Synthesis and radical polymerization of styrene‐based monomer having a five‐membered cyclic dithiocarbonate structure

Abstract

A styrene‐based monomer having a five‐membered cyclic dithiocarbonate structure, 4‐vinylbenzyl 1,3‐oxathiolane‐2‐thione‐5‐ylmethyl ether (VBTE), was synthesized from 4‐vinylbenzyl glycidyl ether (VBGE) and carbon disulfide in the presence of lithium bromide in 86% yield. Radical polymerization of VBTE in dimethyl sulfoxide by 2,2′‐azobisisobutyronitrile was carried out at 60 °C to afford the corresponding the polymer, polyVBTE, in 64% yield. PolyVBTE with number‐averaged molecular weight higher than 31,000 was obtained. The glass transition temperature (Tg) and 5 wt % decomposition temperature (Td5) of the polyVBTE were evaluated to be 66 and 264 °C under nitrogen atmosphere by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBTE repeating unit could also be obtained via polymer reaction, that is, a lithium bromide‐catalyzed addition of carbon disulfide to a polyVBGE prepared from a radical polymerization of VBGE. Copolymerization of VBTE and styrene with various compositions efficiently gave copolymers of VBTE and styrene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Photoimageable Organic Coating Bearing Cyclic Dithiocarbonate for a Multifunctional Surface

“…The shape of the SEC traces of the four copolymers with increased conversion (Figure 1c) changes from unimodal to multimodal when Đ exceeds 3, which is in agreement with the results of previous reports on the free-radical copolymerization of DTCMMA with nBMA. 35 These results imply that, at higher conversion, certain but inconsiderable side reactions, such as chain transfer 37 or ringopening, and the coupling reaction of the polymer chains into a disulfide bond, contribute to the increasing dispersity. 38,39 Despite the increase of the Đ, the monomer was consumed with following the linear trend in Figure 1b, implying that the side reactions do not significantly affect the radical-based propagation process based on the RAFT polymerization mechanism.…”

Protected thiol strategies in macromolecular design

“…In the same context, Endo and co-workers describe the synthesis of a styrene derivative, functionalized with a cyclic dithiocarbonate [254]. The monomer was synthesized from 4-vinyl-benzyl glycidyl ether with carbon disulfide in a yield of 86%.…”

Hybrid Nonisocyanate Polyurethanes (H‐NIPUs): A Pathway towards a Broad Range of Novel Materials

“…Boutevin and co-workers [53] have extensively reviewed the synthesis of such compounds up to 2013, as well as their polymerization behaviors through reaction of the carbon-carbon double bond. They include, among others, vinyl ether, [60,61] vinylic, [62] allylic [63][64][65] and allyl ether, [66] styrenic [67,68] and (meth)acrylic cyclic carbonates [69][70][71][72][73][74][75][76] (Figure 6). Biobased al-lylic cyclic carbonates have also been synthesized.…”