Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization

• US 4,302,565 A
• Filed: 02/16/1979
• Issued: 11/24/1981
• Est. Priority Date: 03/31/1978
• Status: Expired due to Term

• Current Assignee: Clutch Games, Inc.
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Wagner, Burkhard E., Karol, Frederick J., Goeke, George L.
• Primary Examiner(s): Smith, Edward J.
• Application Number:
  US06/012,720
• Time in Patent Office: 1,012 Days
• Field of Search: 526/124, 526/125, 526/88
• US Class Current: 526/88
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 4/6425 containing magnesium
• CPC Class Codes: Y10S 526/904 Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts

Abstract

A catalyst formed from selected organo aluminum compounds and a precursor composition of the formula

Mg.sub.m Ti.sub.l (OR).sub.n X.sub.p [ED].sub.q

wherein ED is a selected electron donor compound

m is ≧0.5 to ≦56

n is 0, 1 or 2

p is ≦2 to ≧116

q is ≧2 to ≦85

R is a C₁ to C₁₄ aliphatic or aromatic hydrocarbon radical, or COR'"'"' wherein R'"'"' is a C₁ to C₁₄ 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 form and impregnated in a porous inert carrier material.

A process for preparing such catalyst.

A process for using said catalyst to readily prepare ethylene copolymers having a density of about ≧0.91 to ≦0.94 and a melt flow ratio of ≧22 to ≦32 in a low pressure gas phase process at a productivity of ≧50,000 pounds of polymer per pound of Ti.

Novel polymers and molded articles are prepared.

Claims

1. A continuous catalytic process for producing ethylene copolymer with a Ti containing catalyst at a productivity of ≧

50,000 pounds of polymer per pound of Ti in a fluid bed reactor under a pressure of <

1000 psi in the gas phase

said polymer being produced in granular form and having a density of ≧

0.91 to ≦

0.94 and a melt flow ratio of ≧

22 to ≦

32

which comprises polymerizing ethylene with at least one C₃ to C₈ alpha olefin at a temperature of about 30°

to 105°

C. by contacting the monomer charge with, in the presence of about 0 to 2.0 mols of hydrogen per mol of ethylene in the gas phase reaction zone, particles of a catalyst composition comprising a precursor composition of the formula

space="preserve" listing-type="equation">Mg.sub.m Ti.sub.1 (OR).sub.n X.sub.p [ED]q

wherein R is a C₁ to C₁₄ aliphatic or aromatic hydrocarbon radical, or COR'"'"' wherein R'"'"' is a C₁ to C₁₄ 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 ≧

0.5 to ≦

56,

n is 0, 1 or 2,

p is ≧

2 to ≦

116, and

q is ≧

2 to ≦

85,

said precursor composition being impregnated in a porous support and being

first partially activated outside of said reactor in a hydrogen slurry with >

0 to ≦

10 mols of activator compound per mol of Ti in said precursor composition, and

then completely activated in said reactor with >

10 to ≦

400 mols of activator compound per mol of Ti in said precursor composition in the absence of a solvent so as to avoid the need for drying the fully active catalyst to remove solvent therefrom,

said activator compound having the formula

space="preserve" listing-type="equation">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 C₁ to C₁₄ saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c+d+e=3,

said electron donor compound being a liquid organic compound in which said precursor composition is soluble and which is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic esters, cyclic ethers and aliphatic ketones.

2. A process as in claim 1 which is conducted under a mass gas flow rate of about 1.5 to 10 times Gmf.

3. A process as in claim 2 which is conducted at a productivity of ≧

100,000.

4. A process as in claim 3 in which said precursor composition is partially activated with about >

0 to ≦

10 mols of said activator compound outside of said reactor and is completely activated in said reactor with sufficient activator compound to provide an Al/Ti ratio of about 15 to 60 in said reactor.

5. A process as in claim 1 in which ethylene is copolymerized with propylene.

6. A process as in claim 1 in which ethylene is copolymerized with butene-1.