# US 7,612,009 B2 · Process for homo-or copolymerization of conjugated olefines

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- Number: US 7,612,009 B2
- Document ID: US7612009B2
- Status: Granted
- Kind: B2
- Application number: 10/543,986
- Filed: 2004-02-18
- Published: 2006-06-29
- Granted: 2009-11-03
- Earliest claimed: 2003-02-21
- Assignees: Dow Global Technologies LLC
- Inventors: Sven K.-H. Thiele
- Web page: https://patentgrep.com/patent/US7612009B2

## CPC

- B01J 31/143: {of aluminium}
- B01J 31/146: {of boron}
- B01J 31/1805: {the ligands containing nitrogen}
- C07F 5/00: Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F 15/00: Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 36/06: Butadiene
- C08F 297/04: polymerising vinyl aromatic monomers and conjugated dienes
- C08F 297/046: {polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes}
- C08F 297/06: using a catalyst of the coordination type
- C08L 53/02: of vinyl-aromatic monomers and conjugated dienes
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/37: Lanthanum
- B01J 2531/38: Lanthanides other than lanthanum
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Metal complexes, catalyst compositions containing the metal complexes, and processes for making the metal complexes and the catalyst compositions are described for the manufacture of polymers from ethylenically unsaturated addition polymerizable monomers. The metal complexes have chemical structures corresponding to one of the following formulae: (Ia) (Ib) (VII) wherein MI. and MII. are metals; T is nitrogen or phosphorus; P is a carbon, nitrogen or phosphorus atom; groups R1, R2 and R3 may be linked to each other; Y is a divalent bridging group; X, X1, and X2 are anionic ligand groups with certain exceptions; D is a neutral Lewis base ligand; and s, o, k, i, ii, p, m, a, b, c, d, e, t, and y are numbers as further described in the claims.

## Claims

### Claim 1

A metal complex catalyst, which is a reaction product of:
A) at least one metal complex represented by Formula 2:
wherein:
MI is lanthanum, cerium, praseodymium, neodymium, or promethium;
N is nitrogen;
X, independently each occurrence, is fluoride, chloride, bromide or iodide or an —OR group, wherein R, independently each occurrence, is hydrogen, or a group having 1 to 80 atoms (not counting hydrogen), selected from hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, acyl-substituted hydrocarbyl, arylcarbonyl-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl-substituted hydrocarbyl, acyl or arylcarbonyl;
D is THF, 1,2-dimethoxyethane, triethylamine, tetramethylethylenediamine, or Et2O or;
y is the number 1, 2, 3, 4, 5, or 6;
t is the number 0, 1, 2 or 3;
RA and RB, independently each occurrence, are each a group having from 1 to 80 atoms (not counting hydrogen), selected from hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl; and
wherein the two ligands (RA)(RB)N are only linked via MI; and
B) at least one activator selected from:
a) C1-30 organoboron or organoaluminum compounds,
b) polymeric or oligomeric alumoxanes,
c) non-polymeric compatible, non-coordinating, ion-forming compounds, and
d) hydrocarbyl sodium, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium halide, and dihydrocarbyl magnesium; and
wherein A) and B) are brought together in a reaction medium at a temperature from −78° C. to 250° C.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein the reaction medium is selected from at least one of the following: an aliphatic hydrocarbon, an aromatic hydrocarbon or a halohydrocabon; and wherein the temperature is from −5° C. to 160° C.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein MI is neodymium.

### Claim 4 (depends on 1)

The catalyst of claim 1, further comprising a support.

### Claim 5 (depends on 4)

The catalyst of claim 4, wherein the support is selected from at least one of the following: clay, silica, layered silicates, alumina, activated carbon, graphite or carbon black.

### Claim 6 (depends on 1)

The catalyst of claim 1, wherein the activator comprises a combination of the following:
a) a trialkyl aluminum compound having from 1 to 4 carbon atoms in each alkyl group, and
b) a halogenated tri(hydrocarbyl)boron compound or halogenated tetrakis(hydrocarbyl)boron or -aluminum compound, each having from 1 to 20 carbon atoms in each hydrocarbyl group.

### Claim 7 (depends on 1)

The catalyst of claim 1, wherein the activator comprises a combination of the following:
a) a tris(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and
b) a polymeric or oligomeric alumoxane.

### Claim 8 (depends on 1)

The catalyst of claim 1, wherein the activator comprises a combination of the following:
a) a trialkyl aluminum or dialkyl aluminum hydride compound, and
b) boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, or titanium tetrafluoride.