US5198399A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polymerization catalyst and method
Assignee: Millennium Petrochemicals Inc
•
Filing: 1992-01-17
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Granted: 1993-03-30
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Expires: 2012-01-17
Abstract
Abstract A catalyst, a method of preparing the catalyst, and a method of using the catalyst with a suitable cocatlayst in the polymerization or copolymerization of 1-olefins are disclosed. The catalyst is prepared by: a) contacting a group IIA organometallic compound, like 2-methylpentanoxymagnesium chloride, or a Group III organometallic compound, like triethylaluminum, or a combination thereof, with a porous or nonporous biodegradable substrate having active surface hydroxyl groups, like cellulose, to provide a modified biodegradable substrate; then b) contacting the modified biodegradable substrate with a transition metal compound, such as a transition metal halide or alkoxide, like titanium tetrachloride or vanadium(V)trichloride oxide, to form discrete catalyst particles. The catalyst particles are used in conjunction with a suitable cocatlalyst, like triethylaluminum, in the homopolymerization or copolymerization of 1-olefins. During polymerization, porous biodegradable catalyst particles are fragmented into small solid particles that are trapped within polymer. The fragmented catalyst particles are allowed to remain within the polymer; do not adversely affect the physical or esthetic properties of the polymer or articles made therefrom; and serve as biodegradable sites that facilitate environmental degradation of the polymer.
Inventors
- 👤 Raymond E. Hoff
- 👤 Leonard V. Cribbs
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 17:49
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/904; Y10S526/943
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
156 words
A solid catalyst component active in the presence of an alkylaluminum cocatalyst in olefin polymerizations prepared by the steps of: a) contacting the interior and exterior surfaces of a particulate biodegradable substrate having surface hydroxyl groups, a surface area of at least 50 square meters per gram and a pore volume of at least 0.50 milliliters per gram, with an organometallic compound selected from the group consisting of Group IIA organometallic compounds, Group III organometallic compounds, Group IIA-Group III organometallic complexes, and combinations thereof, in the presence of a solvent, to form a modified biodegradable substrate; and b) contacting the interior and exterior surfaces of the modified biodegradable substrate with a transition metal compound, in the presence of a solvent, whereby catalytically active sites are provided on the interior and exterior surfaces of the biodegradable substrate to form a solid catalyst component susceptible to fragmentation caused by polymer forming on the interior surfaces thereof during polymerization.
Claim 2
Dependent Claim
156 words
A solid catalyst component active in the presence of an alkylaluminum cocatalyst in olefin polymerizations prepared by the steps of: a) contacting the interior and exterior surfaces of a particulate biodegradable substrate having surface hydroxyl groups, a surface area of at least 50 square meters per gram and a pore volume of at least 0.50 milliliters per gram, with an organometallic compound selected from the group consisting of Group IIA organometallic compounds, Group III organometallic compounds, Group IIA-Group III organometallic complexes, and combinations thereof, in the presence of a solvent, to form a modified biodegradable substrate; and b) contacting the interior and exterior surfaces of the modified biodegradable substrate with a transition metal compound, in the presence of a solvent, whereby catalytically active sites are provided on the interior and exterior surfaces of the biodegradable substrate to form a solid catalyst component susceptible to fragmentation caused by polymer forming on the interior surfaces thereof during polymerization.
Claim 3
Dependent Claim
13 words
The catalyst component of claim 1 wherein the biodegradable substrate is a carbohydrate.
Claim 4
Dependent Claim
22 words
The catalyst component of claim 2 wherein the carbohydrate is a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, or a combination thereof.
Claim 5
Dependent Claim
43 words
The catalyst component of claim 2 wherein the carbohydrate is selected from the group consisting of sucrose, glucose, fructose, xylose, ribose, mannose, maltose, lactose, gentiobiose, starch, cellulose, glycogen, dextran, mannan, chitin, pectin, hemicellulose, carrageenan, alginic acid, plant gums, salts thereof, and combinations thereof.
Claim 6
Dependent Claim
14 words
The catalyst component of claim 1 wherein the biodegradable substrate is a carbohydrate derivative.
Claim 7
Dependent Claim
31 words
The catalyst component of claim 5 wherein the carbohydrate derivative is selected from the group consisting of ethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, hydroxybutylcellulose, carboxymethylhydroxyethylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, methylethylcellulose, chitosan, and combinations thereof.
Claim 8
Dependent Claim
17 words
The catalyst component of claim 1 wherein the biodegradable substrate is lignin, collagen, or a combination thereof.
Claim 9
Dependent Claim
31 words
The catalyst component of claim 1 wherein the biodegradable substrate is selected from the group consisting of cellulose, carboxymethylcellulose, starch, fructose, sucrose, glucose, chitin, chitosan, ethylcellulose, hydroxypropylcellulose, hydroxybutylcellulose, and combinations thereof.
Claim 10
Dependent Claim
23 words
The catalyst component of claim 1 wherein the biodegradable substrate has an average particle size of about 5 microns to about 100 microns.
Claim 11
Dependent Claim
16 words
The catalyst component of claim 9 wherein the biodegradable substrate is microcrystalline cellulose or bacterial cellulose.
Claim 12
Dependent Claim
13 words
The catalyst component of claim 1 wherein the biodegradable substrate is bacterial cellulose.
Claim 13
Dependent Claim
26 words
The catalyst component of claim 1 wherein a metal of the organometallic compound is selected from the group consisting of calcium, magnesium, aluminum, and combinations thereof.
Claim 14
Dependent Claim
56 words
The catalyst component of claim 1 wherein the Group IIA organometallic compound is selected from the group consisting of alkoxymagnesium halides; dialkoxymagnesium compounds; dialkylmagnesium compounds; alkylmagnesium silylamides, having the formula R 3 --Mg--N(Si(CH 3 ) 3 ) 2 , wherein R 3 is an alkyl group including one to about 18 carbon atoms; and combinations thereof.
Claim 15
Dependent Claim
28 words
The catalyst component of claim 13 wherein the alkoxy group or the alkyl group of the Group IIA organometallic compound includes about three to about twenty carbon atoms.
Claim 16
Dependent Claim
28 words
The catalyst component of claim 1 wherein the Group III organometallic compound is selected from the group consisting of trialkylaluminum compounds, dialkylaluminum halides, alkylaluminum dihalides, and combinations thereof.
Claim 17
Dependent Claim
24 words
The catalyst component of claim 15 wherein the alkyl group of the Group III organometallic compound includes about two to about four carbon atoms.
Claim 18
Dependent Claim
70 words
The catalyst component of claim 1 wherein the organometallic compound is a magnesium-aluminum organometallic complex having the formula (R 2 Mg) n AlR 1 3 , wherein R is an alkyl or an alkoxy group including about three to about twenty carbon atoms, R 1 is an alkyl group including about two to about four carbon atoms and n is a number in the range of 1 to about 8.
Claim 19
Dependent Claim
38 words
The catalyst component of claim 1 wherein the organometallic compound is selected from the group consisting of 2-methylpentoxymagnesium chloride, pentoxymagnesium chloride, phenoxymagnesium chloride, di-ethylhexyloxymagnesium, di-2 methylpentoxymagnesium, dibutylmagnesium, dihexyl magnesium, n-butylethylmagnesium, dibutylmagnesium-triethylaluminum complex, triethylaluminum, butylmagnesium silylamide, and combinations thereof.
Claim 20
Dependent Claim
33 words
The catalyst component of claim 1 wherein the organometallic compound is present in a weight ratio with respect to transition metal present in the transition metal compound of about 0.1 to about 100.
Claim 21
Dependent Claim
40 words
The catalyst component of claim 1 wherein the organometallic compound is a Group IIA organometallic compound and is present in a weight ratio with respect to transition metal present in the transition metal compound of about 0.1 to about 20.
Claim 22
Dependent Claim
35 words
The catalyst component of claim 1 wherein the organometallic compound is contacted with the biodegradable substrate at a temperature of about 0° C. to about 100° C. for about 5 minutes to about 120 minutes.
Claim 23
Dependent Claim
23 words
The catalyst component of claim 1 wherein the solvent comprises a hydrocarbon solvent including about five carbon atoms to about ten carbon atoms.
Claim 24
Dependent Claim
32 words
The catalyst component of claim 1 wherein the transition metal compound is a transition metal halide, a transition metal oxyhalide, a transition metal alkoxyhalide, a transition metal alkoxide, or a combination thereof.
Claim 25
Dependent Claim
37 words
The catalyst component of claim 1 wherein a transition metal of the transition metal compound is selected from the group consisting of titanium, vanadium, zirconium, chromium, nickel, cobalt, niobium, tantalum, palladium, rhodium, molybdenum, tungsten, and combinations thereof.
Claim 26
Dependent Claim
28 words
The catalyst component of claim 1 wherein the transition metal of the transition metal compound is a Group IVB metal, a Group VB metal, or a combination thereof.
Claim 27
Dependent Claim
24 words
The catalyst component of claim 1 wherein the transition metal of the transition metal compound is one or more of titanium, vanadium, and zirconium.
Claim 28
Dependent Claim
94 words
The catalyst component of claim 26 wherein the transition metal compound is selected from the group consisting of TiX 4 , Ti(OR 3 ) x X 4-x , VOX 3 , VX 4 , Zr(OR 3 ) x X 4-x , and mixtures thereof, wherein X is chloride or bromide, R 3 is cyclopentadienyl; an alkyl, a cycloalkyl or an alkenyl group including from one to about ten carbon atoms; or an aryl or alkaryl group including about five to about 20 carbon atoms, and x is an integer from 0 to 4 inclusive.
Claim 29
Dependent Claim
37 words
The catalyst component of claim 1 wherein the transition metal compound is selected from the group consisting of titanium tetrachloride, titanium(IV) methoxide, methoxytitanium trichloride, diethoxytitanium dichloride, titanium tetrabromide, vanadium(V)trichloride oxide, vanadium(IV) chloride, bis(cyclopentadienyl)zirconium dichloride, and zirconium propoxide.
Claim 30
Dependent Claim
40 words
The catalyst component of claim 1 wherein the transition metal compound is included in a sufficient amount to provide the transition metal in the range of about 0.05% to about 50%, based on the weight of the modified biodegradable substrate.
Claim 31
Dependent Claim
40 words
The catalyst component of claim 1 wherein the transition metal compound is included in a sufficient amount to provide the transition metal in the range of about 0.5% to about 20%, based on the weight of the modified biodegradable substrate.
Claim 32
Dependent Claim
38 words
The catalyst component of claim 1 wherein the transition metal compound is contacted with the modified biodegradable substrate at a temperature of from about 20° C. to about 120° C. for about 5 minutes to about 120 minutes.
Claim 33
Dependent Claim
58 words
The catalyst component of claim 1 wherein the modified biodegradable substrate is solubilized in a solution of the transition metal compound and the solvent, and after contacting the modified biodegradable substrate with the transition metal compound to form the product mixture, the solvent is separated from the product mixture and the catalyst is formed into a predetermined shape.
Claim 34
Dependent Claim
34 words
The catalyst component of claim 1 wherein the biodegradable substrate is microcrystalline cellulose or bacterial cellulose, the organometallic compound is 2-methylpentoxymagnesium chloride, the transition metal compound is titanium tetrachloride and the solvent is heptane.
Claim 35
Dependent Claim
31 words
The catalyst component of claim 1 wherein the biodegradable substrate is treated prior to interaction with the organometallic compound to reduce the number of hydroxyl groups present on the biodegradable substrate.
Claim 36
Dependent Claim
19 words
The catalyst component of claim 34 wherein the biodegradable substrate is treated by silylation, fluoridation, or a combination thereof.
Claim 37
Dependent Claim
42 words
A catalyst system comprising the solid catalyst component of claim 1 in combination with an alkylaluminum cocatalyst comprising a trialkylaluminum compound, an alkylaluminum hydride, an alkylaluminum halide, or a mixture thereof, wherein the alkyl group includes one to about ten carbon atoms.
Claim 38
Dependent Claim
35 words
The catalyst system of claim 36 wherein the alkylaluminum cocatalyst is selected from the group consisting of triethylaluminum, trioctylaluminum, tri(2-methylpentyl)aluminum, diethylaluminum hydride, methylaluminoxane, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide, and diethylaluminum trimethylsiloxide.
Claim 39
Dependent Claim
31 words
The catalyst system of claim 36 wherein the mole ratio of aluminum in the alkylaluminum cocatalyst to the transition metal in the solid catalyst component is about 3:1 to about 100:1.
Claim 40
Independent Claim
163 words
A method of preparing a solid catalyst component, said catalyst component being active in the presence of an alkylaluminum cocatalyst in olefin polymerizations, comprising the steps of: a) contacting the interior and exterior surfaces of a particulate biodegradable substrate having surface hydroxyl groups, a surface area of at least 50 square meters per gram and a pore volume of at least 0.50 milliliters per gram, with an organometallic compound selected from the group consisting of Group IIA organometallic compounds, Group III organometallic compounds, Group IIA-Group III organometallic complexes, and combinations thereof, in the presence of a solvent, to form a modified biodegradable substrate; and b) contacting the interior and exterior surfaces of the modified biodegradable substrate with a transition metal compound, in the presence of a solvent, whereby catalytically active sites are provided on the interior and exterior surfaces of the biodegradable substrate to form a solid catalyst component susceptible to fragmentation caused by polymer forming on the interior surfaces thereof during polymerization.
Claim 41
Independent Claim
163 words
A method of preparing a solid catalyst component, said catalyst component being active in the presence of an alkylaluminum cocatalyst in olefin polymerizations, comprising the steps of: a) contacting the interior and exterior surfaces of a particulate biodegradable substrate having surface hydroxyl groups, a surface area of at least 50 square meters per gram and a pore volume of at least 0.50 milliliters per gram, with an organometallic compound selected from the group consisting of Group IIA organometallic compounds, Group III organometallic compounds, Group IIA-Group III organometallic complexes, and combinations thereof, in the presence of a solvent, to form a modified biodegradable substrate; and b) contacting the interior and exterior surfaces of the modified biodegradable substrate with a transition metal compound, in the presence of a solvent, whereby catalytically active sites are provided on the interior and exterior surfaces of the biodegradable substrate to form a solid catalyst component susceptible to fragmentation caused by polymer forming on the interior surfaces thereof during polymerization.
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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) | 1996-03-29 | 1996-09-28 | 1997-03-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2000-03-29 | 2000-09-28 | 2001-03-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2004-03-29 | 2004-09-28 | 2005-03-30 | $7700.00 | Window Closed / Lapsed |