Synthesis of living block copolymer with functional groups and its kinetic study
Date Issued
2004
Date
2004
Author(s)
Kuo, Kuo-Hui
DOI
zh-TW
Abstract
The object of this study was to synthesize living block copolymers with functional groups. First, using stable free radical: TEMPO, 4-oxo-TEMPO, and initiator: BPO, AIBN, the ratio of stable free radical and initiator was between 1.2 and 1.4, which was preheated to make initiators decompose completely at 95OC. And then raising the temperature to 130OC, styrene was polymerized to synthesize the polystyrene macro initiator, which PDI is about 1.2.
Later using polystyrene macro initiator can polymerize second acrylic series monomers, for example, BA, tBA, GMA, to synthesize block copolymers under high temperature condition. The effect of the size and concentration of macro initiators, different species of macro initiators, reaction time, and reaction temperature were investigated. And by adding a small amount of polar solvent DMF can improve reaction rate. The molecular weight of second session of PS-b-PBA、PS-b-PtBA and PS-b-PGMA block copolymers can excess 10000, and the molecular weight distribution was between 1.2 and 1.4. PS-b-PtBA was hydrolyzed to obtain PS-b-PAA amphiphilic block copolymer. DSC, NMR, IR, TGA were used to conform the structure of block copolymers.
Another part was to use AIBN as initiator, 4-oxo-TEMPO as stable free radical to synthesize P(S-r-GMA)OXO random copolymer macro initiators. Using this macro initiator can polymerize BA and tBA to synthesize P(S-r-GMA)OXO-b-PBA and P(S-r-GMA)OXO-b-PtBA block copolymers. The molecular weight of second session can excess 10000, and the molecular weight distribution was about 1.4. DSC, NMR, IR, TGA were used to conform the structure of block copolymers.
Besides, we investigated the kinetic study of PS macronitiators and PS-b-PtBA block polymers, and discussed the reaction mechanism. At last, we used TEM and AFM to observe the micro morphology of block copolymers.
Subjects
聚丙稀酸丁酯、聚新丙稀酸丁酯、聚丙稀酸、聚甲基丙稀酸脫水甘油酯
活性聚合法
聚苯乙烯
團聯共聚合物
微相結構
反應動力
穩定自由基
kinetic study
poly (tert butyl acrylate)
living polymerization
stable free radical
poly (glycidyl methacryate)
block copolymer
poly (butyl acrylate)
micro morphology
poly (styrene)
poly (acrylic acid)
Type
thesis
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