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US5461128A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for producing a styrenic polymer

Assignee: Idemitsu Kosan Co Ltd
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Filing: 1993-01-04
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Granted: 1995-10-24
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Expires: 2013-01-04
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Abstract

Abstract There are disclosed a catalyst which comprises (A) a titanium compound having one pi electron-based ligand (e.g. pentamethylcyclopentadienyl group) or two same pi electron-based lignads and (B) an ionic compound comprising a non-coordinate anion and a cation of an element typifying the group 4 elements of the Periodic Table (e.g. triphenylcarbonium tetra(pentafluorophenyl)borate; a catalyst comprising (C) an alkylating agent (e.g. triisobutylaluminum) in addition to the components (A) and (B); and a process for producing a styrenic polymer by the use of any of the aforesaid catalysts. By using the aforementioned catalyst and process, a highly syndiotactic styrenic polymer can be efficiently produced.

Inventors

  • 👤 Mizutomo Takeuchi
  • 👤 Norio Tomotsu

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 20:16
CPC Classifications
C; C08; C08F; C08F12/00; C08F12/02; C08F12/04; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912

Claims Analysis

Total Claims: 28
Claim 1
Independent Claim 418 words
A process for producing a styrenic polymer having a high degree of syndiotactic configuration, comprising polymerizing at least one monomer selected from the group consisting of styrene, alkylstyrenes, alkoxystyrenes, halogenated styrenes and vinylbenzoate esters in the presence of a catalyst comprising (A) a titanium compound having formula (I) TiR.sup.1 XYZ (I) wherein R 1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a halogen atom, or said titanium compound has the formula (II) Ti(R.sup.2).sub.2 R.sup.3 R.sup.4 (II) wherein each R 2 is identical and is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a halogen atom or an amino group; and R 2 may be crosslinked by an alkylidene group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium ions; and (B) an ionic compound comprising a non-coordinate anion and a cation having the formula (V) M.sup.2 R.sup.8 R.sup.9 R.sup.10 (V) wherein M 2 is a silyl cation or germanium cation, and R 8 , R 9 and R 10 , which may be the same or different, are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a thioalkoxy group having 1 to 20 carbon atoms.
Claim 2
Dependent Claim 418 words
A process for producing a styrenic polymer having a high degree of syndiotactic configuration, comprising polymerizing at least one monomer selected from the group consisting of styrene, alkylstyrenes, alkoxystyrenes, halogenated styrenes and vinylbenzoate esters in the presence of a catalyst comprising (A) a titanium compound having formula (I) TiR.sup.1 XYZ (I) wherein R 1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a halogen atom, or said titanium compound has the formula (II) Ti(R.sup.2).sub.2 R.sup.3 R.sup.4 (II) wherein each R 2 is identical and is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a halogen atom or an amino group; and R 2 may be crosslinked by an alkylidene group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium ions; and (B) an ionic compound comprising a non-coordinate anion and a cation having the formula (V) M.sup.2 R.sup.8 R.sup.9 R.sup.10 (V) wherein M 2 is a silyl cation or germanium cation, and R 8 , R 9 and R 10 , which may be the same or different, are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a thioalkoxy group having 1 to 20 carbon atoms.
Claim 3
Dependent Claim 15 words
The process of claim 1, wherein said cation of component (B) is a silyl cation.
Claim 4
Dependent Claim 31 words
The process of claim 2, wherein said silyl cation is selected from the group consisting of triphenylsilyl cation, trimethoxysilyl cation, tri(thioisopropyl)silyl cation, trimethylsilyl cation, 4,4',4"-tri(methoxyphenyl)silyl cation, tri(tolyl)silyl cation and 4,4',4"-tri(chlorophenyl)silyl cation.
Claim 5
Dependent Claim 15 words
The process of claim 1, wherein said cation of component (B) is a germanium cation.
Claim 6
Dependent Claim 19 words
The process of claim 1, wherein said styrenic polymer has a proportion of racemic diads of at least 75%.
Claim 7
Dependent Claim 19 words
The process of claim 5, wherein said styrenic polymer has a proportion of racemic diads of at least 85%.
Claim 8
Dependent Claim 19 words
The process of claim 1, wherein said styrenic polymer has a proportion of racemic pentads of at least 30%.
Claim 9
Dependent Claim 19 words
The process of claim 7, wherein said styrenic polymer has a proportion of racemic pentads of at least 50%.
Claim 10
Dependent Claim 15 words
The process of claim 1, wherein said process produces at least 5.1 kg (polymer)/g (Ti).
Claim 11
Dependent Claim 13 words
The process of claim 9, wherein said process produces 12.0-270.0 kg (polymer)/g (Ti).
Claim 12
Dependent Claim 13 words
The process of claim 10, wherein said process produces 80.3-270 kg (polymer)/g (Ti).
Claim 13
Dependent Claim 425 words
A process for producing a styrenic polymer having a high degree of syndiotactic configuration, comprising polymerizing at least one monomer selected from the group consisting of styrene, alkylstyrenes, alkoxystyrenes, halogenated styrenes and vinylbenzoate esters in the presence of a catalyst comprising (A) a titanium compound having formula (I) TiR.sup.1 XYZ (I) wherein R 1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a halogen atom, or said titanium compound has the formula (II) Ti(R.sup.2).sub.2 R.sup.3 R.sup.4 (II) wherein each R 2 is identical and is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a halogen atom or an amino group; and R 2 may be crosslinked by an alkylidene group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium ions; and (B) an ionic compound comprising a non-coordinate anion and a cation having the formula (V) M.sup.2 R.sup.8 R.sup.9 R.sup.10 (V) wherein M 2 is a carbonium cation, silyl cation or germanium cation, and R 8 , R 9 and R 10 , which may be the same or different, are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a thioalkoxy group having 1 to 20 carbon atoms; and (C) an alkylating agent.
Claim 14
Dependent Claim 425 words
A process for producing a styrenic polymer having a high degree of syndiotactic configuration, comprising polymerizing at least one monomer selected from the group consisting of styrene, alkylstyrenes, alkoxystyrenes, halogenated styrenes and vinylbenzoate esters in the presence of a catalyst comprising (A) a titanium compound having formula (I) TiR.sup.1 XYZ (I) wherein R 1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a halogen atom, or said titanium compound has the formula (II) Ti(R.sup.2).sub.2 R.sup.3 R.sup.4 (II) wherein each R 2 is identical and is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a halogen atom or an amino group; and R 2 may be crosslinked by an alkylidene group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium ions; and (B) an ionic compound comprising a non-coordinate anion and a cation having the formula (V) M.sup.2 R.sup.8 R.sup.9 R.sup.10 (V) wherein M 2 is a carbonium cation, silyl cation or germanium cation, and R 8 , R 9 and R 10 , which may be the same or different, are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a thioalkoxy group having 1 to 20 carbon atoms; and (C) an alkylating agent.
Claim 15
Dependent Claim 15 words
The process of claim 12, wherein said cation of component (B) is a silyl cation.
Claim 16
Dependent Claim 31 words
The process of claim 13, wherein said silyl cation is selected from the group consisting of triphenylsilyl cation, trimethoxysilyl cation, tri(thioisopropyl)silyl cation, trimethylsilyl cation, 4,4',4"-tri(methoxyphenyl)silyl cation, tri(tolyl)silyl cation and 4,4',4"-tri(chlorophenyl)silyl cation.
Claim 17
Dependent Claim 15 words
The process of claim 12, wherein said cation of component (B) is a germanium cation.
Claim 18
Dependent Claim 19 words
The process of claim 12, wherein said styrenic polymer has a proportion of racemic diads of at least 75%.
Claim 19
Dependent Claim 19 words
The process of claim 16, wherein said styrenic polymer has a proportion of racemic diads of at least 85%.
Claim 20
Dependent Claim 19 words
The process of claim 12, wherein said styrenic polymer has a proportion of racemic pentads of at least 30%.
Claim 21
Dependent Claim 19 words
The process of claim 18, wherein said styrenic polymer has a proportion of racemic pentads of at least 50%.
Claim 22
Dependent Claim 15 words
The process of claim 12, wherein said process produces at least 5.1 kg (polymer)/g (Ti).
Claim 23
Dependent Claim 13 words
The process of claim 20, wherein said process produces 12.0-270.0 kg (polymer)/g (Ti).
Claim 24
Dependent Claim 13 words
The process of claim 21, wherein said process produces 80.3-270 kg (polymer)/g (Ti).
Claim 25
Dependent Claim 12 words
The process of claim 2, wherein said titanium compound has formula (I).
Claim 26
Dependent Claim 12 words
The process of claim 4, wherein said titanium compound has formula (I).
Claim 27
Dependent Claim 12 words
The process of claim 13, wherein said titanium compound has formula (I).
Claim 28
Dependent Claim 12 words
The process of claim 15, wherein said titanium compound has formula (I).

References Cited (Backward Citations)

US5155080A Cited
US5132380A Cited
EP0427696A2 Cited
EP0426637B1 Cited
US5066741A Cited
US5272229A Cited

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