Radical thermo‐ and sonopolymerization of methyl methacrylate initiated by iodobenzene 1,1‐diacetate

Abstract

The efficiency of iodobenzene 1,1‐diacetate or (diacetoxyiodo)benzene (DAIB) as a thermo‐ and sono‐initiator of methyl methacrylate (MMA) in radical bulk polymerization is tested. The polymerization kinetics and molecular‐mass characteristics support an assumption for a combined polymerization mechanism including a classical bimolecular termination with chain transfer reaction and iniferter quasi‐living polymerization. In addition to the equilibrium formation and degradation of the ‘dormant’ polymer ends, other possible decomposition reactions of the hypervalent iodine bond are the probable reason for the deviation of this polymerization from the iniferter polymerization mechanism. These reactions bear some similarity to the two‐step addition–fragmentation chain transfer mechanism of controlled radical polymerization. The application of the poly(MMA) obtained as a macroinitiator is evidence of ‘dormant’ chain end formation.© 2001 Society of Chemical Industry

Polymeric Ion Conductors Based on Sono‐Polymerized Zwitterionic Polymers for Electrochromic Supercapacitors with Improved Shelf‐Life Stability

“…Figure 1a depicts the simple one-pot preparation of ZI polymerbased gel electrolytes via sono-polymerization. [43,44] First, the ZI monomer DMAPS and initiator 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) were completely dissolved in the predetermined amount of [EMI][DCA]. Then, the mixture was exposed to sonication, by which the polymerization was initiated and proceeded even at the low temperature of 45 °C.…”

Application of Hypervalent Iodine Compounds in Advanced Green Technologies (In Press)

“…Under photochemical conditions, (diacetoxyiodo)benzene and [bis(trifluoroacetoxy)iodo]benzene are efficient initiators for the homopolymerizations of 2-(dimethylaminoethyl)methacrylate (DMAEM) and methyl methacrylate (MMA) and also for the copolymerizations of DMAEM with MMA or styrene [53]. The mechanism of the photoinitiation involves initial homolytic decomposition of (diacetoxyiodo)benzene (24), producing acetyl 26 and iodanyl 25 radicals (Fig 8) [54,55]. The actual initiators of radical polymerization are methyl radicals 27 generated by the decarboxylation of acetyl radical 26, as proved by the radical scavenger method [56].…”

Responsive and Degradable Highly Branched Polymers with Hypervalent Iodine(III) Groups at the Branching Points

“…(Diacetoxyiodo)arenes ArI(O 2 CR) 2 are known to degrade homolytically upon irradiation or heating with the formation of the corresponding monovalent iodine compound (iodoarene) and carboxylate radicals RCO 2 • , which may decarboxylate to form the radicals R • prior to undergoing further reactions. Owing to the ease with which radicals are formed from ArI(O 2 CR) 2 , these compounds are useful as initiators for the polymerization of various vinyl monomers . In order to be useful as a crosslinker yielding branched polymers with intact HV iodine(III) groups at the branching points, any polymerizations involving PhI(OAcr) 2 had to be performed at temperatures, at which no homolytic degradation of the compound occurred.…”