# US 4,395,359 A · Polymerization catalyst, process for preparing, and use for ethylene homopolymerization

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- Number: US 4,395,359 A
- Document ID: US4395359A
- Status: Granted
- Kind: A
- Application number: 06/249,447
- Filed: 1981-03-31
- Granted: 1983-07-26
- Earliest claimed: 1978-03-31
- Assignees: Union Carbide Corporation
- Inventors: Burkhard E. Wagner; Frederick J. Karol; George L. Goeke; Robert J. Jorgensen; Nils Friis
- Web page: https://patentgrep.com/patent/US4395359A

## CPC

- C08F 110/02: Ethene
- Y10S 526/901: Monomer polymerized in vapor state in presence of transition metal containing catalyst
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A catalyst formed from selected organo aluminum compounds and a precursor composition of the formula Mg.sub.m Ti.sub.1 (OR).sub.n X.sub.p [ED].sub.q wherein ED is a selected electron donor compound m is .gtoreq.0.5 to .ltoreq.56 n is 0 or 1 p is .gtoreq.6 to .ltoreq.116 q is .gtoreq.2 to .ltoreq.85 R is a C.sub.1 to C.sub.14, aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, and X is selected from the group consisting of Cl, Br, I, or mixtures thereof, which catalyst is in particulate from and diluted with an inert carrier material; a process for preparing such catalyst; a process for using said catalyst to readily prepare ethylene homopolymer having a density of about .gtoreq.0.958 to .ltoreq.0.972 and a melt flow ratio of .gtoreq.22 to .ltoreq.32 in a low pressure gas phase process at a productivity of .gtoreq.50,000 pounds of polymer per pound of Ti. Novel polymers and molded articles are prepared.

## Claims

### Claim 1

A process for preparing a catalyst composition which comprises
(A) forming, a precursor composition of the formula
Mg.sub.m Ti.sub.1 (OR).sub.n X.sub.p [ED].sub.q
wherein
R is C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical,
X is selected from the group consisting of Cl, Br, I, or mixtures thereof,
ED is an electron donor compound,
m is .gtoreq.0.5 to .ltoreq.56
n is 0 or 1
p is .gtoreq.6 to .ltoreq.116 and
q is .gtoreq.2 to .ltoreq.85
by dissolving at least one magnesium compound and at least one titanium compound in at least one electron donor compound so as to thereby form a solution of said precursor composition in said electron donor compound, and recovering said precursor composition from said solution,
said magnesium compound having the structure MgX.sub.2,
said titanium compound having the structure Ti(OR).sub.a X.sub.b
wherein a is 0 or 1, b is 2 to 4 inclusive and a+b=3 or 4
said electron donor compound being a liquid organic compound in which said magnesium compound and said titanium compound are soluble and which is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones,
and said magnesium compound, said titanium compound and said electron donor compound being employed in such amounts as to satisfy the values of m, n, p and q,
(B) diluting said precursor composition with about 1 to 10 parts by weight, per part by weight of said precursor composition, of at least one inert carrier material,
(C) partially activating the precursor composition outside the polymerization zone in a hydrocarbon slurry with >0 to <10 mols of activator compound per mol of titanium in said precursor composition, said activator compound having the structure
Al(R").sub.c X'.sub.d H.sub.e
wherein X' is Cl or OR'", R" and R'" are the same or different and are C.sub.1 to C.sub.14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c+d+e=3, and
(D) completely activating the precursor composition in a fluid bed polymerization zone with .gtoreq.10 to about 400 mols of said activator compound in the absence of a solvent so as to avoid the need for drying the fully active catalyst to remove the solvent therefrom.

### Claim 2 (depends on 1)

A process as in claim 1 in which said magnesium compound comprises MgCl.sub.2.

### Claim 3 (depends on 2)

A process as in claim 2 in which said electron donor compound comprises at least one ether.

### Claim 4 (depends on 3)

A process as in claim 3 in which said electron donor compound comprises tetrahydrofuran.

### Claim 5 (depends on 3)

A process as in claim 3 in which said titanium compound comprises TiCl.sub.4.

### Claim 6 (depends on 5)

A process as in claim 5 in which said inert carrier material comprises silica.

### Claim 7 (depends on 1)

A catalyst formed by the process of claim 1.