US4378304A
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Catalyst and methods
Assignee: Enron Chemical Co
•
Filing: 1981-06-03
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Granted: 1983-03-29
•
Expires: 2001-06-03
Abstract
Abstract A catalyst, a method of preparing a catalyst and method of polymerizing olefins with the catalyst in which the catalyst is prepared by reacting a support with a Group IIA organometallic compound essentially free of aluminum alkyls and reacting this product with water or a hydrocarbyl alcohol, then reacting this product with, for example, titanium tetrachloride, followed if necessary by removing unreacted ingredients and finally activating by contacting with a cocatalyst in the absence of oxygen and moisture.
Inventors
- 👤 Robert A. Dombro
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 09:35
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
136 words
A catalyst prepared by the method comprising: (1) reacting a finely divided, difficultly reducible, porous support with (2) a Group IIA organometallic compound essentially free of aluminum alkyls, then reacting the resulting product with (3) water or a hydrocarbyl alcohol in a molar ratio to the compound of step (2) of from 0.5 to 1 to 4 to 1, then reacting the product of this with (4) a Group IVB and/or VB transition metal halide or oxyhalide, (5) removing essentially all unreacted components and by-products from the reactions of steps (1), (2), (3) and (4), followed by (6) activating the resulting reaction product by treating in the substantial absence of air with a cocatalyst that is either hydrogen or a Group IA, IIA, IIIA or IIB organometallic compound or mixture of two or more of these.
Claim 2
Dependent Claim
136 words
A catalyst prepared by the method comprising: (1) reacting a finely divided, difficultly reducible, porous support with (2) a Group IIA organometallic compound essentially free of aluminum alkyls, then reacting the resulting product with (3) water or a hydrocarbyl alcohol in a molar ratio to the compound of step (2) of from 0.5 to 1 to 4 to 1, then reacting the product of this with (4) a Group IVB and/or VB transition metal halide or oxyhalide, (5) removing essentially all unreacted components and by-products from the reactions of steps (1), (2), (3) and (4), followed by (6) activating the resulting reaction product by treating in the substantial absence of air with a cocatalyst that is either hydrogen or a Group IA, IIA, IIIA or IIB organometallic compound or mixture of two or more of these.
Claim 3
Dependent Claim
24 words
The catalyst of claim 1 wherein said support is silica, alumina, zirconia, thoria or magnesia or a mixture of two or more of these.
Claim 4
Dependent Claim
35 words
The catalyst of claim 1 wherein said compound of (2) is essentially MR 2 in which M is beryllium, magnesium, calcium, strontium, barium or mixtures of these and R is hydrogen or a hydrocarbyl radical.
Claim 5
Dependent Claim
14 words
The catalyst of claim 3 wherein said organometallic compound of (2) is a dialkylmagnesium.
Claim 6
Dependent Claim
13 words
The catalyst of claim 4 wherein said organometallic compound of (2) is dimethylmagnesium.
Claim 7
Dependent Claim
13 words
The catalyst of claim 4 wherein said organometallic compound of (2) is ethyl-n-butylmagnesium.
Claim 8
Dependent Claim
13 words
The catalyst of claim 4 wherein said organometallic compound of (2) is di-n-hexylmagnesium.
Claim 9
Dependent Claim
13 words
The catalyst of claim 4 wherein said organometallic compound of (2) is n-butyl-s-butylmagnesium.
Claim 10
Dependent Claim
39 words
The catalyst of claim 1 wherein said support is calcined, the organometallic compound of (2) is a dialkylmagnesium at a molar concentration equal to about 0.25-3 times the molar concentration of the surface hydroxyls on the calcined porous support.
Claim 11
Dependent Claim
34 words
The catalyst of claim 8 wherein said reaction is conducted in a liquid hydrocarbon slurry at a temperature between ambient and about 150° C., said hydrocarbon having from about 4 to 8 carbon atoms.
Claim 12
Dependent Claim
12 words
The catalyst of claim 10 wherein said temperature is about 90°-100° C.
Claim 13
Dependent Claim
31 words
The catalyst of claim 1 wherein the hydrocarbyl alcohol of (3) is of the formula ROH in which R is an alkyl, aryl, alkaryl or aralkyl, each having 1-20 carbon atoms.
Claim 14
Dependent Claim
20 words
The catalyst of claim 1 wherein the reaction of step (3) is at an elevated temperature of about 90°-100° C.
Claim 15
Dependent Claim
43 words
The catalyst of claim 1 wherein the reaction of step (4) is in a molar ratio of Group IVB or VB transition metal halide or oxyhalide to the alkylmagnesium compound reaction product of step (3) of from 0.5 to about 4 to 1.
Claim 16
Dependent Claim
37 words
The catalyst of claim 1 wherein the reaction of step (4) is in a molar ratio of Group IVB or VB transition metal halide or oxyhalide to water or hydrocarbyl alcohol of from about 1-10 to 1.
Claim 17
Dependent Claim
23 words
The catalyst of claim 15 wherein said reaction is conducted in a liquid hydrocarbon slurry and at a temperature of about 90°-150° C.
Claim 18
Dependent Claim
12 words
The catalyst of claim 16 wherein said temperature is about 90°-135° C.
Claim 19
Dependent Claim
30 words
The catalyst of claim 1 wherein said reacted components and by-products are removed by washing with a dry hydrocarbon liquid or gas at temperatures from ambient to about 150° C.
Claim 20
Dependent Claim
16 words
The catalyst of claim 18 wherein the upper temperature limit is less than about 100° C.
Claim 21
Dependent Claim
13 words
The catalyst of claim 1 wherein said cocatalyst of step (6) comprises hydrogen.
Claim 22
Dependent Claim
29 words
The catalyst of claim 1 wherein said cocatalyst of step (6) is present in a molar ratio to the titanium tetrachloride of step (4) of about 0.1-10 to 1.
Claim 23
Dependent Claim
12 words
The catalyst of claim 21 wherein said molar ratio is about 3:1.
Claim 24
Independent Claim
138 words
The method of preparing an active polymerizing catalyst comprising: (1) reacting a finely divided, difficulty reducible, porous support with (2) a Group IIA organometallic compound essentially free of aluminum alkyls, then reacting the resulting product with (3) water or a hydrocarbyl alcohol in a molar ratio to the compound of step (2) of from 0.5 to 1 to 4 to 1, then reacting the product of this with (4) a Group IVB and/or VB transition metal halide or oxyhalide, (5) removing essentially all unreacted components and by-products from the reactions of steps (1), (2), (3) and (4), followed by (6) activating the resulting reaction product by treating in the substantial absence of air with a cocatalyst that is either hydrogen or a Group IA, IIA, IIIA or IIB organometallic compound or mixture of two or more of these.
Claim 25
Independent Claim
138 words
The method of preparing an active polymerizing catalyst comprising: (1) reacting a finely divided, difficulty reducible, porous support with (2) a Group IIA organometallic compound essentially free of aluminum alkyls, then reacting the resulting product with (3) water or a hydrocarbyl alcohol in a molar ratio to the compound of step (2) of from 0.5 to 1 to 4 to 1, then reacting the product of this with (4) a Group IVB and/or VB transition metal halide or oxyhalide, (5) removing essentially all unreacted components and by-products from the reactions of steps (1), (2), (3) and (4), followed by (6) activating the resulting reaction product by treating in the substantial absence of air with a cocatalyst that is either hydrogen or a Group IA, IIA, IIIA or IIB organometallic compound or mixture of two or more of these.
Claim 26
Dependent Claim
24 words
The method of claim 23 wherein said support is silica, alumina, zirconia, thoria or magnesia or a mixture of two or more of these.
Claim 27
Dependent Claim
35 words
The method of claim 23 wherein said compound of (2) is essentially MR 2 in which M is beryllium, magnesium, calcium, strontium, barium or mixtures of these and R is hydrogen or a hydrocarbyl radical.
Claim 28
Dependent Claim
14 words
The method of claim 25 wherein said organometallic compound of (2) is a dialkylmagnesium.
Claim 29
Dependent Claim
13 words
The method of claim 26 wherein said organometallic compound of (2) is dimethylmagnesium.
Claim 30
Dependent Claim
13 words
The method of claim 26 wherein said organometallic compound of (2) is ethyl-n-butylmagnesium.
Claim 31
Dependent Claim
13 words
The method of claim 26 wherein said organometallic compound of (2) is di-n-hexylmagnesium.
Claim 32
Dependent Claim
13 words
The method of claim 26 wherein said organometallic compound of (2) is n-butyl-s-butylmagnesium.
Claim 33
Dependent Claim
39 words
The method of claim 23 wherein said support is calcined, the organometallic compound of (2) is a dialkylmagnesium at a concentration equal to 0.25 up to 3 times the molar concentration of the surface hydroxyls on the calcined support.
Claim 34
Dependent Claim
34 words
The method of claim 31 wherein said reaction is conducted in a liquid hydrocarbon slurry at a temperature between ambient and about 150° C., said hydrocarbon having from about 4 to 8 carbon atoms.
Claim 35
Dependent Claim
12 words
The method of claim 32 wherein said temperature is about 90°-100° C.
Claim 36
Dependent Claim
31 words
The method of claim 23 wherein the hydrocarbyl alcohol of (3) is of the formula ROH in which R is an alkyl, aryl, alkaryl or aralkyl, each having 1-20 carbon atoms.
Claim 37
Dependent Claim
20 words
The method of claim 23 wherein the reaction of step (3) is at an elevated temperature of about 90°-100° C.
Claim 38
Dependent Claim
43 words
The method of claim 23 wherein the reaction of step (4) is in a molar ratio of Group IVB or VB transition metal halide or oxyhalide to the alkylmagnesium compound reaction product of step (3) of from 0.5 to about 4 to 1.
Claim 39
Dependent Claim
37 words
The method of claim 23 wherein the reaction of step (4) is in a molar ratio of Group IVB or VB transition metal halide or oxyhalide to water or hydrocarbyl alcohol of from about 1-10 to 1.
Claim 40
Dependent Claim
23 words
The method of claim 36 wherein said reaction is conducted in a liquid hydrocarbon slurry and at a temperature of about 90°-150° C.
Claim 41
Dependent Claim
12 words
The method of claim 38 wherein said temperature is about 90°-135° C.
Claim 42
Dependent Claim
30 words
The method of claim 23 wherein said reacted components and by-products are removed by washing with a dry hydrocarbon liquid or gas at temperatures from ambient to about 150° C.
Claim 43
Dependent Claim
16 words
The method of claim 40 wherein the upper temperature limit is less than about 100° C.
Claim 44
Dependent Claim
13 words
The method of claim 23 wherein said cocatalyst of step (6) comprises hydrogen.
Claim 45
Dependent Claim
29 words
The method of claim 23 wherein said cocatalyst of step (6) is present in a molar ratio to the titanium tetrachloride of step (4) of about 0.1-10 to 1.
Claim 46
Dependent Claim
12 words
The method of claim 43 wherein said molar ratio is about 3:1.
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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) | 1986-03-28 | 1986-09-27 | 1987-03-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-03-28 | 1990-09-27 | 1991-03-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-03-28 | 1994-09-27 | 1995-03-29 | $7700.00 | Window Closed / Lapsed |