# US 4,400,301 A · Transition metal compound

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

- Number: US 4,400,301 A
- Document ID: US4400301A
- Status: Granted
- Kind: A
- Application number: 05/939,212
- Filed: 1978-09-05
- Granted: 1983-08-23
- Earliest claimed: 1975-05-28
- Assignees: Imperial Chemical Industries PLC
- Inventors: John P. Candlin; Anthony D. Caunt; Ian G. Williams
- Web page: https://patentgrep.com/patent/US4400301A

## CPC

- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A solid compound of a transition metal is ground in the presence of aluminium chloride, titanium tetrachloride and at least one organo-Lewis Base compound. The transition metal compound is typically titanium trichloride. The Lewis Base compound is an organo-phosphorus compound, preferably one which also contains nitrogen, such as 2-dimethylamino-1,3-dimethyl-1,3,2-diazaphospholidine-2-oxide or an organo-sulphur compound such as diphenyl sulphone. The solid compound of the transition metal may include aluminium chloride and if the amount of this aluminium chloride is at least 50% molar, there is no need to make a separate addition of aluminium chloride to the mixture which is ground. The ground product can be used as a component of an olefine polymerization catalyst.

## Claims

### Claim 1

A process for the production of a transition metal composition which comprises the steps of reacting titanium tetrachloride with a solution, in an inert diluent, of a complex material of the formula TiAl.sub.2 Cl.sub.8 (arene); separating from the reaction mixture a titanium trichloride-aluminium chloride composition, and contacting the titanium trichloride-aluminium chloride composition with at least one organo-Lewis Base compound and titanium tetrachloride by grinding the titanium trichloride-aluminium chloride composition in the presence of the at least one organo-Lewis Base compound and the titanium tetrachloride.

### Claim 2 (depends on 1)

The process of claim 1 wherein the titanium trichloride-aluminium chloride composition has the formula TiCl.sub.3 cAlCl.sub.3 wherein c is from 0.50 up to 1.50.

### Claim 3 (depends on 1)

The process of claim 1 in which the organo-Lewis Base compound is an organo-Lewis Base compound containing at least one sulphur, nitrogen or phosphorus atom.

### Claim 4 (depends on 3)

The process of claim 3 in which the organo-Lewis Base compound is a compound of one of the formulae
R.sup.1 R.sup.2 R.sup.3 P(O).sub.m
R.sup.5 R.sup.6 R.sup.7 N ##STR11##
R.sup.11 R.sup.12 P(Q).sub.z ED or ##STR12## where R.sup.1, R.sup.2 and R.sup.3 are each, independently, an alkyl or aryl group, or a group --NR.sup.4.sub.2 or --OR.sup.4 ;
R.sup.4 is an alkyl group of 1 to 4 carbon atoms;
R.sup.5 and R.sup.6 are hydrocarbyl groups;
R.sup.7 is a hydrogen atom, an alkyl group or a group --C.sub.n H.sub.2n NR.sup.5 R.sup.6 ;
or R.sup.5 and R.sup.6, optionally with R.sup.7, together form a substituted or unsubstituted, saturated or unsaturated, condensed or uncondensed ring system;
X, or each X, is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.8 R.sup.9, or two groups X can together form a saturated or unsaturated hydrocarbon ring;
Y, or each Y, is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.8 R.sup.9, or two groups Y can together form a saturated or unsaturated hydrocarbon ring; or a group X and a group Y may be replaced by a link between the two phenyl groups attached to the --SO.sub.2 -- group, the linkage being either direct or through a group --O--, --CH.sub.2 --, --NR.sup.8 --, --S-- or --CO--;
R.sup.8 is a hydrogen atom or a hydrocarbyl group;
R.sup.9 is a hydrocarbyl group;
Z, or each Z, is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.8 R.sup.9, or two groups Z can together form a saturated or unsaturated hydrocarbon ring;
R.sup.10 is a hydrocarbyl group or a group ##STR13## R.sup.11 is a halogen atom, a hydrocarbyl group, a group --NR.sup.9.sub.2 or --OR.sup.9, a heterocyclic group or a group (E--L--G);
R.sup.12 is a halogen atom, a hydrocarbyl group, a group --NR.sup.9.sub.2 or --OR.sup.9, a heterocyclic group, a group (E--L--G) or ED;
each E is --O--, --S--, or --NR.sup.9 --, and may be the same or different;
G is --OR.sup.9, --SR.sup.9, --NR.sup.9.sub.2, --PR.sup.9.sub.2 or a heterocyclic ring system whereof the heteroatom is O, S, N, or P;
D is a group --LG or --P(Q).sub.z R.sup.11 R.sup.12, or, when R.sup.12 is ED, both the D groups may together form a group --L--;
L is a bivalent hydrocarbyl radical such that E and G or E and E are separated by not more than 3 carbon atoms;
Q is an oxygen or sulphur atom;
T is --S--, --O--, --NR.sup.9 --, or --CO--;
Z', or each Z', is, independently a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio or arylthio group, or a group --NR.sup.8 R.sup.9 ;
m is 0 or 1;
n is 1, 2 or 3;
p and q are each, independently, an integer from 0 up tp 5;
s is an integer from 0 up to 5;
y is a positive integer; and
z is 0 or 1.

### Claim 5 (depends on 1)

The process of claim 1 in which grinding is effected in the presence of from 0.01 up to 0.50 mole of titanium tetrachloride for each gramme atom of titanium which is present in the titanium trichloride-aluminium chloride composition.

### Claim 6 (depends on 1)

The process of claim 1 in which grinding is effected in the presence of from 0.10 up to 1.0 mole of the organo-Lewis Base compound for each gramme atom of titanium which is present in the titanium trichloride-aluminium chloride composition.

### Claim 7 (depends on 2)

The process of claim 2 in which grinding is effected in the presence of an amount of the organo-Lewis Base compound which is given by the relationship
L.B.=[TiCl.sub.4 ]+0.5[AlCl.sub.3 ].+-.0.10
where
L.B. is the amount of the organo-Lewis Base compound in moles;
[TiCl.sub.4 ] is the amount of titanium tetrachloride in moles; and
[AlCl.sub.3 ] is the total amount of aluminium chloride in moles which is present in the composition TiCl.sub.3 cAlCl.sub.3.

### Claim 8 (depends on 2)

The process of claim 2 wherein grinding is effected by ball milling at a temperature from -10.degree. C. up to 100.degree. C. for a time of from 5 hours up to 100 hours.

### Claim 9 (depends on 1)

The process of claim 1 wherein, as a final step, the composition obtained from the titanium trichloride-aluminium chloride composition, the at least one organo-Lewis Base compound and titanium tetrachloride is washed with an inert aliphatic or aromatic hydrocarbon liquid.

### Claim 10 (depends on 1)

An olefine polymerisation catalyst comprising
1. a transition metal composition which has been obtained by the process of claim 1; and
2. at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or IIA of the Periodic Table and an organo-aluminium compound.

### Claim 11 (depends on 10)

The catalyst of claim 10 which also contains
3. an organo-Lewis Base compound which is a compound of one of the formulae
R.sup.1 R.sup.2 R.sup.3 P(O).sub.m
R.sup.5 R.sup.6 R.sup.7 N ##STR14##
R.sup.11 R.sup.12 P(Q).sub.z ED or ##STR15## where D, E, Q, R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, X, Y, Z, Z', m, p, q, s and z are all as defined.

### Claim 12 (depends on 11)

The catalyst of claim 11 wherein component 3) is hexamethylphosphoric triamide; 2-dimethylamino-1,3-dimethyl-1,3,2-diazaphospholidine-2-oxide; N,N,N',N',N"-pentamethyl-N"-.beta.-dimethylaminoethylphosphoric triamide; N,N,N',N'-tetrametnylethylene-diamine; tributylamine or diphenylsulphone.

### Claim 13 (depends on 10)

The catalyst of claim 10 which also contains
4. a substituted or unsubstituted polyene.

### Claim 14 (depends on 4)

The process of claim 4 wherein the organo-Lewis Base compound is a compound of one of the formulae ##STR16## where R.sup.9, R.sup.10, T, X, Y, Z, Z', p, q, and s are all as defined.