Process for controlling the MWD of a broad/bimodal resin produced in a single reactor

• US 5,525,678 A
• Filed: 09/22/1994
• Issued: 06/11/1996
• Est. Priority Date: 09/22/1994
• Status: Expired due to Term

• Current Assignee: Univation Technologies LLC (Dow, Inc.)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Shirodkar, Pradeep P., Schregenberger, Sandra D., Nowlin, Thomas E., Mink, Robert I., Tsien, Grace O.
• Primary Examiner(s): Delmendo, Romulo H.
• Application Number:
  US08/310,446
• Time in Patent Office: 628 Days
• Field of Search: 526/84, 526/78, 526/86, 526/80, 526/81, 526/92, 526/114, 526/129, 525/246, 525/270, 525/324, 525/247, 525/268
• US Class Current: 525/246
• 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 2/40 using retarding agents
• CPC Class Codes: C08F 4/61904 in combination with another component of C08F4/60
• CPC Class Codes: C08F 4/61912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/61916 supported on a carrier, e.g. silica, MgCl2, polymer

Abstract

A bimetallic catalyst produces broad or bimodal molecular weight distribution polyolefin resin whose composition depends on the ratio of the concentration of the two metals of the catalyst producing the HMW and LMW components. The bimetallic catalyst produces a broad/bimodal MWD resin whose HMW and LMW components depend on the relative productivity of each of the transition metal sites of the catalyst. Water and/or carbon dioxide are cofed to the polymerization reactor at levels necessary to modify the weight fractions of the HMW and LMW components, thus achieving a target molecular weight distribution, MWD. The invention allows the resin MWD to be adjusted in the reactor. The weight fraction of the high molecular weight component decreases with the addition of the water and or the carbon dioxide and the FI of the overall product increases with a decrease in the HMW component weight fraction in the product.

Claims

1. A process for controlling the relative amount of a high molecular weight component and a low molecular weight component in a bimodal molecular weight distribution resin or a broad molecular weight distribution resin which comprises said high molecular weight component and said low molecular weight component, said process comprising

contacting a feed comprising ethylene, under ethylene polymerization conditions, with a catalyst comprising a support containing two sources of transition metals, wherein the catalyst comprises

a dry, anhydrous, support containing composition comprising an activated metallocene compound of a transition metal and a non-metallocene transition metal compound,

wherein the support is the reaction product of

(1) silica having OH groups, impregnated with RMgR'"'"', wherein each of R and R'"'"' is alkyl of 4 to 10 carbon atoms,

wherein RMgR'"'"' is present in an amount to provide a RMgR'"'"':

OH molar ratio of 0.5;

1 to 4;

1; and

(2) an organic alcohol reagent having a formula R"OH, wherein R" is an alkyl group of 1 to 12 carbon atoms;

wherein said alcohol reagent is used in an amount effective to provide an alcohol/Mg molar ratio of 0.5 to 2.0;

producing said bimodal molecular weight distribution resin or a broad molecular weight distribution resin product;

introducing additional feed for said contacting with said catalyst in which the activated metallocene compound exhibits a first productivity relative to the non-metallocene transition metal compound;

adding an amount of a reagent selected from the group consisting of water, carbon dioxide and admixtures thereof,

wherein the amount of reagent is effective to alter the first productivity relative to the non-metallocene transition metal compound; and

recovering a modified product which has a second relative ratio of said high molecular weight component and said low molecular weight component which second relative ratio differs from said relative amount.

2. The process of claim 1 wherein the amount of reagent is effective to decrease the productivity of the non-metallocene transition metal compound.

3. The process of claim 2, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof effects a decrease in the amount of the high molecular weight component in the resin.

4. The process of claim 1, which further comprises cofeeding a composition containing a single catalyst component which comprises silica and a metallocene activated with an aluminoxane wherein the amount of metallocene on the carrier ranges, on a transition metal elemental basis, from 0,001 to 10 weight percent based on the weight of said single catalyst component.

7. The process of claim 1, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof comprises carbon dioxide.

8. The process of claim 7, wherein the amount of carbon dioxide ranges from 0.1 to 50 ppm based on ethylene.

9. The process of claim 1, wherein the catalyst is free of water.

10. The process of claim 1, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

11. The process of claim 9, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

12. The process of claim 1, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

13. The process of claim 9, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

14. The process of claim 10, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

20. The process of claim 7, wherein the amount of carbon dioxide ranges from 0.1 to 50 ppm based on ethylene.

28. The process of claim 1, which is undertaken in the gas phase.

5. A process for increasing the FI of bimodal molecular weight distribution resin or a broad molecular weight distribution resin of ethylene which comprises a high molecular weight component and a low molecular weight component, by decreasing the relative amount of a high molecular weight component, said process comprising

contacting a feed comprising ethylene, under ethylene polymerization conditions, with a catalyst comprising a support and two sources of transition metals, wherein the catalyst comprises

a dry, anhydrous, support containing composition comprising an activated metallocene compound of a transition metal and a non-metallocene transition metal compound,

wherein the support is the reaction product of

(1) silica having OH groups, impregnated with RMgR'"'"', wherein each of R and R'"'"' is an alkyl group of 4 to 10 carbon atoms,

wherein RMgR'"'"' is present in an amount to provide a RMgR'"'"':

OH molar ratio of 0.5;

1 to 4;

1; and

(2) an organic alcohol reagent having a formula R"OH, wherein R" is an alkyl group of 1 to 12 carbon atoms;

wherein said alcohol reagent is used in an amount effective to provide an alcohol/Mg molar ratio of 0.5 to 2.0;

producing bimodal molecular weight distribution resin or a broad molecular weight distribution resin each of which is further characterized as unmodified;

introducing additional feed for said contacting with said catalyst;

adding an amount of a reagent selected from the group consisting of water, carbon dioxide and admixtures thereof,

wherein the amount of reagent is effective to alter the first productivity relative to the non-metallocene transition metal compound;

wherein the amount ranges from 0-20 ppm H₂ O based on ethylene;

0-10 ppm CO₂ based on ethylene; and

recovering a modified product which has a second relative ratio of said high molecular weight component to said low molecular weight component which second relative ratio is less than the corresponding ratio in said unmodified bimodal molecular weight distribution resin or a broad molecular weight distribution resin.

15. The process of claim 5, wherein the catalyst is free of water.

16. The process of claim 5, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

17. The process of claim 15, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

18. The process of claim 5, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water.

19. The process of claim 17, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

29. The process of claim 5, which is undertaken in the gas phase.

6. A process for increasing the FI of bimodal molecular weight distribution resin or a broad molecular weight distribution resin of ethylene which comprises a high molecular weight component and a low molecular weight component, by decreasing the relative amount of said high molecular weight component, said process comprising

contacting a feed comprising ethylene, under ethylene polymerization conditions, with a catalyst comprising a support and two sources of transition metals, wherein the catalyst comprises

a dry, anhydrous, support containing composition comprising an activated metallocene compound of a transition metal and a non-metallocene transition metal compound,

wherein the support is the reaction product of

(1) silica having OH groups, impregnated with RMgR'"'"', wherein each of R and R'"'"' is an alkyl group of 4 to 10 carbon atoms,

wherein RMgR'"'"' is present in an amount to provide a RMgR'"'"':

OH molar ratio of 0.5;

1 to 4;

1; and

(2) an organic alcohol reagent having a formula R"OH, wherein R" is an alkyl group of 1 to 12 carbon atoms;

wherein said alcohol reagent is used in an amount effective to provide an alcohol/Mg molar ratio of 0.5 to 2.0;

producing bimodal molecular weight distribution resin or a broad molecular weight distribution resin unmodified product;

introducing additional feed for said contacting with said catalyst;

adding an amount of a reagent selected from the group consisting of water, carbon dioxide and admixtures thereof,

wherein the amount of reagent ranges from 0.1 to 1000 ppm H₂ O based on ethylene;

0.1 to 50 ppm CO₂ based on ethylene; and

recovering a modified product which has an FI that is at least 10 percent higher than that of the unmodified product.

21. The process of claim 6, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof comprises carbon dioxide.

22. The process of claim 6, wherein the catalyst is free of water.

23. The process of claim 6, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

24. The process of claim 22, wherein the catalyst comprises a cocatalyst which is free of alumoxane and free of water and free of oxygen containing oligomers and polymers of aluminum alkyl compound.

25. The process of claim 6, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

26. The process of claim 23, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

27. The process of claim 24, wherein the reagent selected from the group consisting of water, carbon dioxide and admixtures thereof is water and is added in amount ranging from 0.1 to 50 ppm based on ethylene.

30. The process of claim 6, which is undertaken in the gas phase.