Radical polymerization of methyl acrylate by use of benzyl N, N‐diethyldithiocarbamate in combination with tetraethylthiuram disulfide as a two‐component iniferter

Abstract

SYNOPSISPolymerization of methyl acrylate ( M A ) with benzyl N,N-diethyldithiocarbamate (BDC ) was carried out in bulk or in benzene under UV irradiation. The polymerization proceeded to give a high yield of polymer, however it was found that BDC did not function as an iniferter in the MA polymerization. Bimolecular termination leading to deactivation of the iniferter site was observed during the polymerization in preference to chain transfer and primary radical termination which reproduce the iniferter site. The deactivation was successfully prevented by combining BDC and tetraethylthiuram disulfide ( T D ) as a twocomponent iniferter. This two-component iniferter system was also applied to synthesis of a star polymer with 1,2,4,5-tetrakis (N,N-diethyldithocarbamylmethyl) benzene (DDC ) as a tetrafunctional photoiniferter.

Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents

“…[11] When S-malonyl N,N-diethyldithiocarbamate (A 1 ) is used in the thermal (AIBN-induced) polymerization of ethyl acrylate (EA), the M -n values at high conversion are close to the theoretical predictions (assuming a negligible contribution of AIBNCommunication: Control of the radical polymerization of acrylates, styrene and vinyl acetate has been achieved by using novel dithiocarbamates as reversible additionfragmentation chain transfer agents. The key parameter for the control with N,N-disubstituted (A) or cyclic (B) dithiocarbamates was found to be the conjugation of the lone pair of electrons of the nitrogen atom with carbonyl or aromatic groups.…”

Resistance of zwitterionic telomers accumulated on metal surfaces against nonspecific adsorption of proteins

“…Of various procedures for pursuing controlled radical polymerization, the use of an iniferter (a compound that pursues initiation, chain transfer, and termination) has received much attention due to its ease [47][48][49][50][51][52][53][54][55][56]. Of the iniferters used, N ,N -diethyldithiocarbamoyl derivatives have been most extensively studied [47][48][49][50][51][53][54][55][56]. Previously, for example, we synthesized a phospholipid carrying a benzyl-N ,N -diethyldithiocarbamoyl (BDC) group as the iniferter and prepared novel block telomer-carrying phospholipids by successive photoirradiation of various vinyl monomers in the presence of the phospholipid iniferter [57].…”

Studies on Photoinduced ATRP in the Presence of Photoinitiator

“…[5] The earlier approach based on photochemical activation and reversible combination of growing radicals with a scavenging radical using dithiocarbamates was known as photoiniferter (photoinitiator-transfer-terminator). [6][7][8][9][10][11] Several attempts were also made to covalently attach different chromphoric groups to the nitroxides moiety for NMRP process. [11][12][13][14][15] A thiocarbonylthio compound, known as a classical RAFT agent, is a photosensitive molecule that readily undergoes reversible b-cleavage at the carbon sulfur bond and thus yields some control over the radical polymerization process under UV irradiation.…”