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  • 1
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The base and transition metal catalyzed isomerization of allyl and crotyl ethers affords a facile, high yield route to the preparation of a variety of mono-, di-, and multifunctional 1-propenyl and 1-butenyl ethers. Employing this novel method, monomers containing epoxide, ester, ether carbonate and urethane groups can be prepared from their readily available allyl and crotyl precursors. In general, these monomers display very high reactivity in cationic polymerizations. In our work, we have focused on photoinduced cationic polymerizations of these monomers using diaryliodonium and triarylsulfonium salt photoinitiators. To study these very fast photopolymerizations, extensive use of real-time infrared spectroscopy was made. Employing this technique, the effects of monomer and photoinitiator structure on the rates of polymerization were studied.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1881-1890 
    ISSN: 0887-624X
    Schlagwort(e): cationic polymerization ; photopolymerization ; epoxy monomers ; terpene epoxides ; isoascaridole ; limonene diepoxide ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The monoterpene diepoxides isoascaridole (III), γ-terpinene diepoxide (V), and limonene diepoxide (VIII) were prepared from the corresponding hydrocarbons and their reactivity in photoinitiated cationic polymerization examined. Both V and VIII underwent facile and rapid polymerization to give crosslinked polyethers III, but although highly reactive, did not undergo crosslinking polymerization. With the aid of model compounds it was determined that the rearrangement of one of the epoxy groups of III takes place in the presence of photogenerated acid to give an epoxy ketone (XIII) as the primary product. XIII undergoes very sluggish polymerization. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2473-2486 
    ISSN: 0887-624X
    Schlagwort(e): cycloaliphatic epoxides ; mechanistic studies ; photoinitiated cationic polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An investigation of the reactivity of the cycloaliphatic diepoxide, 3,4-epoxycyclohexyl 3′, 4′-epoxycycloexane carboxylate (I) in photoinitiated cationic polymerization was carried out with the aid of model compounds. It was shown that the presence of the ester group greatly retards the rate of polymerization of this bisepoxide. Molecular modeling studies indicate that the ester carbonyl group can interact in a number of ways with the initially formed protonated or alkylated oxiranium cation to give bicylic dialkoxycarbenium ions. These latter species are both more sterically hindered and less reactive than the oxiranium cation precursors and undergo propagation at a considerably reduced rate. Reactivity studies em-ploying model compounds also showed that epoxy monomers that contain ester groups undergo polymerization at much slower rates than those in which the ester group is absent. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1579-1591 
    ISSN: 0887-624X
    Schlagwort(e): allyl ethers ; enol ethers ; cationic polymerization ; isomerization-polymerization of allyl ethers ; dicobalt octacarbonyl ; organosilanes ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of silanes bearing Si—H groups, dicobalt octacarbonyl [Co2(CO)8] efficiently catalyzes the cationic polymerization of a wide variety of enol ether and other related monomers including vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, ketene acetals, and allene ethers. In addition, this catalyst system is also effective for the polymerization of complimentary allylic and propargylic ethers by a process involving tandem isomerization and cationic polymerization. This latter process occurs by a stepwise mechanism in which the allylic or propargylic ether is first isomerized, respectively, to the corresponding enol ether or allenic ether and then this latter compound is rapidly cationically polymerized in the presence of the catalyst. In accord with this mechanism, it has been shown that the structure of the polymers prepared from related enol and allyl ethers using the above catalyst system are identical. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1579-1591, 1997
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 31-39 
    ISSN: 0887-624X
    Schlagwort(e): ring-opening polymerization ; epoxide polymerization ; cationic polymerization ; transition metal initiators ; cobalt initiators ; dicobaltoctacarbonyl ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of Si—H containing cocatalysts, dicobaltoctacarbonyl has been found to very efficiently catalyze the ring-opening polymerization of cyclic ethers, especially epoxides, as well as certain vinyl monomers. The reaction conditions employed are very similar to those used in Co2(CO)8 catalyzed hydrogenation and hydrosilylation reactions. Detailed investigations have been carried out to elucidate the nature of the active species for this catalytic system. A cationic mechanism is proposed based on the experimental results of those investigations.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3227-3228 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1985-1997 
    ISSN: 0887-624X
    Schlagwort(e): allyl ethers ; 1-propenyl ethers ; cationic polymerization ; isomerization-polymerization of allyl ethers ; dicobalt octacarbonyl ; organosilanes ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of organosilanes, dicobalt octacarbonyl catalyzes the polymerization of alkyl allyl ethers to give high molecular weight polymers. This article reports the results of a detailed mechanistic study of this new polymerization reaction. The evidence obtained in this study supports a stepwise process involving first, the reaction of dicobalt octacarbonyl with an organosilane to form HCo(CO)4 and R3SiCo(CO)4. In subsequent steps, HCo(CO)4 isomerizes the allyl ether to a 1-propenyl ether and then this compound is polymerized by the formal transfer of a silyl cation from R3SiCo(CO)4. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1985-1997, 1997
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2521-2532 
    ISSN: 0887-624X
    Schlagwort(e): allyl ethers ; 1-propenyl ether monomers ; cationic polymerization ; isomerization-polymerization of allyl ethers ; Group VIII carbonyls ; organosilanes ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Alkyl allyl ethers undergo facile thermally induced isomerization to alkyl 1-propenyl ethers in the presence of Group VIII transition metal carbonyl compounds as catalysts. The addition of a silane containing a Si—H bond to these systems results in a catalyst system that is capable of not only isomerizing the allyl ether to the 1-propenyl ether, but further results in the polymerization of these later compounds. High molecular weight polymers can be obtained directly from the alkyl allyl ether in a single step. The scope and limitations of these polymerizations are described. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2521-2532, 1997
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2414-2414 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1847-1857 
    ISSN: 0887-624X
    Schlagwort(e): multifunctional aryl 2-propenes ; 2-propenyl ether analogues ; allyl-2-propenyl isomerizations ; cationic photopolymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Monomers bearing two, three, four, and six cationically polymerizable aryl 2-propenyl groups were synthesized and characterized. These compounds can be readily prepared by the catalytic isomerization of the corresponding allyl compounds. Strong bases and tris(triphenylphosphine)ruthenium(II) dichloride were used as the catalysts for these isomerizations. A study of the cationic photopolymerizations of these novel monomers was carried out using a diaryliodonium salt photoinitiator. The polymerization involves a stepwise condensation of the monomers followed by an intramolecular ring closure to form polyindanes. The resulting photopolymerized polymers underwent thermal oxidative decomposition at temperatures over 430°C. © 1993 John Wiley & Sons, Inc.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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