Olefin polymerization catalyst compositions and method of preparation

• US 6,825,146 B2
• Filed: 05/01/2002
• Issued: 11/30/2004
• Est. Priority Date: 05/29/2001
• Status: Expired due to Fees

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: Cuthbert, Thomas R., Kilty, Peter A.
• Primary Examiner(s): Rabago, Roberto
• Application Number:
  US10/138,141
• Publication Number:
  US 20030064882A1
• Time in Patent Office: 944 Days
• Field of Search: 502/107, 502/115, 502/104, 502/116, 502/126, 502/127, 502/128, 526/124.3, 526/125.2, 526/125.3, 526/125.7
• US Class Current: 502/107
• CPC Class Codes: C08F 10/06 Propene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6548 magnesium or compounds thereof, not provided for in C08F4/6543 or C08F4/6546

Abstract

A method of making a solid procatalyst composition for use in a Ziegler-Natta olefin polymerization catalyst composition, said method comprising:

contacting a solid precursor composition comprising magnesium, titanium, and alkoxide moieties with a titanium halide compound and an internal electron donor in any order, in a suitable reaction medium to prepare a solid procatalyst composition,

separating the solid procatalyst from the reaction medium,

further exchanging residual alkoxide functionality of the solid procatalyst composition for chloride functionality by contacting the same two or more times with benzoyl chloride halogenating agent under metathesis conditions for a period of time sufficient to prepare a solid procatalyst composition having a decreased alkoxide content compared to the alkoxide content of the solid procatalyst composition before said exchange, and

recovering the solid procatalyst composition.

Claims

1. A method of making a solid procatalyst composition for use in a Ziegler-Natta olefin polymerization catalyst composition, said method comprising:

contacting a solid precursor composition comprising magnesium, titanium, and alkoxide moieties with a titanium halide compound and an internal electron donor in any order, in a suitable reaction medium to prepare a solid procatalyst composition,

separating the solid procatalyst composition from the reaction medium,

further exchanging residual alkoxide functionality of the solid procatalyst composition for chloride functionality by contacting the same two or more times with benzoyl chloride under metathesis conditions for a period of time sufficient to prepare a solid procatalyst composition having a decreased alkoxide content compared to the alkoxide content of the solid procatalyst composition before said exchange and without of the procatalyst composition by greater than 25°

C., and

recovering the solid procatalyst composition.

2. The method of claim 1 wherein the internal electron donor is a C_1-4 alkyl ester of an aromatic monocarboxylic or dicarboxylic acid, or a C_1-4 alkyl ether derivative thereof.

3. The method of claim 2 wherein the internal electron donor is ethylbenzoate, ethyl p-ethoxybenzoate, di(n-butyl)phthalate, or di(isobutyl)phthalate.

4. The method of claim 1 wherein each contacting of the exchange is conducted at a temperature from 45°

C. to 120°

C. for a time from 10 minutes to 3 hours.

5. The method of claim 1 wherein each contacting of the exchange is conducted at a temperature within the range of from 70°

C. to about 115°

C. for a time from 30 to 90 minutes.

6. The method of claim 5 wherein each contacting of the exchange takes place at a temperature within the range of from 85°

C. to 110°

C. for a time from 40 to 80 minutes.

8. The method of claim 1 where the solid procatalyst is also extracted one or more times with an inert diluent simultaneously or subsequently to said exchange.

9. The method of claim 1 wherein the solid procatalyst is contacted with a halide salt compound before or during the exchange step.

10. The method of claim 8 wherein the solid procatalyst is contacted with a halide salt compound before or during the exchange step.

7. The method of claim I wherein the solid procatalyst composition is contacted with benzoyl chloride three times.

11. A method of making a solid procatalyst composition for use in a Ziegler-Natta olefin polymerization catalyst composition, said method comprising:

precontacting a solid precursor composition comprising magnesium, titanium, and alkoxide moieties with a titanium halide compound and optionally a halohydrocarbon for a time from 10 to 30 minutes and thereafter contacting the mixture with an internal electron donor to prepare a solid procatalyst composition,

separating the solid procatalyst composition from the reaction medium,

further exchanging residual alkoxide functionality of the solid procatalyst composition for chloride functionality by contacting the same two or more times with benzoyl chloride under metathesis conditions for a period of time sufficient to prepare a solid procatalyst composition having a decreased alkoxide content compared to the alkoxide content of the solid procatalyst composition before said exchange, and

recovering the solid procatalyst composition.

12. The method of claim 11 wherein the internal electron donor is a C_1-4 alkyl ester of an aromatic monocarboxylic or dicarboxylic acid, or a C_1-4 alkyl ether derivative thereof.

13. The method of claim 12 wherein the internal electron donor is ethylbenzoate, ethyl p-ethoxybenzoate, di(n-butyl)phthalate, or di(isobutyl)phthalate.

14. The method of claim 11 wherein the exchange is conducted without cooling of the procatalyst composition by greater than 25°

C.

15. The method of claim 11 wherein each contacting of the exchange is conducted at a temperature within the range of from 85°

C. to about 110°

C. for a time from 40 to 80 minutes.

16. The method of claim 14 wherein each contacting of the exchange takes place at a temperature within the range of from 85°

C. to 110°

C. for a time from 40 to 80 minutes.

17. The method of claim 11 wherein the solid procatalyst composition is contacted with benzoyl chloride three times.