Modified phosphinimine catalysts for olefin polymerization

• US 9,127,106 B2
• Filed: 09/11/2014
• Issued: 09/08/2015
• Est. Priority Date: 06/09/2011
• Status: Active Grant

• Current Assignee: Nova Chemicals
• Original Assignee: Nova Chemicals
• Inventors: Hoang, Peter Phung Minh, Lam, Patrick, Ker, Victoria, Baar, Cliff Robert, Carter, Charles Ashton Garret, Jiang, Yan
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US14/483,425
• Publication Number:
  US 20140378632A1
• Time in Patent Office: 362 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

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 process for producing a polyethylene copolymer having a density of from 0.910 g/cm³ to 0.927 g/cm³, a melt index (I₂) of from 0.25 to 5.0 g/10 min, a melt flow ratio (I₂₁/I₂)<

20, and a molecular weight distribution (M_w/M_n)≦

3.0;

the process comprising polymerizing ethylene and an alpha olefin in a gas phase reactor with a polymerization catalyst comprising;

i) a phosphinimine catalyst;

ii) an inert support;

iii) a cocatalyst; and

iv) a catalyst modifier;

wherein the catalyst modifier is present in from 0.25 to 6.0 weight percent based on the weight of i), ii) and iii) of the polymerization catalyst and comprises a compound having the formula;

R¹R²_xN((CH₂)_nOH)_y where 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, y is 1 when x is 1, y is 2 when x is 0, each n is independently an integer from 1 to 30 when y is 2, and n is an integer from 1 to 30 when y is 1.

2. The process of claim 1 wherein the catalyst modifier comprises at least one compound represented by the formula:

R¹N((CH₂)_nOH)((CH₂)_mOH) where R¹ is a hydrocarbyl group having from 5 to 30 carbon atoms, and n and m are integers from 1 to 20.

3. The process of claim 1 wherein the catalyst modifier comprises at least one compound represented by the formula:

R¹N((CH₂)_nOH)₂ where R¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and n is independently an integer from 1-20.

4. The process of claim 1 wherein the catalyst modifier comprises at least one compound represented by the formula:

R¹N((CH₂)_nOH)₂ where R¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and n is 2 or 3.

5. The process of claim 1 wherein the catalyst modifier comprises at least one compound represented by the formula:

R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to 22 carbon atoms.

6. The process of claim 1 wherein the catalyst modifier comprises a compound represented by the formula:

C₁₈H₃₇N(CH₂CH₂OH)₂.

7. The process claim 1 wherein the catalyst modifier comprises compounds represented by the formulas:

C₁₃H₂₇N(CH₂CH₂OH)₂ and C₁₅H₃₁N(CH₂CH₂OH)₂.

8. The process of claim 1 wherein the catalyst modifier is a mixture of compounds represented by the formula:

R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to 18 carbon atoms.

9. The process of claim 1 wherein the phosphinimine catalyst has the formula:

(L)(PI)MX₂, where M is Ti, Zr or Hf;

PI is a phosphinimine ligand having the formula R₃P═

N—

, where 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.

10. The process of claim 1 wherein the phosphinimine catalyst has the formula:

(L)((t-Bu)₃P═

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

X is an activatable ligand.

11. The process of claim 1 wherein the phosphinimine catalyst has the formula:

(1,2-(n-R*)(C₆F₅)Cp)Ti(N═

P(t-Bu)₃)X₂ where R* is a straight chain alkyl group; and

X is an activatable ligand.

12. The process of claim 1 wherein the phosphinimine catalyst has the formula:

(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═

P(t-Bu)₃)Cl₂.

13. The process of claim 1 wherein the cocatalyst is selected from ionic activators, alkylaluminoxanes and mixtures thereof.

14. The process of claim 1 wherein the inert support is silica.

15. The process of claim 1 wherein the process is a gas phase process carried out in a fluidized bed reactor.

16. The process of claim 1 wherein the catalyst modifier is present in from 0.5 to 4.5 weight percent based on the weight of i), ii) and iii) of the polymerization catalyst.