- 學位論文
含官能基之活性團聯共聚合物之合成 以及反應動力探討
Synthesis of living block copolymer with functional groups and its kinetic study
摘要
本實驗主要目的是合成具有官能基之活性團聯共聚合物。首先，藉由穩定自由基：TEMPO、4-oxo-TEMPO，以及起始劑：BPO、AIBN，穩定自由基與起始劑的比值是1.2∼1.4，先在95OC先預熱使起始劑完全分解，之後再提高溫度到130OC進行styrene的聚合反應，合成聚苯乙烯的巨起始劑，PDI在1.2左右。 之後利用聚苯乙烯巨起始劑來聚合第二種不同的壓克力單體，例如BA、tBA、GMA，在高溫下進行第二段的聚合反應，合成團聯共聚合物。探討巨起始劑的大小、濃度、不同種類的巨起始劑、反應時間、反應溫度對反應的影響，並發現添加少量的極性溶劑DMF可以提反應速率。合成出PS-b-PBA、PS-b-PtBA、PS-b-PGMA等團聯共聚合物，第二段壓克力的分子量成長可以超過一萬，其分子量分佈為1.2∼1.4，並將PS-b-PtBA水解成PS-b-PAA兩性團聯共聚合物。並利用DSC、NMR、IR、TGA等來鑑定團聯共聚合物。 另外一部份是以AIBN為起始劑、4-oxo-TEMPO為穩定自由基，合成P(S-r-GMA)OXO之random copolymer之巨起始劑，利用此巨起始劑來聚合BA以及tBA，合成出P(S-r-GMA)OXO-b-PBA以及P(S-r-GMA)OXO-b-PtBA之團聯共聚合物，第二段的分子量可以成長超過一萬，PDI也是在1.4左右，並利用DSC、NMR、IR、TGA等來鑑定團聯共聚合物。 此外我們針對PS巨起始劑以及團聯共聚合物PS-b-PtBA之合成的反應動力探討，討論其反應機構。最後，我們利用TEM以及AFM來觀察團聯共聚合物之微相結構。
並列摘要
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.