Polymerization process using a supported constrained geometry catalyst

• US 8,957,167 B2
• Filed: 07/27/2010
• Issued: 02/17/2015
• Est. Priority Date: 07/28/2009
• Status: Active Grant

• Current Assignee: Univation Technologies LLC (Dow, Inc.)
• Original Assignee: Univation Technologies LLC (Dow, Inc.)
• Inventors: Hussein, F. David, Cann, Kevin J., Stakem, F. Gregory, Schoeb-Wolters, Ann M., Mariott, Wesley R., Farley, James M., Awe, Michael D.
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US13/376,669
• Publication Number:
  US 20120130032A1
• Time in Patent Office: 1,666 Days
• Field of Search: 526/74, 526/133, 526/134, 526/143, 526/147, 526/160, 526/943, 502/103, 502/152, 502/155
• US Class Current: 526/74
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/005 by addition of a scale inhibitor to the polymerisation medium
• CPC Class Codes: C08F 2/34 Polymerisation in gaseous state
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/01 Additive used together with the catalyst, excluding compounds containing Al or B
• CPC Class Codes: C08F 2410/02 Anti-static agent incorporated into the catalyst
• CPC Class Codes: C08F 2500/08 Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

A polymerization process includes contacting the following in a gas-phase reactor system under polymerization conditions for making a polymer product: a metallocene-based catalyst system including a supported constrained geometry catalyst, at least one monomer, and an additive selected from a group consisting of an aluminum distearate, an ethoxylated amine, and a mixture thereof. The additive may be selected from a group consisting of an aluminum distearate, an ethoxylated amine, polyethylenimines, and other additives suitable for use in the production of polymers for food contact applications and end products, including a mixture of a polysulfone copolymer, a polymeric polyamine, and oil-soluble sulfonic acid, in a carrier fluid, and mixtures thereof.

Claims

1. A polymerization process, comprising:

contacting in a gas-phase reactor system under polymerization conditions for making a polymer product;

a metallocene-based catalyst system comprising a supported constrained geometry catalyst, wherein the supported constrained geometry metallocene catalyst includes a borate anion;

at least one monomer; and

an additive wherein the additive comprises a mixture of aluminum distearate and ethoxylated amine, wherein the additive is added to the reactor system separately from the catalyst system, and wherein the additive is present in the reactor system at between about 5 and about 20 parts per million weight (ppmw);

wherein the carrier fluid comprises less than 0.1 wt % toluene and other aromatic compounds, less than 0.1 wt % isopropanol and less than 0.1 wt % methanol.

3. The polymerization process of claim 1, wherein the ethoxylated amine is ethoxylated stearyl amine.

7. The metallocene-based catalyst system of claim 3 or 4, wherein z′

is 1 or 2, q is 1, and r is 1.

2. A metallocene-based catalyst system, comprising:

a supported constrained geometry metallocene catalyst, wherein the supported constrained geometry metallocene catalyst includes a borate anion; and

an additive wherein the additive is a mixture of aluminum distearate and ethoxylated amine, wherein the additive is added to the reactor system separately from the catalyst system, and wherein the additive is present in the reactor system at between about 5 and about 20 parts per million weight (ppmw);

wherein the carrier fluid comprises less than 0.1 wt % toluene and other aromatic compounds, less than 0.1 wt % isopropanol and less than 0.1 wt % methanol.

4. The metallocene-based catalyst system of claim 2, wherein the ethoxylated amine is ethoxylated stearyl amine.

5. The metallocene-based catalyst system of claim 2, wherein the borate anion is represented by the formula [BQ4-z′

(Gq(T—

H)r)z′

]d-, wherein;

B is boron in a valence state of 3;

Q is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals;

z′

is an integer in a range from 1 to 4;

G is a polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and

r groups (T—

H);

q is an integer, 0 or 1;

the group (T—

H) is a radical wherein T comprises O, S, NR, or PR, the O, S, N or P atom of which is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical or hydrogen;

r is an integer from 1 to 3; and

d is 1.

6. The metallocene-based catalyst system of claim 2, wherein the borate anion is represented by the formula [BQ4-z′

(Gq(T—

MoRCx-1Xay)r)z′

]d-, wherein;

B is boron in a valence state of 3;

Q is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals;

z′

is an integer in a range from 1 to 4;

G is a polyvalent hydrocarbon radical having r+1 valencies bonded to B and r groups (T—

MoRCx-1Xay);

q is an integer, 0 or 1;

the group (T—

MoRCx-1Xay) is a radical wherein T comprises O, S, NR, or PR, the O, S, N or P atom of which is bonded to Mo, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical or hydrogen;

Mo is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements,

RC independently each occurrence is hydrogen or a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilylhydrocarbyl;

Xa is a noninterfering group having from 1 to 100 nonhydrogen atoms which is halo-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy or halide;

x is a nonzero integer which may range from 1 to an integer equal to the valence of Mo;

y is zero or a nonzero integer which may range from 1 to an integer equal to 1 less than the valence of Mo; and

x+y equals the valence of Mo.

r is an integer from 1 to 3; and

d is 1.