Modified phosphinimine catalysts for olefin polymerization

• US 9,321,859 B2
• Filed: 07/31/2014
• Issued: 04/26/2016
• 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:
  US14/447,720
• Publication Number:
  US 20140357817A1
• Time in Patent Office: 635 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 2410/02 Anti-static agent incorporated into the catalyst
• 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 4/65912 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 polymerization process comprising contacting ethylene and at least one alpha olefin with a polymerization catalyst in a gas phase reactor, the 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 0.5 to 4.5 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; and

wherein the phosphinimine catalyst has the formula;

(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═

N)TiX₂, where X is an activatable ligand.

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 anywhere 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 anywhere 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 anywhere 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 anywhere 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 of 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 anywhere from 8 to 18 carbon atoms.

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

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

11. 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 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;

wherein the phosphinimine catalyst has the formula;

(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═

N)TiX₂, where X is an activatable ligand.

12. The polymerization catalyst of claim 11 wherein the catalyst modifier is present in from 1.0 to 4.0 weight percent based on the weight of i), ii) and iii) of the polymerization catalyst.

13. The polymerization catalyst of claim 11 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 anywhere from 5 to 30 carbon atoms, and n and m are integers from 1 to 20.

14. The polymerization catalyst of claim 11 wherein the catalyst modifier comprises at least one compound represented by the formula:

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

15. The polymerization catalyst of claim 11 wherein the catalyst modifier comprises at least one compound represented by the formula:

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

16. The polymerization catalyst of claim 11 wherein the catalyst modifier comprises at least one compound represented by the formula:

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

17. The polymerization catalyst of claim 11 wherein the catalyst modifier comprises a compound represented by the formula:

C₁₈H₃₇N(CH₂CH₂OH)₂.

18. The polymerization catalyst claim 11 wherein the catalyst modifier comprises compounds represented by the formulas:

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

19. The polymerization catalyst of claim 11 wherein the catalyst modifier is a mixture of compounds represented by the formula:

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

20. The polymerization catalyst of claim 11 wherein the cocatalyst is selected from the group consisting of ionic activators, alkylaluminoxanes and mixtures thereof.

21. The polymerization catalyst of claim 11 wherein the inert support is silica.

22. A polymerization process comprising contacting ethylene and at least one alpha olefin with a polymerization catalyst in a gas phase reactor, the 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 0.5 to 4.5 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; and

wherein the phosphinimine catalyst has the formula;

(1-R^¥

-Indenyl)((t-Bu)₃P═

N)TiX₂, where R^¥

is a benzyl group which is unsubstituted or is substituted by at least one fluoride atom; and

X is an activatable ligand.

23. The process of claim 22 wherein the phosphinimine catalyst has the formula:

(1-R^¥

-Indenyl)((t-Bu)₃P═

N)TiX₂, where R^¥

is a benzyl group and the aryl group of the benzyl group is a perfluorinated phenyl group, a 2,6 (i.e. ortho) fluoro substituted phenyl group, a 2,4,6 (i.e. ortho/para) fluoro substituted phenyl group or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted phenyl group.

24. 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 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;

where 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;

wherein the phosphinimine catalyst has the formula;

(1-R^¥

-Indenyl)((t-Bu)₃P═

N)TiX₂, where R^¥

is a benzyl group which is unsubstituted or is substituted by at least one fluoride atom; and

X is an activatable ligand.

25. The polymerization catalyst of claim 24 wherein the phosphinimine catalyst has the formula:

(1-R^¥

-Indenyl)((t-Bu)₃P═

N)TiX₂, where R^¥

is a benzyl group and the aryl group of the benzyl group is a perfluorinated phenyl group, a 2,6 (i.e. ortho) fluoro substituted phenyl group, a 2,4,6 (i.e. ortho/para) fluoro substituted phenyl group or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted phenyl group.