Synthesis and Polymerization Studies of Cyano Epoxides

Abstract

The polar epoxides bcganoethyl glycidyl ether, cyanomethyl glycidyl ether, Bchloro-bcyanoethyl glycidyl ether, and 3,4-epoxy valeronitrile were prepared, characterized, and their polymerization reactions studied Novel cyanoethylation of glycidol produced the Bcpanoethyl glycidyl ether in a quantitative yield Reported is the first practicable synthesis of epicyanohydrin, which failed to polymerize.Homo-, co-, and terpolymerizations of the polar &epoxy nitriles with various alkylene oddes were achieved by employing a complex catalyst obtained from an aluminum aLkyl, acetyl acetone, and water. The polymers produced a series of vulcantzable elastomers which displayed an excellent balance of solvent resistance and low temperature flexibility, as well as good ozone resistance. The presence of a third monomer such as ally1 glycidyl ether was required to facilitate rubber vulcanization, However, it was possible to vulcanize homo-and copolymers of B-chloro-P-cyanoethyl glycidyl ether through the pendant chlorine atom. Catalyst efficiency in all cases was poor due to the complexing of the aluminum catalyst by the nitrile function. 1483 Copynghc D 1973 bv Marcel Dckker. Inc. All Rights Rncrvcd. Neither !hit work nor any ppn may be reproduced or vanwntttcd in any form or by any means. electronic or mechanical. IncludIng photocopying, microfilming, and recording, or by any Informarlon storage and retncvai syr tnn, without permisston in wnting from the publisher Downloaded by [McGill University Library] at 16:

Epicyanohydrin: Polymerization by Monomer Activation Gives Access to Nitrile-, Amino-, and Carboxyl-Functional Poly(ethylene glycol)

“…According to the literature, EPICH is nonpolymerizable due to the strong electron-withdrawing character of the cyano group and the resulting acidic characteristics of the methylene protons. , However, we assumed that the “activated monomer” technique, introduced by Deffieux and Carlotti et al in 2004, might permit successful polymerization of EPICH, since in this case no strongly basic alkoxide initiators are employed and low reaction temperatures are chosen. , The reaction mechanism is illustrated in Scheme . Triisobutylaluminum (catalyst) forms a nucleophilic “ate” complex with tetrabutylammonium iodide (initiator) (step 1).…”

“…In this work, amino-, amide-, and carboxyl-functional polyethers are named according to the underlying theoretical monomers and abbreviated as follows: “2-oxirane­ethanamine” (OEA) in poly­(2-oxirane­ethanamine), “2-oxirane­acetamide” (OAm) in poly­(2-oxirane­acetamide), and “2-oxirane­acetic acid” (OAa) in poly­(2-oxirane­acetic acid). The homopolymer poly­(epicyanohydrin) is named according to the monomer “epicyanohydrin”, which is generally abbreviated as EPICH. , …”

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

“…This monomer allows the synthesis of amino-functional PEG by simple hydrogenation of the nitrile-group. In contrast to the glycidyl amine derivatives, EPICH cannot be polymerized by conventional AROP. , Recently, our group demonstrated the successful incorporation of 4–16 mol % EPICH into PEG by the “activated monomer” method. However, the nitrile group is a strong electron withdrawing functional group and supports the transfer to monomer reaction described in section , resulting in unsaturated chain ends …”

Synthesis and Properties of (Alkylthio)methyl-Substituted Poly(oxyalkylene)s and (Alkylsulfonyl)methyl-Substituted Poly(oxyalkylene)s

“…[1][2][3][4] High molecular weight poly(oxyethyene)s with more complex and/or polar side groups, such as ester, cyano, nitro, and silyl, have not been synthesized. [4][5][6][7][8][9][10] Researchers have tried to make poly(oxyethylene)s with these functional side groups by direct polymerization. The synthesis of pure monomers proved difficult, and even when pure monomers were prepared, side reactions during polymerization resulted in low molecular weight polymer.…”

“…A large number of vinyl polymers with functional side groups have been synthesized and used for widely varying applications. Poly(oxyethylene) derivatives with simple side chains, such as methyl, vinyl, phenyl, chloromethyl, and ether groups, have been synthesized by direct polymerization of the appropriate oxirane. − High molecular weight poly(oxyethyene)s with more complex and/or polar side groups, such as ester, cyano, nitro, and silyl, have not been synthesized. − Researchers have tried to make poly(oxyethylene)s with these functional side groups by direct polymerization. The synthesis of pure monomers proved difficult, and even when pure monomers were prepared, side reactions during polymerization resulted in low molecular weight polymer.…”