US4721762A
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Process for manufacturing an ethylene-1-butene copolymer from ethylene
Assignee: IFP Energies nouvelles
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Filing: 1985-06-07
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Granted: 1988-01-26
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Expires: 2005-06-07
Abstract
Abstract The invention concerns a process for manufacturing low density linear polyethylene by copolymerizing ethylene and 1-butene, comprising the steps of: (a) dimerizing ethylene to 1-butene in the presence of a soluble catalyst comprising: an alkyl titanate, an aluminum compound of formula AlR 3 or AlR 2 H, wherein R is a hydrocarbyl radical, and an ether; (b) contacting at least a portion of the product obtained in step (a) with an inorganic compound, at least partly insoluble; (c) contacting the insoluble mixture obtained in step (b) with an halogenated aluminum compound of formula Al 2 R' 6-n X n , wherein R' is a hydrocarbyl radical, X a halogen atom, and n a number from 3 to 6, when an halogenated aluminum compound is not already present in said mixture; (d) using the resultant product, containing at least one inorganic carrier, at least one halogenated aluminum compound and at least one titanium compound, as catalyst in the polymerization reactor.
Inventors
- 👤 Dominique Commereuc
- 👤 Francois Hugues
- 👤 Nhuong Le Quan
- 👤 Adberrahim Taouli
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 23:33
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/16; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/907
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
280 words
In a process for manufacturing an ethylene-1-butene copolymer, comprising: (a) dimerizing ethylene to 1-butene by contacting ethylene with a catalyst solution obtained by interaction of at least one alkyltitanate with at least one aluminum compound, (b) contacting at least one portion of the effluent from step (a), wherein at least a part of the dimerization catalyst is dissolved, with at least one inorganic magnesium or aluminum compound, said inorganic compound being at least partly insoluble, so as to obtain an insoluble mixture formed of said inorganic compound impregnated with the dimerization catalyst elements, (c) contacting said insoluble mixture with at least one halogenated aluminum compound of formula Al 2 R' 6-n X n wherein R' is a hydrocarbyl radical, X a halogen atom and n a number in the range of 3-6, when the insoluble mixture obtained in step(b) does not already contain a halogenated aluminum compound, (d) contacting the product obtained in step (c) or the product obtained in step (b), formed of at least one partly insoluble inorganic compound, at least one aluminum halogenated compound and at least one titanium compound, with the ethylene and 1-butene from Step 2), the improvement wherein in step (a) the dimerization catalyst is a product of the reaction of: (1) a solution, in a hydrocarbon solvent, consisting essentially of at least one aluminum compound of the formula AlR 3 or AlR 2 H wherein each of the radicals R represents hydrocarbyl, with (2) a preformed solution consisting essentially of a hydrocarbon solvent, at least one ether and at least one alkyltitanate, the ether/Ti molar ratio in step (a) being about 1:1-30:1 and the Al/Ti molar ratio in step (a) being about 2:1-5:1.
Claim 2
Dependent Claim
280 words
In a process for manufacturing an ethylene-1-butene copolymer, comprising: (a) dimerizing ethylene to 1-butene by contacting ethylene with a catalyst solution obtained by interaction of at least one alkyltitanate with at least one aluminum compound, (b) contacting at least one portion of the effluent from step (a), wherein at least a part of the dimerization catalyst is dissolved, with at least one inorganic magnesium or aluminum compound, said inorganic compound being at least partly insoluble, so as to obtain an insoluble mixture formed of said inorganic compound impregnated with the dimerization catalyst elements, (c) contacting said insoluble mixture with at least one halogenated aluminum compound of formula Al 2 R' 6-n X n wherein R' is a hydrocarbyl radical, X a halogen atom and n a number in the range of 3-6, when the insoluble mixture obtained in step(b) does not already contain a halogenated aluminum compound, (d) contacting the product obtained in step (c) or the product obtained in step (b), formed of at least one partly insoluble inorganic compound, at least one aluminum halogenated compound and at least one titanium compound, with the ethylene and 1-butene from Step 2), the improvement wherein in step (a) the dimerization catalyst is a product of the reaction of: (1) a solution, in a hydrocarbon solvent, consisting essentially of at least one aluminum compound of the formula AlR 3 or AlR 2 H wherein each of the radicals R represents hydrocarbyl, with (2) a preformed solution consisting essentially of a hydrocarbon solvent, at least one ether and at least one alkyltitanate, the ether/Ti molar ratio in step (a) being about 1:1-30:1 and the Al/Ti molar ratio in step (a) being about 2:1-5:1.
Claim 3
Dependent Claim
80 words
A process according to claim 1, wherein the dimerization effluent from step (a) is fed to a fractionation zone wherein are separated: (α) at least one fraction containing 1-butene and ethylene, said fraction being fed to a polymerization reactor, (β) at least one fraction containing hexenes which are at least partly used as solvent for the preparation of the dimerization catalyst of step (a), and (γ) at least one fraction wherein the catalyst already used for the dimerization is dissolved.
Claim 4
Dependent Claim
86 words
A process according to claim 1, wherein the dimerization effluent from step (a) is used in totality in step (b), and the effluent obtained from step (b), after separation of the solid insoluble mixture, is fed to a fractionation zone wherein are separated: (α) at least one fraction containing 1-butene and ethylene, said fraction being fed to a polymerization reactor, and (β) at least one fraction containing hexenes which are at least partly used as solvent for the preparation of the dimerization catalyst of step (a).
Claim 5
Dependent Claim
98 words
A process according to claim 1, wherein the dimerization effluent obtained in step (a) is used in totality in step (b), the totality of the product obtained in step (b) is optionally fed to step (c), when an aluminum halogenated compound is not already present, the whole effluent, containing ethylene, 1-butene, hexenes and a suspended precipitate formed of at least one inorganic compound, at least partly insoluble, at least one halogenated aluminum compound and at least one titanium compound, is fed in totality to a polymerization reactor wherein said total effluent is contacted with an additional ethylene amount.
Claim 6
Dependent Claim
22 words
A process according to claim 1, wherein the inorganic compound used in step (b) consists essentially of at least one magnesium halide.
Claim 7
Dependent Claim
34 words
A process according to claim 1, wherein, in step (b), at least one inorganic magnesium compound is formed in situ by reacting at least one organic magnesium compound with at least one halogenated compound.
Claim 8
Dependent Claim
33 words
A process according to claim 6, wherein at least one organomagnesium compound or is product of association with a trialkyl aluminum is reacted with at least one aluminum halide or one alkylaluminum halide.
Claim 9
Dependent Claim
28 words
A process according to claim 1, wherein the amount of inorganic compound used in step (b) is from about 0.1 to about 100 grams per millimole of titanium.
Claim 10
Dependent Claim
42 words
A process according to claim 1, wherein the amount of halogenated aluminum compound is such that the molar ratio "halide ion/total aluminum" is from about 0.5 to about 1.5 and the molar ratio "total aluminum/titanium" is from about 2.5 to about 25.
Claim 11
Dependent Claim
13 words
A process according to claim 5, wherein the magnesium halide is magnesium chloride.
Claim 12
Dependent Claim
20 words
A process according to claim 1, wherein the ether is diethylether, dimethylether, methyl tert-butyl ether, dihydropyran, tetrahydrofuran, 2-methyl-tetrahydrofuran or 1,4-dioxane.
Claim 13
Dependent Claim
14 words
A process according to claim 11, wherein the ether is tetrahydrofuran, 2-methyl-tetrahydrofuran or 1,4-dioxane.
Claim 14
Dependent Claim
15 words
A process according to claim 1, wherein the hydrocarbon solvent is pentane, hexane or heptane.
Claim 15
Dependent Claim
20 words
A process according to claim 1, wherein the hydrocarbon solvent is a by-product of the dimerization reaction of step (a).
Claim 16
Dependent Claim
24 words
A process according to claim 14, wherein the by-product of the dimerization reaction of step (a) is 2-ethyl-1-butene, 1-hexene, 3-methyl-1-pentene or a mixture thereof.
Claim 17
Dependent Claim
24 words
A process according to claim 1, wherein the ether is tetrahydrofuran and the hydrocarbon solvent is a mixture of 3-methyl pentene, 1-hexene and 2-ethylbutene.
Claim 18
Dependent Claim
35 words
A process according to claim 1, wherein in step (a) the dimerization catalyst results from the interaction of triethylaluminum in a hexene fraction with a solution of butyltitanate and tetrahydrofuran in the same hexene fraction.
Claim 19
Dependent Claim
18 words
A process according to claim 1, wherein the reaction is performed in a solvent comprising an olefinic hydrocarbon.
Claim 20
Dependent Claim
23 words
A process according to claim 1, wherein in the catalyst, the alkyltitanate has the formula Ti(OR") 4 'and R" is C 2-10 alkyl.
References Cited (Backward Citations)
US2943125A
Cited
US3116274A
Cited
US2953552A
Cited
US3336278A
Cited
US3050471A
Cited
SU455082A1
Cited
US4296223A
Cited
US4133944A
Cited
US4172050A
Cited
US3969429A
Cited
US4319011A
Cited
US4312783A
Cited
US4308369A
Cited
US4370456A
Cited
EP0135441A1
Cited
US4532370A
Cited
US4615998A
Cited
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