Polymerization Based On Diaryliodonium Salts And Triple Bonds

Diaryliodonium salts are highly reactive because of their high electron deficient property, which could serve as leaving group. Moreover, their low toxicity, high environmental friendliness, high stability, convenience for preservation and feasible synthesis procedure enable them to find wider and wider applications in complicated organic synthesis. The most important application of diaryliodonium salts in organic synthesis is as an arylation reagent, which is a convenient method to synthesize the molecules with π-conjugated structures. One of the interesting reactions of diaryliodonium salt is to react with alkynes.Alkynes have been identified as one of the versatile building blocks for constructing electroactive polymers. Many polymerizations based on alkynes such as addition and cyclization have been utilized to prepare polymers with double bonds and(hetero) aromatic rings moieties. With π-conjugated structures, these polymers have been found exciting applications in optoelectronics and so on.If the new polymerizations based on diaryliodonium salts and alkynes could be developed, there will be not only a new application for diaryliodonium salts in polymerization, but also many new electroactive polymers.In this thesis, new polymerizations of alkynes and diaryliodonium salts were developed. Firstly, three-component polymerization of cyclodiphenyliodonium trifluorosulfonate, dialkyne and aryldiboronic acid/aryldiboronic pinacol cyclic easter was studied. Polymerization conditions including reaction time, monomer concentration and monomer ratio were optimized. Under the optimized condition, various diynes and aryldiboronic acid/aryldiboronic pinacol cyclic easter were used to synthesize a series of polymers with high yields. All the polymers possess excellent solubility and high thermostability. Several of them present aggregation-induced emission(AIE) property; hence this work presents a novel example of synthesizing AIE-active polymer from non-AIE monomers. The mechanism of AIE of resulting polymer was investigated with the help of theoretical calculation.Secondly, three-component polymerization of diphenyliodonium hexafluorophosphate of dialkyne and dinitrile was developed. Reaction conditions were optimized such as reaction solvent, reaction time, catalyst species and monomer ratio. Under the optimized condition, different dinitrile monomers and diyne monomers were polymerized and a series of polymers with generally high molecular weight were produced. All polymers possess excellent solubility and high thermostability.