Modified phosphinimine catalysts for olefin polymerization

• US 9,127,094 B2
• Filed: 12/12/2014
• 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, Djatmiko, Martina Elissa
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US14/568,689
• Publication Number:
  US 20150099856A1
• Time in Patent Office: 270 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 4/18 Oxides
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence
• 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: C08F 4/76 selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
• 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 to make an ethylene copolymer, the 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 0.25 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;

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;

wherein the phosphinimine catalyst has the formula;

(L)((t-Bu)₃P═

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

X is an activatable ligand; and

wherein the process further comprises feeding the catalyst modifier to the gas phase reactor in an amount of 50 ppm or less based on the weight of the ethylene copolymer produced.

2. The process of claim 1 wherein the catalyst modifier present in the polymerization catalyst and fed to the gas phase reactor 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 present in the polymerization catalyst and fed to the gas phase reactor 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 each n is independently an integer from 1-20.

4. The process of claim 1 wherein the catalyst modifier present in the polymerization catalyst and fed to the gas phase reactor 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 each n is 2 or 3.

5. The process of claim 1 wherein the catalyst modifier present in the polymerization catalyst and fed to the gas phase reactor 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 present in the polymerization catalyst and fed to the gas phase reactor comprises a compound represented by the formula:

C₁₈H₃₇N(CH₂CH₂OH)₂.

7. The process of claim 1 wherein the catalyst modifier present in the polymerization catalyst and fed to the gas phase reactor comprises compounds represented by the formulas:

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

8. The process of claim 1 wherein the catalyst modifier present in the polymerization catalyst and fed to the gas phase reactor 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)((t-Bu)₃P═

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

X is an activatable ligand.

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

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

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

13. The process of claim 1 wherein the catalyst modifier is present in the polymerization catalyst in from about 1.0 to about 4.0 weight percent based on the weight of i), ii) and iii) of the polymerization catalyst.

14. The process of claim 1 wherein the amount of catalyst modifier fed to the gas phase reactor is 25 ppm or less based on the weight of the ethylene copolymer produced.