WO1994012547A3 - Polymerization of functionalized monomers with ziegler-natta catalysts - Google Patents

Polymerization of functionalized monomers with ziegler-natta catalysts Download PDF

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Publication number
WO1994012547A3
WO1994012547A3 PCT/US1993/011186 US9311186W WO9412547A3 WO 1994012547 A3 WO1994012547 A3 WO 1994012547A3 US 9311186 W US9311186 W US 9311186W WO 9412547 A3 WO9412547 A3 WO 9412547A3
Authority
WO
WIPO (PCT)
Prior art keywords
catalysts
pentene
ebthi
zrme
polymerization
Prior art date
Application number
PCT/US1993/011186
Other languages
French (fr)
Other versions
WO1994012547A2 (en
Inventor
Robert M Waymouth
Michael R Kesti
Geoffrey W Coates
Original Assignee
Univ Leland Stanford Junior
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Univ Leland Stanford Junior filed Critical Univ Leland Stanford Junior
Priority to JP6513242A priority Critical patent/JPH07507095A/en
Priority to EP94902289A priority patent/EP0623149A4/en
Publication of WO1994012547A2 publication Critical patent/WO1994012547A2/en
Publication of WO1994012547A3 publication Critical patent/WO1994012547A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Abstract

Catalysts derived from the reaction of Cp*2ZrMe2 with B(C6F5)3 or [N,N-dimethylanilinium][B(C6F5)4] (denoted as [Cp*2ZrMe]+X-, Cp* = pentamethylcyclopentadienyl, X = B(C¿6?F5)4 or CH3B(C6F5)3) are active for the homopolymerization of functionalized dienes and alpha-olefins such as 4-TMSO-1,6-heptadiene (TMSO = trimethylsiloxy), 5-TBDMSO-1-pentene (TBDMSO = tert-butyldimethylsiloxy), 5-N,N-diisopropylamino-1-pentene, 5-diphenylphosphino-1-pentene and N-(1-penten-4-yl)carbazole. Other metallocene catalysts such as [rac-(EBTHI)ZrMe]?+X-¿ and [EBIZrMe¿2]?+X- (EBTHI = ethylene-1,2-bis(n5-4,5,6,7-tetrahydro-1-indenyl, EBI = ethylene-1,2-bis(1-indenyl)) are active polymerization catalysts for the polymerization of functionalized olefins although they are more easily poisoned by silyl ethers; [rac-(EBTHI)ZrMe]+X- catalysts polymerize 4-TBDMSO-1,6-heptadiene and 5-N,N-diisopropylamino-1-pentene. A variety of other silyl ethers were polymerized. Preliminary 13C NMR analyses of polymers obtained from the functionalized alpha-olefins with [(EBTHI)ZrMe]+X- catalysts are consistent with highly isotactic microstructures. Predominantly syndiotactic polymers are produced at -25 °C in the presence of [Cp*¿2?ZrMe]?+X-¿ catalysts which is consistent with chain end control. Treatment of the polysilylethers with HCl affords novel polyalcohols. Addition of HCl to poly(5-N,N-diisopropylamino-1-pentene) yields the corresponding polyelectrolyte. Metallocene/methylaluminoxane catalysts are active for the polymerization of alpha-olefins containing silyl ether groups.
PCT/US1993/011186 1992-11-25 1993-11-17 Polymerization of functionalized monomers with ziegler-natta catalysts WO1994012547A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP6513242A JPH07507095A (en) 1992-11-25 1993-11-17 Polymerization of monomers functionalized with Ziegler-Natta catalysts
EP94902289A EP0623149A4 (en) 1992-11-25 1993-11-17 Polymerization of functionalized monomers with ziegler-natta catalysts.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98169692A 1992-11-25 1992-11-25
US07/981,696 1992-11-25

Publications (2)

Publication Number Publication Date
WO1994012547A2 WO1994012547A2 (en) 1994-06-09
WO1994012547A3 true WO1994012547A3 (en) 1994-07-21

Family

ID=25528582

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/011186 WO1994012547A2 (en) 1992-11-25 1993-11-17 Polymerization of functionalized monomers with ziegler-natta catalysts

Country Status (4)

Country Link
EP (1) EP0623149A4 (en)
JP (1) JPH07507095A (en)
CA (1) CA2128691A1 (en)
WO (1) WO1994012547A2 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3357961A (en) * 1965-05-24 1967-12-12 Exxon Research Engineering Co Copolymers of ethylene and hexadiene 1, 5
US4734472A (en) * 1986-12-24 1988-03-29 Exxon Research And Engineering Company Method for preparing functional alpha-olefin polymers and copolymers
US4794096A (en) * 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US4841004A (en) * 1986-11-29 1989-06-20 Hoechst Aktiengesellschaft Process for the preparation of a 1-olefin stereoblock polymer
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755279A (en) * 1965-06-25 1973-08-28 Exxon Research Engineering Co Copolymerization of alpha olefins with sterically hindered alkenyl amines using ziegler catalysts
GB1094557A (en) * 1965-11-29 1967-12-13 Montedison Spa Polymers of unsaturated tertiary amines

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3357961A (en) * 1965-05-24 1967-12-12 Exxon Research Engineering Co Copolymers of ethylene and hexadiene 1, 5
US4841004A (en) * 1986-11-29 1989-06-20 Hoechst Aktiengesellschaft Process for the preparation of a 1-olefin stereoblock polymer
US4734472A (en) * 1986-12-24 1988-03-29 Exxon Research And Engineering Company Method for preparing functional alpha-olefin polymers and copolymers
US4794096A (en) * 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of Applied Polymer Science, Vol. 35, "C-NMR Characterization of Poly (1,5-hexadiene)", pages 825-829 (1988), (CHENG): see page 825, Synopsis; page 827, first paragraph. *
See also references of EP0623149A4 *

Also Published As

Publication number Publication date
CA2128691A1 (en) 1994-06-09
JPH07507095A (en) 1995-08-03
EP0623149A1 (en) 1994-11-09
EP0623149A4 (en) 1995-09-27
WO1994012547A2 (en) 1994-06-09

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