Benzyl alcohols as accelerators in the photoinitiated cationic polymerization of epoxide monomers

89Citations
Citations of this article
28Readers
Mendeley users who have this article in their library.
Get full text

Abstract

Benzyl alcohols display marked accelerating effects on the onium salt photoinitiated cationic ring-opening polymerizations of epoxide monomers. The participation of radicals in these polymerizations was demonstrated, and a pronounced accelerating effect on the polymerization rate was observed depending on the character of the substituent on the benzene ring of the alcohol. 4-Methoxybenzyl alcohol was considerably more reactive than benzyl alcohol, whereas the analogous chloro- and nitrosubstituted compounds were less reactive. Piperonyl alcohol was even more reactive as an accelerator in these polymerizations. The UV irradiation of an onium salt cationic photoinitiator generates Brönsted acids that initiate the cationic ring-opening polymerization of the epoxide monomer. In the presence of benzyl alcohol, the usual polymerization mechanism is diverted and proceeds by a more-rapid activated monomer mechanism. As a result, benzyl ether groups are incorporated at the termini of the polymer chains. Aryl radicals that are also generated by photolysis of the onium salt abstract labile benzyl ether protons, and the benzyl ether radicals that are produced are subsequently oxidized by the onium salt to afford the corresponding benzyl carbocations. This takes place by a chain process. The polymer bound benzyl cations serve as additional sites for the initiation of cationic polymerization. It is proposed that these two mechanisms acting in synergy with one another account for the observed accelerating effect on the polymerization rate.

References Powered by Scopus

264Citations
29Readers
Get full text
158Citations
15Readers
Get full text
126Citations
31Readers
Get full text

Cited by Powered by Scopus

Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency

666Citations
211Readers
Get full text
314Citations
345Readers
Get full text
266Citations
210Readers
Get full text

Register to see more suggestions

Mendeley helps you to discover research relevant for your work.

Already have an account?

Cite

CITATION STYLE

APA

Crivello, J. V., & Ortiz, R. A. (2002). Benzyl alcohols as accelerators in the photoinitiated cationic polymerization of epoxide monomers. Journal of Polymer Science, Part A: Polymer Chemistry, 40(14), 2298–2309. https://doi.org/10.1002/pola.10311

Readers' Seniority

Tooltip

Researcher 10

50%

PhD / Post grad / Masters / Doc 9

45%

Professor / Associate Prof. 1

5%

Readers' Discipline

Tooltip

Materials Science 6

35%

Chemistry 6

35%

Medicine and Dentistry 3

18%

Chemical Engineering 2

12%

Save time finding and organizing research with Mendeley

Sign up for free