Modified phosphinimine catalysts for olefin polymerization

• US 9,243,092 B2
• Filed: 12/11/2014
• Issued: 01/26/2016
• Est. Priority Date: 06/09/2011
• Status: Active Grant

• Current Assignee: Nova Chemicals
• Original Assignee: Nova Chemicals
• Inventors: Hoang, Peter Phung Minh, Ker, Victoria, Carter, Charles Ashton Garret, Quaiattini, Robert Joseph Louis, Phinney, Amy Elizabeth
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US14/567,035
• Publication Number:
  US 20150094433A1
• Time in Patent Office: 411 Days
• US Class Current: 1/1
• 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 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• 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 2420/04 Cp or analog not bridged to a non-Cp X ancillary anionic donor
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/10 Short chain branches
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/26 Use as polymer for film forming
• CPC Class Codes: C08F 4/6494 containing oxygen
• CPC Class Codes: C08F 4/6495 containing nitrogen
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• 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

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Claims

1. A polymerization process comprising contacting ethylene and an alpha olefin with a polymerization catalyst in a gas phase reactor, wherein the polymerization catalyst comprises a titanium based phosphinimine catalyst, a silica support, an alkylaluminoxane cocatalyst, and a catalyst modifier having the formula:

R¹R²_xN((CH₂)_nOH)_y wherein R¹ is a hydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0;

when x is 1, y is 1, and n is an integer from 1 to 30;

when x is 0, y is 2, and each n is independently an integer from 1 to 30; and

further wherein the process produces a polyethylene copolymer having

i) a bulk density of at least 18 lbs/ft³ and,

ii) a polymer flowability of 30 seconds or less,

at a productivity of at least 2000 grams of polymer per gram of polymerization catalyst.

2. The process of claim 1 wherein the titanium based phosphinimine catalyst has the formula:

(L)(PI)TiX₂, where PI is a phosphinimine ligand having the formula R₃P═

N—

, wherein R is independently selected from hydrogen, halogen, and C₁-C₂₀ hydrocarbyl;

L is a ligand selected from cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, and substituted fluorenyl; and

X is an activatable ligand.

3. The process of claim 1 wherein the titanium based phosphinimine catalyst has the formula:

(L)((t-Bu)₃P═

N)TiX₂, wherein L is a cyclopentadienyl ligand, a substituted cyclopentadienyl ligand, an indenyl ligand, or a substituted indenyl ligand; and

X is an activatable ligand.

4. The process of claim 1 wherein the titanium based phosphinimine catalyst has the formula:

(L)((t-Bu)₃P═

N)TiX₂, where L is a substituted cyclopentadienyl ligand, or a substituted indenyl ligand; and

X is an activatable ligand.