AGET ATRP In Ionic Liquid-based Microemulsions And The Self-assembly Of Poly(Ionic Liquids)

Ionic liquids (ILs) are organic salts at room temperature which are entirely composedof anion and cation. They have unique properties, such as low volatility, excellent chemicalstability, high thermal stability, recycling advantages. At the same time, designability isanother feature of ILs, which makes it to obtain specific needs ILs by adjusting thecombination of anion and cation or grafting appropriate functional groups.Activators generated by electron transfer atom transfer radical polymerization (AGETATRP) is an “living”/controlled radical polymerization method utilizing high statetransition metal complexes as catalyst which is reduced to low state transition metalcomplexes by reducing agent. We researched on AGET ATRP of methyl methacrylate(MMA) in an IL-based microemulsion and the recycling of ILs, emulsifier and catalyst.The results combine the recycling property of ILs and the nanostructure of microemulsionpolymerization. We can solve the problem of hardness to remove or reuse the emulsifierand catalyst. It is greatly helpful for the development and application of microemulsionpolymerization in ATRP technology.Because the physical and chemical properties of ionic liquids can be simply regulatedby anionic exchanging of ILs, we further studied the self-assembly of poly-(ionic liqiuds).Effects on the morphology of self-assembly of the molecular weight distribution,molecular weight, alkyl chain of imidazole, the ratio of ions and other factors were studied.Self-assembly refers to a kind of technology which formed orderly structure by thebasic units spontaneously. The basic units organized or gathered to the geometric structurewith stable and certain morphology by the interaction of covalent bonds. However, moststudies have focused on the self-assembly of amphiphilic well-defined block copolymersor random copolymers. Only few study did concern the self-assembly of amphiphilicrandom polymers which composed of ions.The main work is as follows:(1) AGET ATRP reaction was carried out in the oil/IL (MMA/[Bmim][BF4]) microemulsions with the surfactant DMIBr. Surfacatnt IL ligands with the emulsificationwere synthesized. The recycling of the ILs and catalysts were also studied. The results areas follows: AGET ATRP of MMA in IL-based microemulsions initiated byEBiB/AA/CuCl2/BPMOA was an efficient radical polymerization process. The using ofsurfactant IL catalyst ligands show rate enhanced polymerization. The catalyst keeps activeafter several cycles. An unexpected but very significant result is that the desired smallPMMA particles (~5nm diameter) obtained. The results of this study suggest a feasibleapproach for the practical applications of AGET ATRP in microemulsions and should beexpected to promote the widespread use of CLRP techniques.(2) Self-assembly of amphiphilic random poly(ionic liquids) was studied. Weobtained desired molecular weight of PILs using radical polymerization or RAFT. Effectson the morphology of self-assembly of the molecular weight distribution, molecular weight,alkyl chain of imidazole, the ratio of ions and other factors were studied. The results are asfollows: With the increasement of the molecular weight, molecular weight distribution, thespherical micelles got bigger. In addition, we researched on the vinylimidazole-typedpoly-ILs. After the cross-link of the shell, the morphology of double shell-core wasobtained differing from the above study.