US4478952A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Supported catalyst for olefin polymerization
Assignee: EIDP Inc
•
Filing: 1983-03-18
•
Granted: 1984-10-23
•
Expires: 2003-03-18
Abstract
Abstract A method for the preparation of supported Ziegler-Natta catalysts comprising contacting a transition metal alkoxide and/or siloxide compound with a magnesium-containing reagent. The magnesium reagent is prepared in the presence of a magnesium chloride support utilizing an anhydrous and oxygen-free mixture of magnesium halide and magnesium metal, slurried in a hydrocarbon solvent. A halogenated hydrocarbon is added to produce the magnesium-containing reagent. Thereafter the transition metal alkoxide and/or siloxide compound is mixed with the slurry. An alkylating agent is added to form an active supported olefin polymerization catalyst.
Inventors
- 👤 Mark P. Mack
- 👤 Charles T. Berge
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 11:28
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
81 words
A method for forming a supported activated catalyst for olefin polymerization comprising (a) contacting a mixture of magnesium metal and magnesium dihalide with alkyl halides or aryl halides or mixtures of these to form an organometallic substance in-situ; (b) contacting transition metal alkoxides, siloxides or mixtures of these with (a), then (c) adding alkylating agents to the product of (b) to form a polymerization catalyst, with the proviso that substantially all unreacted alkyl or aryl halides are removed before step (c).
Claim 2
Independent Claim
81 words
A method for forming a supported activated catalyst for olefin polymerization comprising (a) contacting a mixture of magnesium metal and magnesium dihalide with alkyl halides or aryl halides or mixtures of these to form an organometallic substance in-situ; (b) contacting transition metal alkoxides, siloxides or mixtures of these with (a), then (c) adding alkylating agents to the product of (b) to form a polymerization catalyst, with the proviso that substantially all unreacted alkyl or aryl halides are removed before step (c).
Claim 3
Independent Claim
120 words
A method for forming a supported activated catalyst for olefin polymerization comprising (a) reacting magnesium metal with at least one organic halide to yield a dialkyl magnesium composition, magnesium dihalide and unreacted magnesium metal; (b) separating the magnesium dihalide and magnesium metal from the dialkyl magnesium composition in the substantial absence of oxygen and moisture, then treating the magnesium dihalide and magnesium metal with alkyl halides or aryl halides or mixtures of these to form an organometallic substance in-situ; (c) contacting transition metal alkoxides, siloxides or mixtures of these with the mixture of (b) then (d) adding alkylating agents to form a polymerization catalyst, with the proviso that substantially all unreacted alkyl or aryl halides are removed before step (d).
Claim 4
Independent Claim
120 words
A method for forming a supported activated catalyst for olefin polymerization comprising (a) reacting magnesium metal with at least one organic halide to yield a dialkyl magnesium composition, magnesium dihalide and unreacted magnesium metal; (b) separating the magnesium dihalide and magnesium metal from the dialkyl magnesium composition in the substantial absence of oxygen and moisture, then treating the magnesium dihalide and magnesium metal with alkyl halides or aryl halides or mixtures of these to form an organometallic substance in-situ; (c) contacting transition metal alkoxides, siloxides or mixtures of these with the mixture of (b) then (d) adding alkylating agents to form a polymerization catalyst, with the proviso that substantially all unreacted alkyl or aryl halides are removed before step (d).
Claim 5
Dependent Claim
15 words
A method as described in claim 2 wherein a chlorinating agent is added after (c).
Claim 6
Dependent Claim
27 words
A method as described in claim 3 wherein step (b) is carried out in the presence of excess alkyl halides or aryl halides or mixtures of these.
Claim 7
Dependent Claim
27 words
A method as described in claim 4 wherein the excess alkyl halides of (b) are normal or branched paraffin halides containing from 1 to 30 carbon atoms.
Claim 8
Dependent Claim
14 words
A method as described in claim 5 wherein the excess halides are alkyl halides.
Claim 9
Dependent Claim
61 words
A method as described in claim 6 wherein the halides of step (b) are selected from the group consisting of allyl bromide, allyl chloride, benzyl bromide, benzyl chloride, 1-bromobutane, 2-bromobutane, 1-bromodecane, 3-bromodecane, bromoethane, 1-bromoheptane, 1-bromohexane 1-bromopentane, 2-bromopentane, 1-bromopropane, 2-bromopropane, 1-chlorobutane, 2-chlorobutane, 1-iodobutane, 1-iodopropane, 2-iodopropane, vinyl bromide, o-bromoanisole, m-bromoanisole, p-bromoanisole, 9-bromoanthracene, 4-bromotoluene, 2-bromo-m-xylene, 4-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, chlorobenzene, cyclopentylbromide, cyclopentylchloride, and cyclopropylbromide.
Claim 10
Dependent Claim
20 words
A method as described in claim 3 wherein after addition of the chlorinating agent a solid forms which is isolated.
Claim 11
Dependent Claim
16 words
A method as described in claim 8 wherein the isolated solid is washed with inert hydrocarbons.
Claim 12
Dependent Claim
81 words
A method as described in claim 3 wherein the transition metal alkoxide have the general formula R x M(OR) y wherein each R is, independently, hydrogen, alkyl or silyl groups containing from 1 to 20 carbon atoms, aryl groups, aralkyl groups or alkaryl groups containing from 6 to 20 carbon atoms, x+y equals the valence of M, and M is a transition metal selected from the group consisting of titanium, chromium, zirconium, vanadium, tungsten, manganese, molybdenum, ruthenium, rhodium, cobalt and nickel.
Claim 13
Dependent Claim
229 words
A method as described in claim 10 wherein the transition metal alkoxides are selected from the group consisting of Ti(OCH 2 CH 3 ) 4 Ti(O-i-propyl) 4 Ti(O-n-propyl) 4 Ti(O-n-butyl) 4 Ti(O-sec-butyl) 4 TiCH 3 (O-n-hexyl) 3 Ti(OSi(CH 3 ) 3 ) 4 Ti(CH 2 CH 3 ) 2 (O-n-propyl) 2 Ti[CH 2 (CH 2 ) 18 CH 3 ](O-n-dodecyl) 3 Ti(CH 2 C 6 H 5 ) 2 (O-n-hexyl) 2 Ti(cyclopentadiene) 2 (OCH 3 ) 2 Ti(cyclopentadiene)(OCH 2 CH 3 ) 3 Ti(OSi(butyl) 3 ) 2 (O-i-propyl) 2 Ti(OSi(CH 3 )(CH 2 CH 3 )(C 6 H 5 ))(O-n-heptyl) 3 Zr(O-i-propyl) 4 Zr(O-n-propyl) 4 Zr(OCH 3 ) 4 Zr(OCH 3 )(OCH 2 CH 3 ) 3 Zr(O-n-butyl) 2 (O-C 6 H 5 ) 2 Ti(OSi(CH 2 CH 3 ) 3 ) 4 Ti(OSi(i-propyl) 3 ) 4 Ti(OSi(n-propyl) 3 ) 4 Ti(OSi(sec-butyl) 3 ) 4 TiCH 2 CH 3 (OSi(n-hexyl) 3 ) 3 Ti(CH 3 ) 2 (OSi(n-dodecyl) 3 ) 2 Ti(cyclopentadiene) 2 (OSi(CH 3 )(C 2 H 5 ) 2 ) 2 Zr(O-n-butyl) 4 Zr(OSi(CH 3 ) 3 ) 4 CH 3 Ti(O-i-propyl) 3 CH 3 Ti(O-i-dodecyl) 3 Ti(O-i-hexyl) 4 CH 3 CH 2 Ti(O-n-butyl) 3 (cyclopentadiene 2 Ti(O-n-hexyl) 2 (cyclopentadiene)Ti(OCH 3 ) 3 Ti(O-Si(CH 3 ) 2 (CH 2 CH 3 ))(O-n-heptyl) 3 Zr(OSi(n-propyl) 3 ) 4 Zr(o-n-hexyl) 2 (OSi(n-butyl) 3 ) 2 Zr(O-i-butyl)(OSi(i-dodecyl) 3 ) 3
Claim 14
Dependent Claim
74 words
A method as described in claim 10 wherein the chlorinating agent added after (c) is selected from the group consisting of methylaluminum dichloride, methylaluminum sesquichloride, isobutylaluminum dichloride, isobutylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum chloride, ethyl-aluminum sesquichloride, tin tetrachloride, silicon tetrachloride, hydrogen chloride, trichlorosilane, aluminum chloride, ethylboron dichloride, boron chloride, diethylboron chloride, chloroform, phosphorus trichloride, phosphorus oxychloride, acetyl chloride, thionyl chloride, sulfur chloride, methyl trichlorosilane, dimethyl dichlorosilane, titanium tetrachloride, vanadium tetrachloride, zirconium tetrachloride and vanadium trichloride.
Claim 15
Dependent Claim
26 words
A method as described in claim 12 wherein the reaction of (a) takes place at a temperature of from about 20° C. to about 200° C.
Claim 16
Dependent Claim
25 words
A method as described in claim 13 wherein any excess alkyl or aryl halides are removed before step (d), followed by washing with inert hydrocarbons.
Claim 17
Dependent Claim
19 words
A method as described in claim 4 wherein the solids of (b) can be separated by filtration or decantation.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-10-23 | 1988-04-23 | 1988-10-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-10-23 | 1992-04-23 | 1992-10-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-10-23 | 1996-04-23 | 1996-10-23 | $7700.00 | Window Closed / Lapsed |