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US4190555A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalyst system for polymerizing alpha-olefins and method of making same

Assignee: Mitsui Toatsu Chemicals Inc
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Filing: 1977-01-27
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Granted: 1980-02-26
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Expires: 1997-01-27
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Abstract

Abstract A method is disclosed for preparing a catalyst system for polymerizing alpha -olefins. This method comprises admixing with at least an organoaluminum compound an activated titanium component which is prepared by first reacting a titanium compound of the general formula, TiXn(OR)4-n (in which X is a halogen atom, R is an alkyl group or a phenyl group, and n is 2 to 4), with a metal of Group II or III of the Periodic Table and a halide of a metal of Group II or III of the Periodic Table in the presence of an aromatic compound, then treating the resulting reaction product with an oxygen-containing organic compound, and further treating with a tetrahalide of titanium, vanadium or both at a temperature of from -80 DEG C. to 80 DEG C., and finally aging at a temperature above 30 DEG C. for from 30 minutes to 24 hours.

Inventors

  • 👤 Yoshinori Takamura
  • 👤 Hakusei Hamada
  • 👤 Kiyoyuki Kitamura
  • 👤 Tetsuro Inada
  • 👤 Kunio Kodama
  • 👤 Katuyuki Usami

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 02:52
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 21
Claim 1
Independent Claim 273 words
A method of preparing an activated titanium component for use in an α-olefin polymerization catalyst system having at least one organo-aluminum compound admixed therein, said method comprising: (a) reacting at a temperature in the range of 50°-200° C. and in the presence of an aromatic compound selected from aromatic hydrocarbons and halogenated aromatic hydrocarbons (i) a titanium compound having the general formula Tix n (OR) 4-n , wherein X is a halogen, R is a hydrocarbon group radical and n is 2 to 4, (ii) a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, and (iii) at least one halide of a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound; (b) treating the thus obtained reaction product with 0.1-20 moles of an organic compound selected from hydrocarbyl and chlorohydrocarbyl ethers, ketones and esters per mole of product at a temperature in the range of -50° to 150° C.; (c) further treating the thus treated reaction product with 0.1-20 moles of a tetrahalide of a metal selected from the group consisting of titanium, vanadium and mixtures thereof, per mole of product at a temperature in the range of -80° to 80° C.; and (d) aging the thus further treated reaction product at a temperature greater than 30° C. for a time ranging from 30 minutes to 24 hours.
Claim 2
Independent Claim 273 words
A method of preparing an activated titanium component for use in an α-olefin polymerization catalyst system having at least one organo-aluminum compound admixed therein, said method comprising: (a) reacting at a temperature in the range of 50°-200° C. and in the presence of an aromatic compound selected from aromatic hydrocarbons and halogenated aromatic hydrocarbons (i) a titanium compound having the general formula Tix n (OR) 4-n , wherein X is a halogen, R is a hydrocarbon group radical and n is 2 to 4, (ii) a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, and (iii) at least one halide of a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound; (b) treating the thus obtained reaction product with 0.1-20 moles of an organic compound selected from hydrocarbyl and chlorohydrocarbyl ethers, ketones and esters per mole of product at a temperature in the range of -50° to 150° C.; (c) further treating the thus treated reaction product with 0.1-20 moles of a tetrahalide of a metal selected from the group consisting of titanium, vanadium and mixtures thereof, per mole of product at a temperature in the range of -80° to 80° C.; and (d) aging the thus further treated reaction product at a temperature greater than 30° C. for a time ranging from 30 minutes to 24 hours.
Claim 3
Dependent Claim 26 words
The method according to claim 1, wherein said hydrocarbon group radical of said titanium compound is selected from the group consisting of alkyl and phenyl groups.
Claim 4
Dependent Claim 19 words
The method according to claim 1, wherein said metal is selected from the group consisting of aluminum and magnesium.
Claim 5
Dependent Claim 34 words
The method according to claim 1, wherein said halide is selected from the group consisting of iodides, bromides and chlorides of a metal selected from the group consisting of aluminum, magnesium and mixtures thereof.
Claim 6
Dependent Claim 33 words
The method according to claim 1, wherein said aromatic compound is present in the reaction in a molar amount of from 20 to 50 times the moles of the titanium compound reactant (a).
Claim 7
Dependent Claim 29 words
The method according to claim 1, wherein said organic compound is selected from the group consisting of n-propyl ether, n-butyl ether, iso-amyl ether, anisole, diethyl ketone and butyl acetate.
Claim 8
Dependent Claim 27 words
The method according to claim 1, wherein said organic compound is employed in a molar amount of 0.5-5 moles per mole of the said obtained reaction product.
Claim 9
Dependent Claim 45 words
The method according to claim 1, wherein said further treating with said tetrahalide is effected at a temperature in the range of -50° to 30° C. with a molar amount of tetrahalide in the range of 0.1-20 moles per mole of said obtained reaction product.
Claim 10
Dependent Claim 19 words
The method according to claim 1, wherein said aging is effected at temperatures of from 40° to 150° C.
Claim 11
Dependent Claim 275 words
A catalyst system for use in the polymerization of α-olefins, which comprises, admixed with at least one organo-aluminum compound, in an amount of from 0.1 to 100 moles per mole of said organo-aluminum compound, an activated titanium component which is the product of the reaction among (i) a titanium compound of the general formula TiX n (OR) 4-n , wherein X is a halogen, R is a hydrocarbon group radical and n is 2 to 4, (ii) a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, and (iii) at least one halide of a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, said reaction being carried out in the presence of an aromatic compound selected from aromatic hydrocarbons and halogenated aromatic hydrocarbons at a temperature of 50° to 200° C., said reaction product having been treated with 0.1-20 moles of an organic compound selected from hydrocarbyl and chlorohydrocarbyl ethers, ketones and esters per mole of product at a temperature of -50° to 150° C., and further treated with 0.1-20 moles of a tetrahalide of a metal selected from the group consisting of titanium, vanadium and mixtures thereof per mole of product, at a temperature of -80° to 80° C., and subsequently aged at a temperature greater than 30° C. for a time ranging from 30 minutes to 24 hours.
Claim 12
Dependent Claim 275 words
A catalyst system for use in the polymerization of α-olefins, which comprises, admixed with at least one organo-aluminum compound, in an amount of from 0.1 to 100 moles per mole of said organo-aluminum compound, an activated titanium component which is the product of the reaction among (i) a titanium compound of the general formula TiX n (OR) 4-n , wherein X is a halogen, R is a hydrocarbon group radical and n is 2 to 4, (ii) a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, and (iii) at least one halide of a metal selected from the class consisting of groups II and III of the Periodic Table and present in the reaction in a molar amount of from 0.5 to 20 times the moles of the titanium compound, said reaction being carried out in the presence of an aromatic compound selected from aromatic hydrocarbons and halogenated aromatic hydrocarbons at a temperature of 50° to 200° C., said reaction product having been treated with 0.1-20 moles of an organic compound selected from hydrocarbyl and chlorohydrocarbyl ethers, ketones and esters per mole of product at a temperature of -50° to 150° C., and further treated with 0.1-20 moles of a tetrahalide of a metal selected from the group consisting of titanium, vanadium and mixtures thereof per mole of product, at a temperature of -80° to 80° C., and subsequently aged at a temperature greater than 30° C. for a time ranging from 30 minutes to 24 hours.
Claim 13
Dependent Claim 42 words
The catalyst system according to claim 10, wherein said organo-aluminum compound has a general formula selected from AlR 2 X and AlR 3 , wherein R is selected from the class consisting of alkyl and aryl radicals and X is a halogen.
Claim 14
Dependent Claim 27 words
The catalyst system according to claim 10, wherein said hydrocarbon group radical of said titanium compound is selected from the group consisting of alkyl and phenyl groups.
Claim 15
Dependent Claim 20 words
The catalyst system according to claim 10, wherein said metal is selected from the group consisting of aluminum and magnesium.
Claim 16
Dependent Claim 35 words
The catalyst system according to claim 10, wherein said halide is selected from the group consisting of iodides, bromides and chlorides of a metal selected from the group consisting of aluminum, magnesium and mixtures thereof.
Claim 17
Dependent Claim 34 words
The catalyst system according to claim 10, wherein said aromatic compound is present in the reaction in a molar amount of from 20 to 50 times the moles of the titanium compound reactant (a).
Claim 18
Dependent Claim 30 words
The catalyst system according to claim 10, wherein said organic compound is selected from the group consisting of n-propyl ether, n-butyl ether, iso-amyl ether, anisole, diethyl ketone and butyl acetate.
Claim 19
Dependent Claim 28 words
The catalyst system according to claim 10, wherein said organic compound is employed in a molar amount of 0.5-5 moles per mole of the said obtained reaction product.
Claim 20
Dependent Claim 46 words
The catalyst system according to claim 10, wherein said further treating with said tetrahalide is effected at a temperature in the range of -50° to 30° C. with a molar amount of tetrahalide in the range of 0.1-20 moles per mole of said obtained reaction product.
Claim 21
Dependent Claim 19 words
The catalyst system according to claim 10, wherein said aging is effected at temperatures of 40° to 150° C.

References Cited (Backward Citations)

US3492281A Cited
US3769233A Cited
US3984350A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1983-02-25 1983-08-27 1984-02-26 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1987-02-25 1987-08-27 1988-02-26 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1991-02-25 1991-08-27 1992-02-26 $7700.00 Window Closed / Lapsed

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