The Design, Synthesis And Application Of Star Polymers Based On Functionalized Polymethylene

Star polymers are different from linear polymers. Their synthesis, structure and functionality have become a research focus in polymer field. In this thesis, a series of well-defined AB2-type star polymers based on polymethylene were synthesized via the combination of living polymerization of ylides and atomic transfer radical polymerization(ATRP). The structures of such AB2-type star polymers were characterized by high temperature1NMR, GPC and fourier transform infrared spectroscopy (FT-IR). The micellization behavior of PM1-b-(PS)2in CS2and the porous films fabricated by such AB2-type star polymers(PM1-b-(PS)2) were primarily researched.1. Synthesis of ATRP macroinitiator (PM1-(CI)2).Firstly, hydroxyl terminated polymethylene (PM-OH) was synthesized via living polymerization of ylides. The structure of PM segment was characterized by high temperature1H-NMR. The ATRP macroinitiator (PM1-(Cl)2) was obtained by the reaction of PM1-OH and dichloroacetyl chloride. PM1-OH was transformed under optimized experimental condition into ATRP polymethylene-based macroinitiators in-100%conversion.2. Synthesis of AB2-type star polymers via ATRPs of different monomer using PM1-(CI)2.The macroinitiator (PM1-(Cl)2) initiated the ATRP of styrene, tert-butyl acrylate or methyl methacrylate to obtain PM1-b-(PS)2,PM1-b-(PtBA)2or PMq-b-(PMMA)2AB2-type star polymers based on polymethylene. The chain structure, molecular weight and its distribution of such AB2-type star polymers were characterized by GPC and high temperature1H-NMR.3. Synthesis of A(BC)2-type star polymers via ATRP of tert-butyl acrylate using PM1-b-(PS)2.The macroinitiator (PM1-b-(PS)2) initiated the ATRP of tert-butyl acrylate to obtain PM1-b-(PS-b-PtBA)2A(BC)2-type star polymers based on polymethylene. The molecular weight and its distribution of such A(BC)2-type star polymers were characterized by gel permeation chromatography(GPC), high temperature1H-NMR and fourier transform infrared spectroscopy (FT-IR).4. The micellization behavior of PM1-b-(PS)2and fabrication of porous film of AB2star polymers.The micelles of PM1-b-(PS)2can form in specific solvent. The solution behavior of PM1-b-(PS)2in CS2was observed. Porous films of such star polymers were fabricated via static breathe-figure method with carbon disulfide as solvent. The morphology of such porous film was observed by SEM. The effects of temperature, molecular weight and concentration on the morphology of porous film were primarily investigated.