Multiple chromium compound-containing catalyst composition and olefin polymerization therewith

• US 5,034,364 A
• Filed: 11/09/1989
• Issued: 07/23/1991
• Est. Priority Date: 11/09/1989
• Status: Expired due to Fees

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Wu, Chisung, Tsien, Grace O., Kral, Bohumil V.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): WEBER, THOMAS
• Application Number:
  US07/438,814
• Time in Patent Office: 621 Days
• Field of Search: 526/101, 526/97, 526/96, 526/106, 526/104, 502/158, 502/117, 502/256, 502/319
• US Class Current: 502/117
• CPC Class Codes: B01J 23/26 Chromium
• 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 2410/04 Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/22 of chromium, molybdenum or tungsten
• CPC Class Codes: C08F 4/69 Chromium, molybdenum, tungsten or compounds thereof

Abstract

An olefin, particularly alpha-olefin, polymerization catalyst composition, supported on a refractory oxide support comprises two chromium specie: (1) CrO₃ or any chromium compound calcinable to CrO₃ ; and (2) at least one silylchromate compound. The composition is prepared by sequentially depositing specie (1) and (2) onto the same support.

Claims

1. A refractory oxide-supported olefin polymerization catalyst composition comprising two chromium specie:

(1) CrO₃ or any compound of chromium calcinable to CrO₃ ; and

(2) at least one silylchromate compound.

2. A catalyst composition of claim 1 wherein the weight ratio of the chromium species (2) to the chromium species (1) is about 0.7 to about 3.7.

3. A catalyst composition of claim 2 additionally comprising an organoaluminum compound having one or two oxyhadrocarbyl groups attached to the aluminum atom.

4. A catalyst composition of claim 3 wherein the silylchromate compound is characterized by the presence therein of the group of the formula ##STR4## wherein R is a hydrocarbyl group having 1 to 14 carbon atoms.

5. A catalyst composition of claim 4 wherein the silylchromate compound is a bis-trihydrocarbyl silylchromate of the formula ##STR5## wherein R is a hydrocarbyl group having 1 to 14 carbon atoms.

7. A catalyst composition of claim 5 wherein the support is silica, silica-alumina, silica-titania, alumina, zirconia or thoria.

8. A catalyst composition of claim 7 wherein the support is silica having deposited theron about 0.18% wt. of chromium trioxide (CrO₃) and having about 88% of its pore volume in the pores of about 250 to about 450 Angstrom diameter.

9. A catalyst composition of claim 8 wherein each R in the silylchromate compound is an alkyl, alkaryl, aralkyl or an aryl radical containing 3 to 10 carbon atoms.

10. A catalyst composition of claim 9 wherein each R in the silylchromate compound is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, 2-methyl-pentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, tetradecyl, benzyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl.

11. A catalyst composition of claim 10 wherein the silylchromate compound is selected from the group consisting of bis-trimethylsilylchromate, bis-triethylsilylchromate, bis-tributylsilylchromate, bis-triisopentylsilylchromate, bis-tri-2-ethylhexylsilylchromate, bis-tridecylsilylchromate, bis-tri(tetradecyl)silylchromate, bis-tribenzylsilylchromate, bis-triphenethylsilylchromate, bis-triphenylsilylchromate, bis-tritolylsilylchromate, bis-trixylylsilylchromate, bis-trinaphthylsilylchromate, bis-triethylphenylsilylchromate, bis-trimethylnaphthylsilylchromate, polydiphenylsilylchromate, and polydiethylsilylchromate.

12. A catalyst composition of claim 11 wherein the silylchromate compound is bis-triphenylsilylchromate.

13. A catalyst composition of claim 12 wherein the organoaluminum compound has the formula

14. A catalyst composition of claim 13 wherein each R in the organoaluminum compound is the same or different and it is selected from the group consisting of alkyl, aralkyl, aryl, alkaryl, alicyclic or bicyclic groups.

15. A catalyst composition of claim 14 wherein each R in the organoaluminum compound is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, cyclohexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, cyclohexylmethyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, benzyl, pinyl, pinylmethyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl, dimethylnaphthyl, norbornyl, and norbornyl methyl.

16. A catalyst composition of claim 15 wherein the organoaluminum compound is diethyl-aluminum ethoxide.

6. A method of preparing a refractory oxide-supported olefin polymerization catalyst composition comprising depositing onto a support material a first chromium species which is CrO₃ or any compound of chromium calcinable to CrO₃ to produce the first chromium species-containing support, activating the first chromium species-containing support, and depositing onto the support a second chromium species which is at least one silylchromate compound.

17. A method of claim 6 wherein the weight ratio of the chromium species (2) to the chromium species (1) is about 0.7 to about 3.7.

18. A method of claim 17 wherein the catalyst composition additionally comprises an organoaluminum compound having one or two oxyhydrocarbyl groups attached to the aluminum atom.

19. A method of claim 18 wherein the silylchromate compound is characterized by the presence therein of the group of the formula ##STR6## wherein R is a hydrocarbyl group having 1 to 14 carbon atoms.

20. A method of claim 19 wherein the silylchromate compound is a bis-trihydrocarbyl silylchromate of the formula ##STR7## wherein R is a hydrocarbl group having 1 to 14 carbon atoms.

21. A method of claim 20 wherein the support is silica, silica-alumina, silica-titania, alumina, zirconia or thoria.

22. A method of claim 21 wherein the support is silica having deposited theron about 0.18% wt. of chromium trioxide (CrO₃) and having about 88% of its pore volume in the pores of about 250 to about 450 Angstrom diameter.

23. A method of claim 22 wherein each R in the silylchromate compound is an alkyl, alkaryl, aralkyl or an aryl radical containing 3 to 10 carbon atoms.

24. A method of claim 23 wherein each R in the silylchromate compound is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, 2-methyl-pentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, tetradecyl, benzyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl.

25. A method of claim 24 wherein the silylchromate compound is selected from the group consisting of bis-trimethylsilylchromate, bis-triethylsilylchromate, bis-tributylsilylchromate, bis-triisopentylsilylchromate, bis-tri-2-ethylhexylsilylchromate, bis-tridecylsilylchromate, bis-tri(tetradecyl)silylchromate, bis-tribenzylsilylchromate, bis-triphenethylsilylchromate, bis-triphenylsilylchromate, bis-tritolylsilylchromate, bis-trixylylsilylchromate, bis-trinaphthylsilylchromate, bis-triethylphenylsilylchromate, bis-trimethylnaphthylsilylchromate, polydiphenylsilylchromate, polydiethylsilylchromate.

26. A method of claim 25 wherein the silylchromate compound is bis-triphenylsilylchromate.

27. A method of claim 26 wherein the organoaluminum compound has the formula

28. A method of claim 27 wherein each R in the organoaluminum compound is the same or different and it is selected from the group consisting of alkyl, aralkyl, aryl, alkaryl, alicyclic or bicyclic groups.

29. A method of claim 28 wherein each R in the organoaluminum compound is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, cyclohexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, cyclohexylmethyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, benzyl, pinyl, pinylmethyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl, dimethylnaphthyl, norbornyl, and norbornyl methyl.

30. A method of claim 29 wherein the organoaluminum compound is diethyl-aluminum ethoxide.