# US 10,766,979 B2 · Bis-imine pyridine complex of lanthanides catalytic system comprising said bis-imine pyridine complex and process for the (co)polymerization of conjugated dienes

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,766,979 B2
- Document ID: US10766979B2
- Status: Granted
- Kind: B2
- Application number: 15/342,786
- Filed: 2016-11-03
- Published: 2017-06-15
- Granted: 2020-09-08
- Earliest claimed: 2011-09-14
- Assignees: Versalis S.P.A.
- Applicants: Versalis S.P.A.
- Inventors: Giovanni Ricci; Anna Sommazzi; Giuseppe Leone; Aldo Boglia; Francesco Masi; Maria Caldararo
- Web page: https://patentgrep.com/patent/US10766979B2

## CPC

- C08F 36/08: Isoprene
- C08F 36/00: 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)
- C08F 36/04: conjugated
- C08F 36/06: Butadiene
- C08F 136/00: 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)
- C08F 2410/04: Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## 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.

## Claims

### Claim 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:
R1 and R2, equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
R3 and R4, equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups optionally substituted, aryl groups optionally substituted;
or R2 and R4 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 C1-C20 alkyl groups, said cycle optionally containing other heteroatoms;
or R1 and R3 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 C1-C20 alkyl groups, said cycle optionally containing other heteroatoms; and
X1, X2 and X3, equal to or different from each other, represent a halogen atom; or they are selected from linear or branched C1-C20 alkyl groups, —OCOR5 or —OR5 groups wherein R5 is selected from linear or branched C1-C20 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%.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 1)

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:
R1 and R2, the same as each other, are a hydrogen atom; or they are selected from linear or branched C1-C20 alkyl groups; or they are selected from cycloalkyl groups optionally substituted;
R3 and R4, equal to or different from each other, are selected from phenyl groups, optionally substituted; or they are selected from cycloalkyl groups optionally substituted;
X1, X2 and X3, the same as each other, are a halogen atom.

### Claim 4 (depends on 1)

The process for (co)polymerization of conjugated dienes according to claim 1, wherein the at least one co-catalyst is selected from:
(b1) aluminum alkyls having general formula (II):
Al(X′)n(R5)3_n (II)
wherein x′ represents a halogen atom; R6 is selected from linear or branched C1-C20 alkyl groups, C3-C20 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
(b2) aluminum oxanes having general formula (III):
(R7)2—Al—O—[—Al(R8)—O—]p—Al—(R9)2 (III)
wherein R7, R8 and R9, equal to or different from each other, represent a hydrogen atom, a halogen atom; or they are selected from linear or branched C1-C20 alkyl groups, C3-C20 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.

### Claim 5 (depends on 4)

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).

### Claim 6 (depends on 1)

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.

### Claim 7 (depends on 1)

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.