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

Patent metadata

Field	Value
Publication number	US-11518776-B2
Application number	US-201816345015-A
Country	US
Kind code	B2
Filing date	Jan 18, 2018
Priority date	Jan 20, 2017
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

Oxo-nitrogenated iron complex having general formula (I): in which: R1 and R2, identical or different, represent a hydrogen atom; or they are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R3 represents a hydrogen atom, or it is selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15 alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or they are selected from. linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR4 groups or —OR4 groups in which R4 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups; n is 2 or 3. Said oxo-nitrogenated iron 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. Oxo-nitrogenated iron complex having general formula (I):

in which:
R 1 and R 2 are methyl groups;
R 3 is selected from the group consisting of phenyl and phenyl groups substituted with one or more methyl, ethyl, iso-propyl, or tert-butyl groups;
X is chlorine; and
n is 2 or 3.

2. Catalytic system for the (co)polymerization of conjugated dienes comprising:
(a) at least one oxo-nitrogenated iron complex 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 the Elements.

3. Catalytic system for the (co)polymerization of conjugated dienes according to claim 2 , in which said at least one co-catalyst (b) is selected from (b 1 ) an aluminum alkyl having general formula (V):
Al(X′) n (R 5 ) 3-n   (V)

in which X′ represents a halogen atom;
R 5 , identical or different, represents a hydrogen atom, or is selected from a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group, or an aryl group, each of which may be optionally substituted with one or more silicon or germanium atoms; and n is an integer ranging from 0 to 2.

4. Catalytic system for the (co)polymerization of conjugated dienes according to claim 3 , in which said aluminum alkyl (b1) having general formula (V) is di-iso-butyl-aluminum hydride (DIBAH), di-ethyl-aluminum chloride (DEAC), mono-ethyl aluminum dichloride (EADC), or ethyl aluminum-sesquichloride (EASC).

5. Catalytic system for the (co)polymerization of conjugated dienes according to claim 2 , in which said at least one co-catalyst (b) is selected from an organo-oxygenated compound (b 2 ) of an element M′ different from carbon belonging to groups 13 or 14 of the Periodic Table of the Elements.

6. Catalytic system for the (co)polymerization of conjugated dienes according to claim 5 , in which said organo-oxygenated compound (b2) is selected from an aluminoxane having general formula (VI):
(R 6 ) 2 —Al—O—[—Al(R 7 )—O—] p -Al—(R 8 ) 2   (VI)

in which R 6 , R 7 and R 8 , identical or different, represent a hydrogen atom, a halogen atom, or are independently selected from a linear or branched C 1 -C 20 alkyl group, a cycloalkyl group, or an aryl group, each of which may be optionally substituted with one or more silicon or germanium atoms; and p is an integer ranging from 0 to 1000.

7. Catalytic system for the (co)polymerization of conjugated dienes according to claim 6 , in which said organo-oxygenated compound (b2) is methylaluminoxane (MAO).

8. Catalytic system for the (co)polymerization of conjugated dienes according to claim 2 , in which said at least one co-catalyst (b) is selected from an organometallic compound or a mixture of organometallic compounds (b3) of an element M′ different from carbon that reacts with the oxo-nitrogenated iron complex having general formula (I) by abstracting from the oxo-nitrogenated iron complex an σ-linked substituent.

9. Catalytic system for the (co)polymerization of conjugated dienes according to claim 8 , in which said organometallic compound or mixture of organometallic compounds (b 3 ) is selected from organic compounds of 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 Pir; [Ph 3 C] + .[B(R D ) 4 ] − ;
[(R C ) 3 PirH] + .[B(R D ) 4 ] − ;
[Li] + .[B(R D ) 4 ] − ; [Li] + .[Al(R D ) 4 ] −

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

10. Catalytic system for the (co)polymerization of conjugated dienes according to claim 2 , in which said at least one co-catalyst (b) is selected from an organometallic compound or mixture of organometallic compounds (b3) of an element M′ different from carbon that reacts with the oxo-nitrogenated iron complex having the general formula (I),
wherein an σ-linked substituent is abstracted by the least one co-catalyst to form:
at least one neutral compound, and
an ionic compound comprising a cation containing the metal (Fe) coordinated by a ligand and a non-coordinating organic anion containing the element M′, whose negative charge is delocalized on a multicentric structure.

11. Process for the polymerization of 1,3-butadiene or isoprene, the process comprising polymerizing 1,3-butadiene or isoprene in the presence of the catalytic system according claim 2 .

Assignees

• Versalis Spa

Inventors

• Sommazzi Anna
• Pampaloni Guido
• Ricci Giovanni
• Masi Francesco
• Renili Filippo

Classifications

• C08F136/06

  Butadiene · CPC title

• C08F4/7008

  NO · CPC title

• C08F36/00

  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) · CPC title

• C08F36/08

  Isoprene · CPC title

• C07C251/08

  being acyclic · CPC title