# US 8,772,521 B2 · Metal alkyl-arenes and processes for the preparation thereof

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- Number: US 8,772,521 B2
- Document ID: US8772521B2
- Status: Granted
- Kind: B2
- Application number: 13/996,842
- Filed: 2011-12-23
- Published: 2013-11-07
- Granted: 2014-07-08
- Earliest claimed: 2010-12-27
- Assignees: Versalis S.P.A.
- Applicants: Guido Pampaloni; Filippo Renili; Anna Sommazzi; Fabio Marchetti; Francesco Masi; Mario Polesello
- Inventors: Guido Pampaloni; Filippo Renili; Anna Sommazzi; Fabio Marchetti; Francesco Masi; Mario Polesello
- Web page: https://patentgrep.com/patent/US8772521B2

## CPC

- C07F 19/00: Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- B01J 31/122: {Metal aryl or alkyl compounds}
- C07F 7/003: {without C-Metal linkages}
- C08F 4/42: Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Metal alkyl-arene having general formula (I) or (Ia): M (η6-arene)2AlqXrRs (I) M (η6-arene)AlqXrRs (Ia) wherein: —M represents zirconium (Zr), hafnium (Hf), or mixtures thereof, preferably zirconium; —arene represents a benzene, or a benzene 10 substituted with from 1 to 6 linear or branched C1-C6 alkyl groups, or mixtures thereof; —X represents a halogen atom selected from chlorine, bromine, fluorine, iodine, preferably chlorine; —R represents a linear or branched C1-C15 alkyl group; —q is a number ranging from 2 to 6, preferably 3 for a metal alkyl-arene having general formula (I), 2 for a metal alkyl-arene having general formula (Ia); —r is a number ranging from 1 to 20, preferably 9 for a metal alkyl-arene having general formula (I), 6 for a metal alkyl-arene having general formula (Ia); —s is a number ranging from 1 to 6, preferably 2. Said metal alkyl-arene can be advantageously used for the preparation of solid components of catalysts for the (co)polymerization of α-olefins.

## Claims

### Claim 1

A metal alkyl-arene having general formula (I) or (Ia):
M(η6-arene)2AlqXrRs (I)
M(η6-arene)AlqXrRs (Ia)
wherein:
M represents zirconium (Zr), hafnium (Hf), or mixtures thereof;
arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C1-C6 alkyl groups, or mixtures thereof;
X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine, and iodine;
R represents a linear or branched C1-C15 alkyl group;
q is a number ranging from 2 to 6;
r is a number ranging from 1 to 20; and
s is a number ranging from 1 to 6.

### Claim 2 (depends on 1)

The metal alkyl-arene according to claim 1, wherein M represents zirconium.

### Claim 3 (depends on 1)

The metal alkyl-arene according to claim 1, wherein X represents chlorine.

### Claim 4 (depends on 1)

The metal alkyl-arene according to claim 1, wherein q is 3 in the case of the metal alkyl-arene having general formula (I), 2 in the case of the metal alkyl-arene having general formula (Ia).

### Claim 5 (depends on 1)

The metal alkyl-arene according to claim 1, wherein r is 9 in the case of the metal alkyl-arene having general formula (I), 6 in the case of the metal alkyl-arene having general formula (Ia).

### Claim 6 (depends on 1)

The metal alkyl-arene according to claim 1, wherein s is 2.

### Claim 7 (depends on 1)

The metal alkyl-arene according to claim 1, wherein in the metal alkyl-arene having general formula (I) or (Ia), said arene is selected from the croup consisting of: benzene, toluene, ortho-xylene, meta-xylene, para-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene (mesitylene), hexamethylbenzene, and mixtures thereof.

### Claim 8 (depends on 1)

The metal alkyl-arene according to claim 1, wherein in the metal alkyl-arene having general formula (I) or (Ia), said group R is selected from the group consisting of: ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-tridecyl.

### Claim 9 (depends on 1)

A process for the preparation of a metal alkyl-arene having general formula (I) or (Ia) according to claim 1, which comprises reacting the following components:
(i) at least one metal halide having general formula (II):
MX4 (II)
wherein:
M represents zirconium (Zr), hafnium (Hf), or mixtures thereof;
X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine, and iodine;
(ii) metallic aluminium;
(iii) optionally, at least one aluminium halide having general formula (III):
AlX3 (III)
wherein:
X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine, and iodine;
(iv) at least one arene;
(v) at least one alkylating agent selected from:
metal alkyls having general formula (IV):
M1(R1)m (IV)
wherein:
M1 represents aluminium, magnesium, zinc, or lithium; R1 represents a linear or branched C1-C20 alkyl group; m is 1, 2 or 3;
aluminium alkyl chlorides having general formula (V):
Al(R2)nCl3-n
wherein R2 represents a linear or branched C1-C20 alkyl group; n is 1 or 2.

### Claim 10 (depends on 9)

The process according to claim 9, wherein said process is carried out operating at a molar ratio between the aluminium present in the aluminium halide having general formula (III) and the metal present in the metal halide having general formula (II), ranging from 1 to 4.

### Claim 11 (depends on 9)

The process according to claim 9, wherein the molar ratio between the metal present in the metal alkyls having general formula (IV) and the metal present in the metal halide having general formula (II), ranges from 1 to 10.

### Claim 12 (depends on 9)

The process according to claim 9, wherein said process is carried out operating at a molar ratio between the aluminium present in the aluminium alkyl chlorides having general formula (V) and the metal present in the metal halide having general formula (II), ranging from 1 to 6.

### Claim 13 (depends on 9)

The process according to claim 9, wherein said process is carried out in the presence of an aliphatic or aromatic hydrocarbon solvent.

### Claim 14 (depends on 9)

The process according to claim 9, wherein said process is carried out at a temperature ranging from 70° C. to the reflux temperature of the suspension obtained by putting the above components (i), (ii), (iv), (v) and optionally (iii), in contact.

### Claim 15 (depends on 9)

The process according to claim 9, wherein said process is carried out for a time ranging from 1 hour to 10 hours.

### Claim 16 (depends on 1)

A solution, or oil, comprising at least one metal alkyl-arene having general formula (I) or (Ia) according to claim 1.

### Claim 17 (depends on 16)

A process using the solution or oil according to claim 16, for the preparation of solid catalyst components for the (co)polymerization of α-olefins.

### Claim 18

A process for the preparation of a metal alkyl-arene having general formula (I) or (Ia) which comprises putting the following components in contact:
(i′) at least one metal arene having general formula (VI) or (VIa):
M(η6-arene)2AlqXr (VI)
M(η6-arene)AlqXr (VIa)
wherein:
M represents zirconium (Zr), hafnium (Hf), or mixtures thereof;
arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C1-C6 alkyl groups, or mixtures thereof;
X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine, and iodine;
q is a number ranging from 2 to 6;
r is a number ranging from 8 to 20;
(ii′) at least one alkylating agent selected from:
metal alkyls having general formula (IV):
M1(R1)m (IV)
wherein M1 represents aluminium, magnesium, zinc, or lithium; R1 represents a linear or branched C1-C20 alkyl group; m is 1, 2, or 3;
aluminium alkyl chlorides having general formula (V):
Al(R2)nCl3-n (V)
wherein R2 represents a linear or branched C1-C20 alkyl group; n is 1 or 2.

### Claim 19 (depends on 18)

The process according to claim 18, wherein said process is carried out operating at a molar ratio between the metal present in the metal alkyls having general formula (IV), or the aluminium present in the aluminium chlorides having general formula (V), and the metal present in the metal arene having general formula (VI) or (VIa), ranging from 1 to 20.

### Claim 20 (depends on 18)

The process according to claim 18, wherein said process is carried out in the presence of an aliphatic or aromatic hydrocarbon solvent, under the operating conditions at a temperature ranging from 70° C. to the reflux temperature of the suspension.