Polymerization catalyst, production and use

• US 4,558,024 A
• Filed: 08/06/1984
• Issued: 12/10/1985
• Est. Priority Date: 08/06/1984
• Status: Expired due to Fees

• Current Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Original Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Inventors: Best, Steven A.
• Primary Examiner(s): GARVIN, PATRICK
• Application Number:
  US06/638,165
• Time in Patent Office: 491 Days
• Field of Search: 502/115, 502/117, 502/125
• US Class Current: 502/115
• 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 110/02 Ethene
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/14 Die swell or die swell ratio or swell ratio
• CPC Class Codes: C08F 4/6555 and magnesium or compounds thereof
• CPC Class Codes: C08F 4/6565 and magnesium or compounds thereof
• CPC Class Codes: C08F 4/6574 and magnesium or compounds thereof
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

Ethylene and alpha-olefins are homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, optionally an oxygen containing compound, titanium tetrachloride and a Group IIIa metal hydrocarbyl dihalide.

Claims

1. A transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a Group IIIa metal hydrocarbyl dihalide with the proviso that if the oxygen containing alcohol, aldehyde, ketone or siloxane is employed the inert solid support material can be treated with (i) the (A) organometallic compound and the (B) oxygen containing compound simultaneously, (ii) the reaction product of the (A) organometallic compound and (B) oxygen containing compound or (iii) the (B) oxygen containing compound followed by treating with the (A) organometallic compound.

2. The transition metal containing catalyst component of claim 1 wherein the (A) organometallic compound is a dihydrocarbon magnesium compound represented by R¹ MgR² wherein R¹ and R² which can be the same or different are selected from alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen containing compounds are selected from alcohols and ketones represented by the formula R³ OH and R⁴ COR⁵ wherein R³ and each of R⁴ and R⁵ which may be the same or different can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group.

3. The transition metal containing catalyst component of claim 2 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

4. The transition metal containing catalyst component of claim 2 wherein R¹, R², R³, R⁴ and R⁵ are alkyl groups having from 1 to 10 carbon atoms.

5. The transition metal containing catalyst component of claim 2 wherein R¹ and R² are different.

6. The transition metal containing catalyst component of claim 5 wherein R¹, R² and R³ are alkyl groups having from 1 to 6 carbon atoms.

7. The transition metal containing catalyst component of claim 6 wherein R¹ is butyl.

8. The transition metal containing catalyst component of claim 7 wherein R² is ethyl.

9. The transition metal containing catalyst component of claim 6 wherein R¹, R², R³, R⁴ and R⁵ have 2 to 4 carbon atoms.

10. The transition metal containing catalyst component of claim 9 wherein the oxygen containing component is an alcohol.

11. The transition metal containing catalyst component of claim 10 wherein R³ is butyl.

12. The transition metal containing catalyst component of claim 2 wherein the transition metal compound or mixtures thereof is represented by the formula TrX'"'"'_4-q (OR⁷)_q, TrX'"'"'_4-q R_q⁸, VOX'"'"'₃ or VO(OR⁷)₃ wherein Tr is a transition metal, R⁷ is a hydrocarbyl group having from 1 to 20 carbon atoms, R⁸ is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X'"'"' is halogen and q is 0 or a number equal to or less than 4.

13. The transition metal containing catalyst component of claim 12 wherein Tr is titanium, vanadium or zirconium.

14. The transition metal containing catalyst component of claim 13 wherein the transition metal compound is TiCl₄.

15. The transition metal containing catalyst component of claim 2 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

16. A catalyst system for the polymerization or copolymerization of ethylene and alpha-olefins having from 3 to 12 carbon atoms comprising (a) an organo aluminum compound of the formula AlR"_n X"_3-n wherein R" is hydrogen or a hydrocarbon group having from 1 to 20 carbon atoms, X is halogen and n is a number from 1 to 3, and (b) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a Group IIIa metal hydrocarbyl dihalide and with the proviso that if the oxygen containing alcohol, aldehyde, ketone or siloxane is employed the inert solid support material can be treated with (i) the (A) organometallic compound and the (B) oxygen containing compound simultaneously, (ii) the reaction product of the (A) organometallic compound and (B) oxygen containing compound or (iii) the (B) oxygen containing compound followed by treating with the (A) organometallic compound.

17. The catalyst system of claim 16 wherein the (A) organometallic compound is a dihydrocarbon magnesium compound represented by R¹ MgR² wherein R¹ and R² which can be the same or different are selected from alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen containing compounds are selected from alcohols and ketones represented by the formula R³ OH and R⁴ COR⁵ wherein R³ and each of R⁴ and R⁵ which may be the same or different can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group.

18. The catalyst system of claim 17 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

19. The catalyst system of claim 17 wherein R¹, R², R³, R⁴, R⁵ and R⁶ are alkyl groups having from 1 to 10 carbon atoms.

20. The catalyst system of claim 17 wherein R¹ and R² are different.

21. The catalyst system of claim 20 wherein R¹, R² and R³ are alkyl groups having from 1 to 6 carbon atoms.

22. The catalyst system of claim 21 wherein R¹ is butyl.

23. The catalyst system of claim 22 wherein R² is ethyl.

24. The catalyst system of claim 21 wherein R¹, R², R³, R⁴ and R⁵ have 1 to 4 carbon atoms.

25. The catalyst system of claim 24 wherein the oxygen containing component is an alcohol.

26. The catalyst system of claim 25 wherein R³ is butyl.

27. The catalyst system of claim 17 wherein the transition metal compound or mixtures thereof is represented by the formula TrX'"'"'_4-q (OR⁷)_q, TrX'"'"'_4-q R_q⁸, VOX'"'"'₃ or VO(OR⁷)₃ wherein Tr is a transition metal, R⁷ is a hydrocarbyl group having from 1 to 20 carbon atoms, R⁸ is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X'"'"' is halogen and q is 0 or a number equal to or less than 4.

28. The catalyst system of claim 27 wherein Tr is titanium, vanadium or zirconium.

29. The catalyst system of claim 28 wherein the transition metal compound is TiCl₄.

30. The catalyst system of claim 17 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

31. The catalyst system of claim 30 wherein the oxygen containing compound is an alkyl alcohol having from 1 to 4 carbon atoms and the magnesium containing compound is ethyl-n-butylmagnesium.

32. The catalyst system of claim 17 wherein the aluminum compound is a trialkyl aluminum wherein the alkyl group has from 1 to 10 carbon atoms.

33. The catalyst system of claim 32 wherein the aluminum alkyl is tri-n-hexyl aluminum.