US4243552A
Expired / Lapsed
US
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Polymerization catalyst and process
Assignee: Phillips Petroleum Co
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Filing: 1978-12-11
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Granted: 1981-01-06
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Expires: 1998-12-11
Abstract
Abstract Alpha-olefins are polymerized employing a catalyst which forms on mixing a catalyst component A formed by milling together a magnesium halide or manganous halide with selected catalyst adjuvants followed by treatment of the resulting milled product with a halogenated tetravalent titanium compound and combining the product thus formed with a cocatalyst component B comprising at least one of an organoaluminum compound and an organoaluminum monohalide with or without an aromatic ester as a part of the cocatalyst system.
Inventors
- 👤 Melvin B. Welch
- 👤 Richard E. Dietz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 00:00
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
388 words
A catalyst which forms on mixing: A. a catalyst component A formed by milling (1) a magnesium halide or manganous halide with (2) at least one catalyst adjuvant selected from (a) hydrocarbyl metal oxides of the formula M(OR) n wherein M is aluminum, boron, magnesium, titanium or zirconium, n is an integer representing the valence of M and ranges from 2-4, and R is a hydrocarbyl group having from 1 to 24 carbon atoms per molecule, (b) organo phosphites of the formula ##STR8## wherein R 2 is an aryl, aralkyl, alkaryl or haloaryl having from 6 to 20 carbon atoms, (c) aromatic phenols of the formula HOR 3 wherein R 3 is an aryl group containing from 6 to about 20 carbon atoms, (d) aromatic ketones of the formula ##STR9## wherein R 4 is a thiophene, aryl or alkyl group and R 5 is an aryl group containing from 6 to 20 carbon atoms, (e) organo silanols of the formula ##STR10## wherein R 6 , R 7 , R 8 are the same or different and are hydrocarbyl groups containing from 4-20 carbon atoms, (f) organo phosphates and phosphines of the formula ##STR11## wherein each R is the same or different hydrocarbyl or hydrocarbyloxy group containing from 1 to 20 carbon atoms, (g) oxygenated terpenes selected from among carvone, dihydrocarvone, carvenone and carvomenthane, (h) triarylphosphites having from 6 to 24 carbon atoms in each aryl group, and (i) halogen-containing organo phosphorus compounds of the formula PX 3-a (OR 3 ) a , ##STR12## where R 3 is an aryl group containing from 6 to 20 carbon atoms, X is a halogen, a is 1 or 2, and b is 0 or 2 to form a milled composite wherein the molar ratio of (1) to (2) ranges from 4:1 to 100:1; (3) treating the composite thus obtained from (1) and (2) with a tetravalent titanium halide for a period of time sufficient to incorporate titanium tetrahalide on at least a portion of the surface of said milled composite; and B. a cocatalyst component B comprising at least one organoaluminum compound wherein the molar ratio of component B to titanium compound ranges from 0.5:1 to 2,000:1 and the amount of titanium present in the finished catalyst ranges from about 0.1 to about 10 weight percent based on the dry composite.
Claim 2
Dependent Claim
388 words
A catalyst which forms on mixing: A. a catalyst component A formed by milling (1) a magnesium halide or manganous halide with (2) at least one catalyst adjuvant selected from (a) hydrocarbyl metal oxides of the formula M(OR) n wherein M is aluminum, boron, magnesium, titanium or zirconium, n is an integer representing the valence of M and ranges from 2-4, and R is a hydrocarbyl group having from 1 to 24 carbon atoms per molecule, (b) organo phosphites of the formula ##STR8## wherein R 2 is an aryl, aralkyl, alkaryl or haloaryl having from 6 to 20 carbon atoms, (c) aromatic phenols of the formula HOR 3 wherein R 3 is an aryl group containing from 6 to about 20 carbon atoms, (d) aromatic ketones of the formula ##STR9## wherein R 4 is a thiophene, aryl or alkyl group and R 5 is an aryl group containing from 6 to 20 carbon atoms, (e) organo silanols of the formula ##STR10## wherein R 6 , R 7 , R 8 are the same or different and are hydrocarbyl groups containing from 4-20 carbon atoms, (f) organo phosphates and phosphines of the formula ##STR11## wherein each R is the same or different hydrocarbyl or hydrocarbyloxy group containing from 1 to 20 carbon atoms, (g) oxygenated terpenes selected from among carvone, dihydrocarvone, carvenone and carvomenthane, (h) triarylphosphites having from 6 to 24 carbon atoms in each aryl group, and (i) halogen-containing organo phosphorus compounds of the formula PX 3-a (OR 3 ) a , ##STR12## where R 3 is an aryl group containing from 6 to 20 carbon atoms, X is a halogen, a is 1 or 2, and b is 0 or 2 to form a milled composite wherein the molar ratio of (1) to (2) ranges from 4:1 to 100:1; (3) treating the composite thus obtained from (1) and (2) with a tetravalent titanium halide for a period of time sufficient to incorporate titanium tetrahalide on at least a portion of the surface of said milled composite; and B. a cocatalyst component B comprising at least one organoaluminum compound wherein the molar ratio of component B to titanium compound ranges from 0.5:1 to 2,000:1 and the amount of titanium present in the finished catalyst ranges from about 0.1 to about 10 weight percent based on the dry composite.
Claim 3
Dependent Claim
89 words
A catalyst according to claim 1 which additionally contains an aromatic ester as part of cocatalyst component b, said aromatic ester being represented by the formula ##STR13## wherein R 15 represents alkyl groups having from 1 to about 4 carbon atoms and wherein R" represents monovalent radicals selected from the group consisting of --F, --Cl, --Br, --I, --OH, --OR', --OOCR', --SH, --NH 2 , --NR 2 ', NO 2 , --CN, --CHO, --COR', --COOR', --CONH 2 , CONR 2 ', --SO 2 R', --CF 3 , --NHCOR', and hydrogen.
Claim 4
Dependent Claim
20 words
A catalyst according to claim 2 wherein the molar ratio of B to aromatic ester is about 1:1 to 8:1.
Claim 5
Dependent Claim
34 words
A catalyst according to claim 1 wherein 2d is a ketone of the formula ##STR14## wherein R 4 is thiophene, and R 5 is an aryl group containing from 6 to 20 carbon atoms.
Claim 6
Dependent Claim
17 words
A catalyst according to claim 1 wherein (1) is MgCl 2 and (3) is TiCl 4 .
Claim 7
Dependent Claim
17 words
A catalyst according to claim 5 wherein B is triethylaluminum and the catalyst additionally contains ethyl anisate.
Claim 8
Dependent Claim
15 words
A catalyst according to claim 6 wherein the catalyst adjuvant is triphenyl phosphite or phenol.
Claim 9
Dependent Claim
40 words
A catalyst according to claim 6 wherein a catalyst adjuvant is selected from triphenoxyaluminum, triphenylborate, triphenyl phosphite, diphenyl phosphite, p-phenylphenol, p-chlorophenol, p-methylphenol, 2-cyclohexylphenol, 2,6-di-t-butyl-4-methylphenol, di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, 2-naphthol, 1-naphthol, 2-benzoylthiophene, triphenylsilanol, triphenylphosphine oxide, triphenyl phosphate, d-carvone, 1-carvenone, catechylphosphotrichloride, diphenylphosphorochloridate, phenylphosphorodichloridite, o-phenylenephosphorochloridate, 2-phenylphenol.
Claim 10
Dependent Claim
19 words
A catalyst according to claim 1 further including a solid particulate material which is inert to the catalyst components.
Claim 11
Dependent Claim
33 words
A catalyst according to claim 9 wherein the solid particulate material is selected from silica, alumina, calcium carbonate and solid organic material selected from polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mixtures thereof.
Claim 12
Dependent Claim
20 words
A catalyst according to claim 10 wherein said solid particulate materials are milled in the presence of (1) and (2).
Claim 13
Dependent Claim
45 words
A catalyst according to claim 1 wherein the catalyst composite obtained after treating the product of (1) and (2) with (3) is washed with an inert solvent to remove excess titanium tetrahalide and the resulting composite is dried prior to combining with cocatalyst component B.
Claim 14
Dependent Claim
28 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is triphenoxyaluminum or triphenylborate, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 15
Dependent Claim
27 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is diphenyl phosphite, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 16
Dependent Claim
34 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is p-phenylphenol, p-chlorophenol, p-methylphenol, 2-cylohexylphenol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol, 1-naphthol, or 2-phenylphenol, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 17
Dependent Claim
26 words
A catalyst according to claim 4 wherein (1) is MgCl 2 , (2) is 2-benzoylthiophene, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 18
Dependent Claim
26 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is triphenylsilanol, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 19
Dependent Claim
30 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is triphenylphosphine oxide or triphenyl phosphate, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 20
Dependent Claim
29 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is d-carvone or 1, carvenone, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
Claim 21
Dependent Claim
25 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is triphenyl phosphite, and B comprises triethylaluminum, ethyl anisate and diethylaluminum chloride.
Claim 22
Dependent Claim
30 words
A catalyst according to claim 1 wherein (1) is MgCl 2 , (2) is catechylphosphotrichloride, diphenylphosphorochloridate, phenylphosphorodichloridite, or o-phenylenephosphorochloridate, (3) is TiCl 4 and B comprises triethylaluminum and ethyl anisate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-01-06 | 1984-07-07 | 1985-01-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-01-06 | 1988-07-07 | 1989-01-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-01-06 | 1992-07-07 | 1993-01-06 | $7700.00 | Window Closed / Lapsed |