Bis-imine pyridine complex of lanthanides catalytic system comprising said bis-imine pyridine complex and process for the (co)polymerization of conjugated dienes

Patent metadata

Field	Value
Publication number	US-10766979-B2
Application number	US-201615342786-A
Country	US
Kind code	B2
Filing date	Nov 3, 2016
Priority date	Sep 14, 2011
Publication date	Sep 8, 2020
Grant date	Sep 8, 2020

Abstract

A bis-imine pyridine complex of lanthanides having general formula (I):

Said bis-imine pyridine complex of lanthanides 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 process for (co)polymerization of conjugated dienes comprising:
(co)polymerizing the conjugated dienes in the presence of a catalytic system comprising: (a) a bis-imine pyridine complex of lanthanides having general formula (I):

wherein:
R 1 and R 2 , equal to or different from each other, 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;
R 3 and R 4 , equal to or different from each other, 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;
or R 2 and R 4 can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 6 carbon atoms, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing other heteroatoms;
or R 1 and R 3 can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 6 carbon atoms, optionally substituted with linear or branched C 1 -C 20 alkyl groups, said cycle optionally containing other heteroatoms; and
X 1 , X 2 and X 3 , equal to or different from each other, represent a halogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, —OCOR 5 or —OR 5 groups wherein R 5 is selected from linear or branched C 1 -C 20 alkyl groups; and
(b) at least one co-catalyst; wherein the co-catalyst contains aluminum and the molar ratio (Al/Nd) between the aluminum (Al) present in the co-catalyst (b) and neodymium (Nd) present in the bis-imine pyridine complex of lanthanides (a) having general formula (I) ranges from 100 to 1,000;
wherein the (co)polymers of conjugated dienes have a content of 1,4-cis units 98%.

2. The process for (co)polymerization of conjugated dienes according to claim 1 , wherein the conjugated dienes are selected from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and cyclo-1,3-hexadiene.

3. The process for (co)polymerization of conjugated dienes according to claim 1 , wherein the catalytic system comprises the bis-imine pyridine complex of lanthanides having general formula (I), wherein:
R 1 and R 2 , the same as each other, are a hydrogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups; or they are selected from cycloalkyl groups optionally substituted;
R 3 and R 4 , equal to or different from each other, are selected from phenyl groups, optionally substituted; or they are selected from cycloalkyl groups optionally substituted;
X 1 , X 2 and X 3 , the same as each other, are a halogen atom.

4. The process for (co)polymerization of conjugated dienes according to claim 1 , wherein the at least one co-catalyst is selected from:
(b 1 ) aluminum alkyls having general formula (II):
Al(X′) n (R 5 ) 3_n   (II)

wherein x′ represents a halogen atom; R 6 is selected from linear or branched C 1 -C 20 alkyl groups, C 3 -C 20 cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more atoms of silicon or germanium; and n is an integer ranging from 0 to 2; and
(b 2 ) aluminum oxanes having general formula (III):
(R 7 ) 2 —Al—O—[—Al(R 8 )—O—] p —Al—(R 9 ) 2   (III)

wherein R 7 , R 8 and R 9 , equal to or different from each other, represent a hydrogen atom, a halogen atom; or they are selected from linear or branched C 1 -C 20 alkyl groups, C 3 -C 20 cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more atoms of silicon or germanium; and p is an integer ranging from 0 to 1,000.

5. The process for (co)polymerization of conjugated dienes according to claim 4 , wherein said co-catalyst (b) is selected from: tri-iso-butyl-aluminum (TIBA), di-iso-butyl-aluminum hydride (DIBAH), methylaluminumoxane (MAO), or tetra-iso-butyl-aluminumoxane (TIBAO).

6. The process for (co)polymerization of conjugated dienes according to claim 1 , wherein the conjugated dienes are (co)polymerized in the presence of an inert organic solvent selected from: saturated aliphatic hydrocarbons; saturated cyclo-aliphatic hydrocarbons; mono-olefins, aromatic hydrocarbons; and halogenated hydrocarbons.

7. The process for (co)polymerization of conjugated dienes according to claim 1 , wherein the conjugated dienes are (co)polymerized in the presence of a polymerization solvent comprising from 5% by weight to 50% by weight of conjugated dienes based on the total weight of the conjugated diene/solvent mixture.

Assignees

• Versalis Spa

Inventors

• Ricci Giovanni
• Sommazzi Anna
• Leone Giuseppe
• Boglia Aldo
• Masi Francesco
• Caldararo Maria

Classifications

• C08F36/00 Primary

  Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds (C08F32/00 takes precedence) · CPC title

• C08F136/00

  Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds (C08F132/00 takes precedence) · CPC title

• C08F36/06

  Butadiene · CPC title

• C08F136/06

  Butadiene · CPC title

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title