 2 σ-bound, to form at least one neutral compound, and an ionic compound including a cation containing the metal (Co) coordinated by the ligand, and a non-coordinating organic anion containing the metal M′, wherein the negative charge is delocalized on a multicentric structure.

7. The catalytic system for the (co)polymerization of conjugated dienes according to claim 4 , wherein said aluminium alkyls (b 1 ) having general formula (II) are di-ethyl-aluminium chloride (DEAC), mono-ethyl-aluminium dichloride (EADC), ethylaluminiumsesquichloride (EASC).

8. The catalytic system for the (co)polymerization of conjugated dienes according to claim 5 , wherein said organo-oxygenated compounds (b 2 ) are selected from aluminoxanes having general formula (III):
(R 6 ) 2 —Al—O—[—Al(R 7 )—O-] p -Al—(R 8 ) 2   (III)

wherein R 6 , R 7 and R 8 , the same or different, represent a hydrogen atom, a halogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, or aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and p is an integer ranging from 0 to 1,000.

9. The catalytic system for the (co)polymerization of conjugated dienes according to claim 8 , wherein said organo-oxygenated compound (b 2 ) is methylaluminoxane (MAO).

10. The catalytic system for the (co)polymerization of conjugated dienes according to claim 6 , wherein said compounds or mixtures of compounds (b 3 ) are selected from organic compounds of aluminium and boron represented by the following general formulae:
[(R C ) W H 4-W ].[B(R D ) 4 ] − ; B(R D ) 3 ; Al(R D ) 3 ; B(R D ) 3 P; [Ph 3 C] + .[B(R D ) 4 ] − ; [(R C ) 3 PH] + .[B(R D ) 4 ] − ; [Li] + .[B(R D ) 4 ] − ; [Li] + .[Al(R D ) 4 ] −

wherein w is an integer ranging from 0 to 3, each group R C independently represents an alkyl group or an aryl group having from 1 to 10 carbon atoms and each group R D independently represents an aryl group partially or totally fluorinated, having from 6 to 20 carbon atoms, P represents a pyrrole radical optionally substituted.

11. A process for the (co)polymerization of conjugated dienes, comprising subjecting conjugated dienes to said catalytic system according to claim 1 and forming a (co)polymer of said conjugated dienes.

12. The (co)polymerization process according to claim 11 , wherein said conjugated dienes are 1,3-butadiene or isoprene.

13. A polymerization process comprising subjecting 1,3-butadiene or isoprene to said catalytic system according to claim 4 and forming a polymer of 1,3-butadiene or isoprene.

Assignees

• Versalis Spa

Inventors

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

Classifications

• C08F36/06

  Butadiene · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title

• C08F136/06

  Butadiene · CPC title

• C07C251/08 Primary

  being acyclic · CPC title

• C08F4/7096

  Cobalt or compounds thereof · CPC title