Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions

Abstract

Organotelluriummediated living radical polymerizations (TERPs) and organostibinemediated living radical polymerizations (SBRPs) provide well-defined polymers with a variety of polar functional groups via degenerative chain-transfer polymerization. The high controllability of these polymerizations can be attributed to the rapid degenerative-transfer process between the polymer-end radicals and corresponding dormant species. The versatility of the methods allows the synthesis of AB diblock, ABA triblock, and ABC triblock copolymers by the successive addition of different monomers. This review summarizes the current status of TERP and SBRP.

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

“…The most widely used CRP methods are atom transfer radical polymerization (ATRP), [26][27][28][29] stable free radical polymerization [SFRP, the most popular of which is nitroxide-mediated polymerization (NMP), [30][31][32][33][34] but also including polymerizations mediated by Co/porphyrin complexes [35][36][37] ], and degenerative transfer polymerization 38 [with reversible additionfragmentation chain transfer (RAFT) polymerization [39][40][41][42][43] as the most successful example but including polymerizations in the presence of tellurium or antimony compounds 44 ]. Metal complexes can mediate controlled polymerization via two mechanisms: 45 (i) the reversible formation of a metal-carbon bond upon reaction with the propagating radical (SFRP) or (ii) the reversible transfer of an atom or a group from the polymer chain end to the metal center (ATRP).…”

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

“…Recently, organotellurium-mediated living radical polymerization (TERP) [1][2][3] has been proposed and developed by Yamago and coworkers. as a novel controlled/living radical polymerization (CLRP) technique.…”

Tert-butyl-diphenylmethylnitroxyl radical formation with the reaction of triphenylbismuth dicrotonate and C-phenyl-N-tert-butylnitrone in benzene

“…При облучении таких соединений видимым светом происходит гомолиз связи Bi-C(пирен) с образованием пи-ренильного радикала и катион-ради-кала триарилвисмута, который в даль-нейшем и инициирует полимеризацию. Также известно, что металлорганиче-ские соединения висмута(III) способ-ны вызывать контролируемую живую радикальную полимеризацию [5,6]. Недавно, фенил-трет-бутилнитрок-сильный стабильный радикал был зафиксирован в реакции дикротона-та трифенилвисмута с 2-метил-2-ни-трозопропаном [7].…”

“…When such compounds were irradiated by visible light, the homolysis of Bi-C(pyrene) bond occured with the formation of pyrenyl radical and cation radical of triarylbismuth, which subsequently initiated polymerization. It is also known that organometallic compounds of bismuth(III) can cause the controlled living radical polymerization [5,6]. Recently a phenyl-tert-butylnitroxyl stable radical was fixed in the triphenylbismuth dicrotonate reaction with 2-methyl-2-nitrosopropane [7].…”