Supported polymerization catalyst

• US 5,424,263 A
• Filed: 04/23/1993
• Issued: 06/13/1995
• Est. Priority Date: 04/23/1993
• Status: Expired due to Fees

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: Quantum Chemical Corporation (Heidelberg Materials AG)
• Inventors: Buehler, Charles K.
• Primary Examiner(s): Pal, Asok
• Assistant Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US08/052,317
• Time in Patent Office: 781 Days
• Field of Search: 502/115, 502/116, 502/120, 502/125, 502/127, 502/119
• US Class Current: 502/116
• CPC Class Codes: B01J 31/0212 Alkoxylates
• CPC Class Codes: B01J 31/0214 Aryloxylates, e.g. phenolates
• CPC Class Codes: B01J 31/0274 containing silicon ligands in coordination complexes B01J31/1608
• CPC Class Codes: B01J 31/128 Mixtures of organometallic compounds
• CPC Class Codes: B01J 31/143 of aluminium
• 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 4/025 Metal oxides
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds

Abstract

A catalyst component useful in the polymerization of olefins is disclosed. The catalyst component comprises the product obtained by steps of (a) contacting silica with at least one hydrocarbon soluble magnesium-containing compound; (b) contacting the product of step (a) with component (1), a heterocyclic fused ring compound substituted with at least one oxygen atom, and component (2), a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof, with the proviso that components (1) and (2) be present such that the molar ratio of component (2) to component (1) is at least about 4:1; and (c) contacting the product of step (b) with a titanium-containing compound having the structural formula TiX_m (OR)_n, where X is halogen; R is hydrocarbyl; m is an integer of 1 to 4; and n is 0 or an integer of 1 to 3 with the proviso that the sum of m and n is 4. A catalyst system, used in the polymerization of alpha-olefins, which comprises the catalyst component of this disclosure, an aluminum-containing compound and a silane compound is also taught. Finally, a process for the polymerization of alpha-olefins, utilizing the catalyst system of the present disclosure, is described.

Claims

1. A catalyst component comprising the product formed by the steps of:

(a) contacting silica with at least one hydrocarbon soluble magnesium-containing compound;

(b) contacting the product of said step (a) with components (1) and (2) in random order, component (1) being A heterocyclic fused ring compound substituted with at least one oxygen atom and component (2) being a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof, with the proviso that the molar ratio of said hydrocarbon soluble magnesium-containing compound to said heterocyclic fused ring compound is at least about 4;

1; and

(c) contacting the product of said step (b) with a first titanium-containing compound having the structural formula TiX_m (OR)_n, where X is halogen;

R is hydrocarbyl;

m is an integer of 1 to 4; and

n is 0 or an integer of 1 to 3, with the proviso that the sum of m and n is 4.

2. A catalyst component in accordance with claim 1 comprising contacting said product of step (b), prior to step (c), with a second titanium-containing compound, said second titanium-containing compound having the structural formula Ti(OR¹)_p X¹_q, where R¹ is hydrocarbyl;

X¹ is halogen;

p is an integer of 1 to 4; and

q is 0 or an integer of 1 to 3, with the provisos that the sum of p and q is 4 and that said second titanium-containing compound is not identical to said first titanium-containing compound.

3. A catalyst component in accordance with claim 1 wherein said hydrocarbon soluble magnesium-containing compound and said heterocyclic fused ring compound are present in a concentration such that the molar ratio of said hydrocarbon soluble magnesium-containing compound to said heterocyclic fused ring compound is in the range of between about 5:

1 and about 25;

1.

4. A catalyst component in accordance with claim 3 wherein said molar ratio is in the range of between about 12:

1 and about 21;

1.

5. A catalyst component in accordance with claim 4 wherein said molar ratio is in the range of between about 14:

1 and about 20;

1.

6. A catalyst component in accordance with claim 1 wherein the product of step (a) contacts said component (1) prior to contact of said product with said component (2).

7. A catalyst component in accordance with claim 1 wherein the product of said step (b) is characterized by a flour-like consistency.

8. A catalyst component in accordance with claim 2 wherein the product of said step (b) which contacts said second titanium-containing compound is characterized by a flour-like consistency.

9. A catalyst component in accordance with claim 1 wherein said silica includes a surface characterized by the structural formula ##STR7##

10. A catalyst component in accordance with claim 1 wherein said heterocyclic fused ring compound substituted with at least one carbon atom is selected from the group consisting of 3-benzylidenephthalate, 1,2,4,5-benzenetetracarboxylicdianhydride, dicresol phthalein, diphenic anhydride and benz[CD]indol-2(1H)one.

11. A catalyst component in accordance with claim 10 wherein said heterocyclic fused ring compound substituted with at least one carbon atom is 3-benzyl-idenephthalide.

12. A catalyst component in accordance with claim 1 wherein said hydrocarbon soluble magnesium-containing compound is 2-methyl-1-pentyloxymagnesium chloride.

13. A catalyst component in accordance with claim 1 wherein said modifying compound is silicon tetrachloride.

14. A catalyst component in accordance with claim 1 wherein said first titanium-containing compound is titanium tetrachloride.

15. A catalyst component in accordance with claim 2 wherein said second titanium-containing compound is titanium tetracresylate.

25. A catalyst system comprising the catalyst component of claim 1, an aluminum-containing compound and at least one silane compound.

16. A catalyst component comprising the product formed by the steps of:

(a) contacting silica, said silica being at least 90% by weight pure silica, with a hydrocarbon soluble magnesium-containing compound selected from the group consisting of dihyhydrocarbyloxymagnesium compounds, hydrocarbyloxymagnesium halides and mixtures thereof;

(b) contacting the product of said step (a) with

(1) a heterocyclic fused ring compound substituted with at least one oxygen atom; and

(2) a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides and mixtures thereof;

said components (1) and (2) contacting the product of said step (a) in random order; and

said hydrocarbon soluble magnesium-containing compound and said heterocyclic fused ring compound being present in a concentration such that the molar ratio of said hydrocarbon soluble magnesium-containing compound to said heterocyclic fused ring compound is at least about 5;

1; and

(c) contacting the product of said step (b) with a first titanium-containing compound having the structural formula TiX_m (OR)_n, where X is chlorine or bromine;

R is hydrocarbyl;

m is an integer of 2 to 4; and

n is 0 or an integer of 1 or 2, with the proviso that the sum of m and n is 4.

17. A catalyst component in accordance with claim 16 wherein said soluble magnesium-containing compound is 2-methylpentyloxymagnesium chloride.

18. A catalyst component in accordance with claim 17 wherein the titanium-containing compound of step (c) is titanium tetrachloride.

19. A catalyst component in accordance with claim 18 wherein said component (2) of step (b) is silicon tetrachloride.

20. A catalyst component in accordance with claim 19 wherein said product of step (b) is characterized by a flour-like consistency.

21. A catalyst component in accordance with claim 20 wherein said dried flour-like consistency product is contacted with a second titanium-containing compound having the structural formula Ti(OR¹)_p X_q, where R¹ is hydrocarbyl;

X¹ is halogen;

pr is an integer of 1 to 4; and

q is 0 or an integer of 1 to 3, with the proviso that the sum of p and q are 4, prior to said step (c).

22. A catalyst component in accordance with claim 21 wherein said second titanium compound is titanium tetracresylate.

23. A catalyst component in accordance with claim 22 wherein said component (1) of step (b) is 3benzylidenephthalide.

24. A catalyst component in accordance with claim 23 wherein said silica includes a surface characterized by the structural formula ##STR8##

26. A catalyst system comprising the catalyst component of claim 16, an aluminum-containing compound selected from the group consisting of alkyl aluminums, alkyl aluminum halides and mixtures thereof and a hydrocarbylalkoxysilane.

27. A catalyst system comprising the catalyst component of claim 16, triethylaluminum and isobutyl-isopropyldimethyoxysilane.