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US5494872A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalyst and solid catalyst component for preparing polyolefins with broad molecular weight distribution

Assignee: Toho Titanium Co Ltd
•
Filing: 1994-07-27
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Granted: 1996-02-27
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Expires: 2014-07-27
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Abstract

Abstract A novel catalyst and solid catalyst component useful for preparing polyolefins having a broad molecular weight distribution and high stereoregularity.

Inventors

  • 👤 Motoki Hosaka
  • 👤 Minoru Terano
  • 👤 Kazuhiro Ishii

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-01 18:07
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 24
Claim 1
Independent Claim 134 words
A catalyst for preparing polyolefins with a broad molecular weight distribution, consisting essentially of a solid catalyst component A1, an organic aluminum compound B1, and an organic silicon compound C1 having the formula: Si(C.sub.6 H.sub.11).sub.2 (OR.sup.0).sub.2 wherein C 6 H 11 is a cyclohexyl group and R 0 is a an alkyl group having 1 to 5 carbon atoms, said polyolefin has a molecular weight distribution of 6 or more, and wherein said solid catalyst component A1 is prepared by a process comprising the steps of: (i) suspending a dialkoxyl magnesium in an aromatic hydrocarbon, (ii) contacting and reacting said dialkoxyl magnesium with a diester of phthalic acid and titanium tetrachloride to obtain a solid material, washing said solid material with an aromatic hydrocarbon, and (iii) contacting said washed solid material with titanium tetrachloride.
Claim 2
Dependent Claim 134 words
A catalyst for preparing polyolefins with a broad molecular weight distribution, consisting essentially of a solid catalyst component A1, an organic aluminum compound B1, and an organic silicon compound C1 having the formula: Si(C.sub.6 H.sub.11).sub.2 (OR.sup.0).sub.2 wherein C 6 H 11 is a cyclohexyl group and R 0 is a an alkyl group having 1 to 5 carbon atoms, said polyolefin has a molecular weight distribution of 6 or more, and wherein said solid catalyst component A1 is prepared by a process comprising the steps of: (i) suspending a dialkoxyl magnesium in an aromatic hydrocarbon, (ii) contacting and reacting said dialkoxyl magnesium with a diester of phthalic acid and titanium tetrachloride to obtain a solid material, washing said solid material with an aromatic hydrocarbon, and (iii) contacting said washed solid material with titanium tetrachloride.
Claim 3
Dependent Claim 13 words
The catalyst of claim 1, wherein said organic silicon compound C1 is dicyclohexyldimethoxysilane.
Claim 4
Dependent Claim 12 words
The catalyst of claim 1 wherein said dialkoxy magnesium is diethoxy magnesium.
Claim 5
Dependent Claim 13 words
The catalyst of claim 1, wherein said dialkoxy magnesium is spherical dialkoxy magnesium.
Claim 6
Dependent Claim 13 words
The catalyst of claim 1, wherein said dialkoxy magnesium is spherical diethoxy magnesium.
Claim 7
Dependent Claim 25 words
The catalyst of claim 1, wherein the volume ratio of said titanium tetrachloride in contacting step (ii) is 1 or less to the aromatic hydrocarbon.
Claim 8
Dependent Claim 21 words
The catalyst of claim 1, wherein said reaction is carried out at a temperature of from 80° C. to 125° C.
Claim 9
Dependent Claim 227 words
A solid catalyst component A2 for olefin polymerization prepared by contacting together a Mg compound (a) represented by the following general formula (II): Mg(OR.sup.1).sub.2-m X.sub.m (II) wherein R 1 indicates at least one selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups, X is halogen atom such as chlorine, bromine or iodine and m is an integer of 0 or 1; a titanium compound (b) represented by the following general formula (III); Ti(OR.sup.2).sub.n X.sub.4-n (III) wherein R 2 is an alkyl group having 1 to 4 carbon atoms, X is halogen atom such as chlorine, bromine or iodine and n is an integer of 0, 1 or 2; at least one diester of phthalic acid (c) represented by the following general formula (IV); φ(COOR.sup.3)(COOR.sup.4) (IV) wherein φ indicates a phenyl group. R 3 and R 4 each are an alkyl group having 1 to 4 carbon atoms and are identical with or different from each other; and at least one diester of phthalic acid (d) represented by the following general formula (V): φ(COOR.sup.5)(COOR.sup.6) (V) wherein R 5 and R 6 each are an alkyl group having 4 to 12 carbon atoms, in which the number of carbon atoms in total in R 5 and R 6 is 10 to 20, and are identical with or different from each other.
Claim 10
Dependent Claim 227 words
A solid catalyst component A2 for olefin polymerization prepared by contacting together a Mg compound (a) represented by the following general formula (II): Mg(OR.sup.1).sub.2-m X.sub.m (II) wherein R 1 indicates at least one selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups, X is halogen atom such as chlorine, bromine or iodine and m is an integer of 0 or 1; a titanium compound (b) represented by the following general formula (III); Ti(OR.sup.2).sub.n X.sub.4-n (III) wherein R 2 is an alkyl group having 1 to 4 carbon atoms, X is halogen atom such as chlorine, bromine or iodine and n is an integer of 0, 1 or 2; at least one diester of phthalic acid (c) represented by the following general formula (IV); φ(COOR.sup.3)(COOR.sup.4) (IV) wherein φ indicates a phenyl group. R 3 and R 4 each are an alkyl group having 1 to 4 carbon atoms and are identical with or different from each other; and at least one diester of phthalic acid (d) represented by the following general formula (V): φ(COOR.sup.5)(COOR.sup.6) (V) wherein R 5 and R 6 each are an alkyl group having 4 to 12 carbon atoms, in which the number of carbon atoms in total in R 5 and R 6 is 10 to 20, and are identical with or different from each other.
Claim 11
Dependent Claim 18 words
The solid catalyst component A2 as defined in claim 9, wherein said titanium compound (b) is titanium tetrahalide.
Claim 12
Dependent Claim 52 words
A solid catalyst component A2 as defined in claim 9, wherein a difference between the total number of carbon atoms of R 3 and R 4 in the diester of phthalic acid (c) and that of R 5 and R 6 in the diester of phthalic acid (d) is 6 or more.
Claim 13
Dependent Claim 168 words
The solid catalyst component A2 as defined in claim 8, wherein said component prepared by contacting said magnesium compound (a), said titanium compound (b) and two different diesters of phthalic acid (c) and (d) contains at least three types of diester of phthalic acid ingredients (e), (f) and (g) represented by the following general formulas (VIII); (IX) and (X), respectively: φ(COOR.sup.10)(COOR.sup.11) (VIII) wherein R 10 and R 11 each are an alkyl group having 1 to 4 carbon atoms and are identical with or different from each other; φ(COOR.sup.14)(COOR.sup.15) (IX) wherein R 14 and R 15 are an alkyl group having 1 to 12 carbon atoms, and R 14 and R 15 are identical with or different from each other; and φ(COOR.sup.12)(COOR.sup.13) (X) wherein R 12 and R 13 each are an alkyl group having 4 to 12 carbon atoms, in which the number of carbon atoms in total in R 12 and R 13 is 10 to 20, and are identical with or different from each other.
Claim 14
Dependent Claim 43 words
The solid catalyst component A2 as difined in claim 11, wherein the contents of said ingredients (e), (f) and (g) in said solid catalyst component are 1 to 15 weight %, 0 to 10 weight % and 0.5 to 15 weight %, respectively.
Claim 15
Dependent Claim 34 words
The solid catalyst component A2 as defined in claim 11, wherein the contents of said ingredients (e), (f) and (g) in said solid catalyst component are 5 to 50 parts by weight in total.
Claim 16
Dependent Claim 371 words
A catalyst system for olefin polymerization comprising: a solid catalyst component A2 prepared by contacting together a Mg compound (a) represented by the following general formula (II): Mg(OR.sup.1).sub.2-m X.sub.m (II) wherein R 1 indicates at least one selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups, X is a chlorine or a bromine, and m is an integer of 0 or 1; a titanium compound (b) represented by the following general formula (III); Ti(OR.sup.2).sub.n X.sub.4-n (III) wherein R 2 is an alkyl group having 1 to 4 carbon atoms and n is an integer of 0, 1 or 2; at least one diester of phthalic acid (c) represented by the following general formula (IV); φ(COOR.sup.3)(COOR.sup.4) (IV) wherein φ indicates a phenyl group, R 3 and R 4 each are an alkyl group having 1 to 4 carbon atoms and may be identical with or different from each other; and at least one diester of phthalic acid (d) represented by the following general formula (V): φ(COOR.sup.5)(COOR.sup.6) (V) wherein R 5 and R 6 each are an alkyl group having 4 to 12 carbon atoms, in which the number of carbon atoms in total is 10 to 20, and may be identical with or different from each other; a component B2 which is at least one organic aluminum compound represented by the following general formula (VI): R.sup.7.sub.y AlY.sub.3-y (VI) wherein R 7 is an alkyl group having 1 to 4 carbon atoms, Y is any one of hydrogen, chlorine, bromine and iodine, and y is in the range of 0<y≦3; and a component C2 which is at least one silicon compound represented by the following general formula (VII): R.sup.8.sub.z Si(OR.sup.9).sub.4-z (VII) wherein R 8 is selected from the group consisting of an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an aryl group and an aralkyl group and may be identical or different; R 9 is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group and an aralkyl group and may be identical or different; and z is an integer of 0 to 3.
Claim 17
Dependent Claim 371 words
A catalyst system for olefin polymerization comprising: a solid catalyst component A2 prepared by contacting together a Mg compound (a) represented by the following general formula (II): Mg(OR.sup.1).sub.2-m X.sub.m (II) wherein R 1 indicates at least one selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups, X is a chlorine or a bromine, and m is an integer of 0 or 1; a titanium compound (b) represented by the following general formula (III); Ti(OR.sup.2).sub.n X.sub.4-n (III) wherein R 2 is an alkyl group having 1 to 4 carbon atoms and n is an integer of 0, 1 or 2; at least one diester of phthalic acid (c) represented by the following general formula (IV); φ(COOR.sup.3)(COOR.sup.4) (IV) wherein φ indicates a phenyl group, R 3 and R 4 each are an alkyl group having 1 to 4 carbon atoms and may be identical with or different from each other; and at least one diester of phthalic acid (d) represented by the following general formula (V): φ(COOR.sup.5)(COOR.sup.6) (V) wherein R 5 and R 6 each are an alkyl group having 4 to 12 carbon atoms, in which the number of carbon atoms in total is 10 to 20, and may be identical with or different from each other; a component B2 which is at least one organic aluminum compound represented by the following general formula (VI): R.sup.7.sub.y AlY.sub.3-y (VI) wherein R 7 is an alkyl group having 1 to 4 carbon atoms, Y is any one of hydrogen, chlorine, bromine and iodine, and y is in the range of 0<y≦3; and a component C2 which is at least one silicon compound represented by the following general formula (VII): R.sup.8.sub.z Si(OR.sup.9).sub.4-z (VII) wherein R 8 is selected from the group consisting of an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an aryl group and an aralkyl group and may be identical or different; R 9 is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group and an aralkyl group and may be identical or different; and z is an integer of 0 to 3.
Claim 18
Dependent Claim 15 words
The catalyst system as defined in claim 14, wherein said component B2 is trialkyl aluminum.
Claim 19
Dependent Claim 15 words
The catalyst system as defined in claim 14, wherein said component C2 is cycloalkyl alkoxysilane.
Claim 20
Dependent Claim 15 words
The catalyst system as defined in claim 14, wherein said component C2 is dicycloalkyl dialkoxysilane.
Claim 21
Dependent Claim 15 words
The catalyst system as defined in claim 14, wherein said component C2 is dialkyl dialkoxysilane.
Claim 22
Dependent Claim 15 words
The catalyst system as defined in claim 14, wherein said component C2 is alkyl trialkoxysilane.
Claim 23
Dependent Claim 14 words
The catalyst system as defined in claim 14, wherein said component C2 is tetraalkoxysilane.
Claim 24
Dependent Claim 73 words
The catalyst system as defined in claim 14, wherein said component C2 is at least one selected from the group consisting of di-n-propyl dimethoxysilane, di-iso-propyl dimethoxy silane, di-n-butyl dimethoxy silane, di-iso-butyl dimethoxysilane, di-t-butyl dimethoxysilane, di-n-butyl diethoxysllane, t-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl diethoxysilane, cyclohexylethyl dimethoxysilane, cyclohcxylethyl diethoxysilane, dicyclopentyl dimethoxysilane, dicyclopentyl diethoxysilane, cyclopentylmethyl dimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl diethoxysilane, n-butylmethyl dimethoxysilane, cyclohexyl(iso-propyl) dimethoxysilane, cyclopentyl(iso-propyl) dimethoxysilane, cyclopentyl(iso-butyl) dimethoxysilane and cyclohexylcyclopentyl dimethoxysilane.

References Cited (Backward Citations)

US4315835A Cited
US4816433A Cited
US4990479A Cited
US4983561A Cited
US5194531A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1999-02-26 1999-08-28 2000-02-27 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2003-02-26 2003-08-28 2004-02-27 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2007-02-26 2007-08-28 2008-02-27 $7700.00 Window Closed / Lapsed

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