Modified phosphinimine catalysts for olefin polymerization

• US 20120316297A1
• Filed: 09/19/2011
• Published: 12/13/2012
• Est. Priority Date: 06/09/2011
• Status: Active Grant

• Current Assignee: Nova Chemicals
• Original Assignee: Nova Chemicals
• Inventors: Hoang, Peter Phung Minh, Shaw, Benjamin Milton, Ker, Victoria, Baar, Cliff Robert, Henderson, Lee Douglas, Carter, Charles Ashton Garret, Jiang, Yan
• Granted Patent: US 8,952,111 B2
• Time in Patent Office: Days
• US Class Current: 526/100
• 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 4/65912 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 process for polymerizing ethylene and optionally an alpha olefin in a reactor, the process comprising introducing a polymerization catalyst into the reactor to polymerize the ethylene and optionally an alpha olefin, 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.

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)_xOH)₂ where R¹ is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, and x 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)_xOH)₂ where R¹ is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, and x 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 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 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 the group consisting of hydrogen, halogen, and C₁-C₂₀ hydrocarbyl;

L is a ligand selected from the group consisting of 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:

(1,2-(R*)(Ar—

F)Cp)Ti(N═

P(t-Bu)₃)X₂, where R* is a straight chain alkyl group, Ar—

F is a perfluorinated aryl group, a 2,6 fluoro substituted phenyl group, a 2,4,6 fluoro substituted phenyl group, or a 2,3,5,6 fluoro substituted phenyl group, and X is an activatable ligand.

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

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

13. The process of claim 12 wherein the silica support has been treated with a source of Zr(SO₄)₂ or ZrO₂.

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

15. The process of claim 1 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.

16. 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.

17. The catalyst of claim 16 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.

18. The catalyst of claim 16 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.

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

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

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

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

21. The catalyst of claim 16 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.

22. The catalyst of claim 16 wherein the catalyst modifier comprises a compound represented by the formula:

C₁₈H₃₇N(CH₂CH₂OH)₂.

23. The catalyst claim 16 wherein the catalyst modifier comprises compounds represented by the formulas:

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

24. The catalyst of claim 16 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.

25. The catalyst of claim 16 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 the group consisting of hydrogen, halogen, and C₁-C₂₀ hydrocarbyl;

L is a ligand selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, and substituted fluorenyl; and

X is an activatable ligand.

26. The catalyst of claim 16 wherein the phosphinimine catalyst has the formula:

(1,2-(R*)(Ar—

F)Cp)Ti(N═

P(t-Bu)₃)X₂, where R is a straight chain alkyl group, Ar—

F is a perfluorinated aryl group, a 2,6 fluoro substituted phenyl group, a 2,4,6 fluoro substituted phenyl group, or a 2,3,5,6 fluoro substituted phenyl group, and X is an activatable ligand.

27. The catalyst of claim 16 wherein the cocatalyst is selected from the group consisting of ionic activators, alkylaluminoxanes and mixtures thereof.

28. The catalyst of claim 16 wherein the inert support is silica.

29. The catalyst of claim 28 wherein the silica support has been treated with a source of Zr(SO₄)₂ or ZrO₂.