# US 2013/0253153 A1 · Processes for the Polymerization of Olefins with Extracted Metal Carboxylate Salts

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- Number: US 2013/0253153 A1
- Document ID: US20130253153A1
- Status: Published application
- Kind: A1
- Application number: 13/988,956
- Filed: 2011-11-10
- Published: 2013-09-26
- Earliest claimed: 2010-11-30
- Assignees: Univation Technologies, LLC
- Inventors: R. Eric Pequeno; Fathi David Hussein; Kevin Joseph Cann; Chi-I Kuo; Bruce Jon Savatsky; Eric J. Markel; Daniel Paul Zilker, Jr.; Agapios Kyriacos Agapiou; David M. Glowczwski
- Web page: https://patentgrep.com/patent/US20130253153A1

## CPC

- C08F 4/642: Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 4/602: Component covered by group C08F4/60 with an organo-aluminium compound {(C08F4/60003 - C08F4/60196 take precedence)}
- C08F 4/646: Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/6428: {with an aluminoxane, i.e. a compound containing an Al-O-Al- group}
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B
- C08F 2410/02: Anti-static agent incorporated into the catalyst
- Y10S 526/943: Polymerization with metallocene catalysts
- 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

Processes for the polymerization of olefins with extracted metal carboxylate salts are provided. The polymerization processes have increased productivity and/or increased resin bulk density.

## Claims

### Claim 1

A polymerization process comprising: polymerizing an olefin in a reactor in the presence of a catalyst composition and an extracted metal carboxylate salt, wherein the extracted metal carboxylate salt was produced by extraction of a metal carboxylate salt with an organic solvent having a dielectric constant at 25° C. of greater than or equal to 3.0.

### Claim 2 (depends on 1)

The process of claim 1 wherein the extracted metal carboxylate salt is essentially free of free carboxylic acids.

### Claim 3 (depends on 1)

The process of claim 1, wherein the extracted metal carboxylate salt contains less than 1 wt % of total free acid based on the total weight of the extracted metal carboxylate salt.

### Claim 4 (depends on 1)

The process of claim 1, wherein the organic solvent is selected from the group consisting of a C1-C10 alcohol, a C1-C10 ketone, a C1-C10 ester, a C1-C10 ether, a C1-C10 alkyl halide, a C1-C10 alkylonitrile, a C1-C10 dialkyl sulfoxide, and combinations thereof.

### Claim 5

(canceled)

### Claim 6 (depends on 1)

The process of claim 1, wherein the metal carboxylate salt is represented by the formula:
MQx(OOCR)y
where M is a Group 13 metal from the Periodic Table of Elements;
Q is a halogen, hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group;
R is a hydrocarbyl radical having from 12 to 30 carbon atoms;
x is an integer from 0 to 3;
y is an integer from 1 to 4; and
the sum of x and y is equal to the valence of the metal M.

### Claim 7 (depends on 1)

The process of claim 1, wherein the extracted metal carboxylate salt comprises an aluminum carboxylate.

### Claim 8 (depends on 1)

The process of claim 1, wherein the metal carboxylate salt comprises an aluminum stearate selected from the group consisting of an aluminum mono-stearate, an aluminum di-stearate, an aluminum tri-stearate, and combinations thereof.

### Claim 9 (depends on 1)

The process of claim 1, further comprising the step of adding a continuity additive comprising the extracted metal carboxylate salt into the reactor, wherein the continuity additive and the catalyst composition are added to the reactor separately.

### Claim 10 (depends on 1)

The process of claim 1, further comprising adding the catalyst compound to the reactor in combination with a continuity additive comprising the extracted metal carboxylate salt.

### Claim 11 (depends on 1)

The process of claim 1, wherein the catalyst composition further comprises a support, and wherein the catalyst compound is a metallocene catalyst compound, and wherein the metallocene catalyst compound and the support are combined utilizing incipient wetness impregnation.

### Claim 12 (depends on 1)

The process of claim 1, wherein the catalyst composition further comprises a support and an activator, and wherein the catalyst compound is a metallocene catalyst compound comprising at least one atom selected from the group consisting of a titanium atom, a zirconium atom, and a hafnium atom.

### Claim 13 (depends on 1)

The process of claim 1, wherein the catalyst compound is a metallocene compound, and wherein the metallocene compound is selected from the group consisting of (Pentamethylcyclopentadienyl) (Propyl cyclopentadienyl) MX2, Tetramethylcyclopentadienyl) (Propyl cyclopentadienyl) MX2, (Tetramethylcyclopentadienyl) (Butyl cyclopentadienyl) MX2, Me2Si(Indenyl)2MX2, Me2Si(Tetrahydroindenyl)2 MX2, (n-propyl cyclopentadienyl)2 MX2, (n-butyl cyclopentadienyl)2 MX2, (1-Methyl, 3-Butyl cyclopentadienyl)2 MX2, HN(CH2CH2N(2,4,6-Me3-Phenyl))2 MX2, HN(CH2CH2N(2,3,4,5,6-Me5-Phenyl))2 MX2, (Propyl cyclopentadienyl) (Tetramethylcyclopentadienyl) MX2, (Butyl cyclopentadienyl)2 MX2, (Propyl cyclopentadienyl)2 MX2, and combinations thereof, wherein M is Zr or Hf, and X is selected from the group consisting of F, Cl, Br, I, Me, Bnz, CH2SiMe3, C1 to C5 alkyls, and C1 to C5 alkenyls.

### Claim 14 (depends on 1)

The process of claim 1, wherein the catalyst composition comprises a support and an activator, and wherein the catalyst compound is a metallocene catalyst compound selected from (1-Methyl, 3-Butyl cyclopentadienyl)2 ZrX2, where X is selected from the group consisting of F, Cl, Br, I, and Me.

### Claim 15 (depends on 1)

The process of claim 1, wherein the catalyst composition comprises a metallocene catalyst compound and at least one other catalyst compound selected from a Ziegler-Natta catalyst, a chromium-based catalyst, a metallocene catalyst, a Group-15 catalyst, and combinations thereof.

### Claim 16 (depends on 1)

The process of claim 1, wherein the process has increased catalyst productivity versus the same process except that the metal carboxylate salt has not been extracted.

### Claim 17 (depends on 1)

A polymer product comprising a polyolefin produced by the process of claim 1.

### Claim 18 (depends on 17)

The polymer of claim 17 wherein the polymer has increased resin bulk density versus a polymer produced by the same process except that the metal carboxylate salt has not been extracted.

### Claim 19

A polymerization process for the production of an ethylene alpha-olefin copolymer, the polymerization process comprising:
contacting ethylene and an alpha-olefin with a catalyst composition in a reactor under polymerization conditions to produce the ethylene alpha-olefin copolymer, wherein the catalyst composition comprises a polymerization catalyst and a first extracted metal carboxylate salt, wherein the first extracted metal carboxylate salt was produced by extraction of a metal carboxylate salt with an organic solvent having a dielectric constant at 25° C. of greater than or equal to 3.0; and
adding a continuity additive comprising a second extracted metal carboxylate salt into the reactor, wherein the continuity additive and the catalyst composition are added to the reactor separately, wherein the second extracted metal carboxylate salt was produced by extraction of a metal carboxylate salt with an organic solvent having a dielectric constant at 25° C. of greater than or equal to 3.0.

### Claim 20 (depends on 19)

The process of claim 19, wherein the first extracted metal carboxylate salt and the second extracted metal carboxylate salt are each essentially free of free carboxylic acids.

### Claim 21 (depends on 19)

The process of claim 19, wherein the metal carboxylate salts extracted to produce the first and second extracted metal carboxylate salts are independently selected from aluminum mono-stearate, an aluminum di-stearate, an aluminum tri-stearate, and combinations thereof.