IP Library Granted Patent US 8,211,819
Granted Patent B2
US 8,211,819 · App. 12/655,007 · Granted Jul 3, 2012

Internal and external donor compounds for olefin polymerization catalysts

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Quick Facts
Patent No.
US 8,211,819
App. No.
12/655,007
Granted
Jul 3, 2012
Kind
B2
Abstract

The present invention relates to catalyst systems containing solid catalyst components comprising titanium, magnesium, halogen and a 1,8-naphthyl diaryloate internal electron donor compound; organoaluminum compounds and alkyl benzoate derivatives as external electron donors. The present invention also relates to methods of making the catalyst systems, and methods of polymerizing or copolymerizing alpha-olefins using the catalyst systems.

Claims (34)

1. A catalyst system for use in olefinic polymerization, comprising:

(i) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound;

(ii) an organoaluminum compound; and

(iii) an alkyl benzoate derivative,

wherein the internal electron donor compound comprises a 1,8-naphthyl diaryloate compound.

2. The catalyst system according to claim 1 , wherein the solid catalyst component comprises a titanium compound having at least one titanium-halogen bond and a 1,8-naphthyl diaryloate compound supported on a magnesium halide crystal lattice.

3. The catalyst system according to claim 1 , wherein the solid catalyst component comprises a titanium compound having at least one titanium-halogen bond and a 1,8-naphthyl diaryloate compound supported on a magnesium dichloride crystal lattice.

4. The catalyst system according to claim 2 or 3 , wherein the titanium compound is TiCl 4 or TiCl 3 .

5. A catalyst system for use in olefinic polymerization, comprising:

(i) a solid catalyst component comprising a reaction product of a titanium compound, a magnesium compound, and an internal electron donor compound;

(ii) an organoaluminum compound; and

(iii) an alkyl benzoate derivative,

wherein the internal electron donor compound comprises a 1,8-naphthyl diaryloate compound.

6. The catalyst system according to claim 5 , wherein the magnesium compound is a magnesium halide, an alkoxy magnesium halide, an aryloxy magnesium halide, aryloxy magnesium, or a carboxylic acid salt of magnesium.

7. The catalyst system according to claim 5 , wherein the titanium compound has a general formula:

TiX n (OR) 4-n ,

wherein R is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen, and n is from 1 to 4.

8. The catalyst system according to claim 1 or 5 , wherein the 1,8-naphthyl diaryloate compound having a general formula (I):

wherein R 1 -R 16 are independently hydrogen, halogen, C 1 -C 6 linear or branched alkyl, C 1 -C 6 linear or branched alkoxyl, phenyl, C 7 -C 10 arylalkyl, or C 7 -C 18 alkylaryl radicals.

9. The catalyst system according to claim 8 , wherein the 1,8-naphthyl diaryloate compound of the formula (I) comprises at least one selected from the group consisting of 1,8-naphthyl dibenzoate; 1,8-naphthyl di-4-methylbenzoate; 1,8-naphthyl di-3-methylbenzoate; 1,8-naphthyl di-2 methylbenzoate; 1,8-naphthyl di-4-ethylbenzoate; 1,8-naphthyl di-4-n-propylbenzoate; 1,8-naphthyl di-4-isopropylbenzoate; 1,8-naphthyl di-4-n-butylbenzoate; 1,8-naphthyl di-4-isobutylbenzoate; 1,8-naphthyl di-4-t-butylbenzoate; 1,8-naphthyl di-4-phenylbenzoate; 1,8-naphthyl di-4-fluorobenzoate; 1,8-naphthyl di-3-fluorobenzoate; 1,8-naphthyl di-2-fluorobenzoate; 1,8-naphthyl di-4-chlorobenzoate; 1,8-naphthyl di-3-chlorobenzoate; 1,8-naphthyl di-2-chlorobenzoate; 1,8-naphthyl di-4-bromobenzoate; 1,8-naphthyl di-3-bromobenzoate; 1,8-naphthyl di-2-bromobenzoate; 1,8-naphthyl di-4-cyclohexylbenzoate; 1,8-naphthyl di-2,3-dimethylbenzoate; 1,8-naphthyl di-2,4-dimethylbenzoate; 1,8-naphthyl di-2,5-dimethylbenzoate; 1,8-naphthyl di-2,6-dimethylbenzoate; 1,8-naphthyl di-3,4-dimethylbenzoate; 1,8-naphthyl di-3,5-dimethylbenzoate; 1,8-naphthyl di-2,3-dichlorobenzoate; 1,8-naphthyl di-2,4-dichlorobenzoate; 1,8-naphthyl di-2,5-dichlorobenzoate; 1,8-naphthyl di-2,6-dichlorobenzoate; 1,8-naphthyl di-3,4-dichlorobenzoate; 1,8-naphthyl di-3,5-dichlorobenzoate; and 1,8-naphthyl di-3,5-di-t-butylbenzoate.

10. The catalyst system according to claim 1 or 5 , wherein the solid catalyst component comprises from about 1 to about 50% by weight of the 1,8-naphthyl diaryloate compound.

11. The catalyst system according to claim 1 or 5 , wherein the alkyl benzoate derivative having a general formula (II):

wherein R 1 ′ is C 1 -C 6 linear or branched alkyl; and R 2 ′-R 6 ′ are independently hydrogen, halogen, C 1 -C 6 linear or branched alkyl, or C 1 -C 6 linear or branched alkoxyl radicals.

12. The catalyst system according to claim 11 , wherein the alkyl benzoate derivative of the formula (II) comprises at least one selected from group consisting of methylbenzoate, ethylbenzoate, propylbenzoate, butylbenzoate, isobutylbenzoate, amylbenzoate, hexylbenzoate, methyl-4-methylbenzoate, ethyl-3-methylbenzoate, ethyl-4-methylbenzoate, methyl-4-tert-butylbenzoate, methyl-3-butylbenzoate, methyl-2-methoxybenzoate, methyl-3-methoxybenzoate, methyl-4-methoxybenzoate, ethyl-2-methoxybenzoate, ethyl-3-methoxybenzoate, propyl-4-methoxybenzoate, butyl-2-methoxybenzoate, butyl-4-methoxybenzoate, pentyl-2-methoxybenzoate, pentyl-4-methoxybenzoate, 2-methylpropyl-4-methoxybenzoate, 2-methylbutyl-4-methoxybenzoate, 3-methylbutyl-4-methoxybenzoate, 2-ethylbutyl-4-methoxybenzoate, methyl-3-fluoro-4-methoxybenzoate, methyl-3-chloro-4-methoxybenzoate, methyl-5-chloro-2-methoxybenzoate, methyl-4-bromo-2-methoxybenzoate, methyl-4-bromo-3-methoxybenzoate, ethyl-3-iodo-5-methoxybenzoate, methyl-2-ethoxybenzoate, methyl-4-ethoxybenzoate, ethyl-2-ethoxybenzoate, ethyl-3-ethoxybenzoate, ethyl-4-ethoxybenzoate, methyl-2-fluorobenzoate, methyl-4-fluorobenzoate, ethyl-4-fluorobenzoate, methyl-2-chlorobenzoate, ethyl-4-chlorobenzoate, methyl-2-bromobenzoate, methyl-3-bromobenzoate, methyl-4-bromobenzoate, ethyl-4-bromobenzoate, and tert-butyl-4-bromobenzoate.

13. The catalyst system according claim 1 or 5 , wherein the solid catalyst component having a surface area (by B.E.T. method) between about 10 and about 1,000 m 2 /g.

14. The catalyst system according to claim 1 or 5 , wherein the oragnoaluminum compound is an alkyl-aluminum compound.

15. The catalyst system of claim 14 , wherein the alkyl-aluminum compound is a trialkyl aluminum compound.

16. The catalyst system of claim 15 , wherein the trialkyl aluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum and tri-n-octylaluminum.

17. The catalyst system according to claim 1 or 5 , wherein the ratio of the solid catalyst component (i) to the organoaluminum compound (ii) and to the alkyl benzoate derivative (iii) is about 1:5-1000:1-500, in terms of molar ratio of titanium:aluminum:alkyl benzoate derivative.

18. A process for polymerizing or copolymerizing an olefin, comprising the steps of:

(i) providing the catalyst system according to claim 1 or 5 ;

(ii) polymerizing or copolymerizing the olefin in the presence of the catalyst system to form a polymer or a copolymer; and

(iii) recovering the polymer or copolymer.

19. The process according to claim 18 , wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butylene, 4-methyl-1-pentent, 1-hexene and 1-octene.

Assignments (5)
RELEASE OF SECURITY INTEREST Recorded Sep 23, 2021
From: GOLDMAN SACHS BANK USA
To: W. R. GRACE & CO.-CONN.
Reel/Frame 057594/0026 →
SECURITY INTEREST Recorded Apr 3, 2018
From: W. R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 045828/0683 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 22, 2016
From: BASF CORPORATION
To: W. R. GRACE & CO. - CONN.
Reel/Frame 040255/0136 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 18, 2012
From: BASF CATALYSTS LLC
To: BASF CORPORATION
Reel/Frame 028230/0337 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 27, 2010
From: CHANG, MAIN
To: BASF CATALYSTS LLC
Reel/Frame 023858/0301 →