Dibenzyl trithiocarbonate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile

Abstract

Reversible addition–fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain‐transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain‐transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain‐transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry and 1H NMR analyses have confirmed the chain‐end functionality of the resultant polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 490–498, 2006

Living Radical Polymerization by the RAFT Process—A First Update

“…Quinonoid species are well known as excellent hydrogen atom donors. The effect on kinetics would be similar to the Buback-Vana proposal [144] but would lead to the formation of a new RAFT agent 99 which might be detectable under appropriate conditions but, for the case of acrylate polymerization, may not be readily distinguished 47 [104] HPMAM [104] NIPAM [104] 48 DMA [105] 49 [106] MA [106] C [12] MMA [4,12] 51 [30] (S) [30] 52* [106] AA [107] AN [108] MA [106] 53 [31] BA [31] 54* BA [31] MA [71] MMA [109] 55 [31] AA [110] BA [31] NIPAM [110] C 56 [111] NIPAM [111,112] 57 [111] NIPAM [111] [31] (BA) [31] 60 [31] BA [31] 61* AA [110] BA [31,109] MA [71] NIPAM [110] [30] BA [56] NIPAM [56] (NVP) [56] 63 [30] S [30] 64 ...…”

Well-Defined High-Molecular-Weight Polyacrylonitrile via Activators Regenerated by Electron Transfer ATRP

“…[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] All the major CRP processes, atom transfer radical polymerization (ATRP), 25,26 nitroxide-mediated polymerization (NMP), 27,28 and reversible addition-fragmentation chain transfer polymerization (RAFT) 29,30 have been successfully used to prepare PAN with low-to-moderate chain length and narrow molecular weight distribution. However, there has been no report on a CRP of PAN with molecular weight in excess of 100 000 g/mol and narrow MWD.…”

The dependence of diffusivity of hydrocarbons in polyvyniltrimethylsilane on molecular mobility level

“…PAN was synthesized by RAFT polymerization using BDTB as the RAFT agent 49, 50. Figure 1(a) is the NMR spectrum.…”