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Dicobalt octacarbonyl-catalyzed cationic polymerization of allylic and enolic ethers

✍ Scribed by James V. Crivello; Surésh K. Rajaraman

Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
224 KB
Volume
35
Category
Article
ISSN
0887-624X

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✦ Synopsis

In the presence of silanes bearing Si{H groups, dicobalt octacarbonyl [Co 2 (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.

📜 SIMILAR VOLUMES

Transition metal-catalyzed isomerization
Transition metal-catalyzed isomerization and polymerization of allylic and enolic ethers
✍ James V. Crivello; Surésh K. Rajaraman 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 194 KB 👁 1 views

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 isome

Transition metal-catalyzed tandem isomer
Transition metal-catalyzed tandem isomerization and cationic polymerization of allyl ethers. I. Discovery and scope
✍ James V. Crivello; Surésh K. Rajaraman 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 231 KB 👁 1 views

Allyl ethers are readily polymerized using a new polymerization reaction termed: transition metal-catalyzed tandem isomerization and cationic polymerization. Employing dicobalt octacarbonyl in combination with organosilanes, polymerization takes place rapidly and exothermically to give high molecula

Transition metal-catalyzed tandem isomer
Transition metal-catalyzed tandem isomerization and cationic polymerization of allyl ethers. II. Structural and mechanistic studies
✍ James V. Crivello; Surésh K. Rajaraman 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 227 KB 👁 1 views

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 step