含吡啶之星狀起始劑利用ATRP法進行聚合與探討

Synthesis and Properties of Polymers via ATRP from a Pyridine-containing Star Initiator

郭昫成(Xu-Cheng Kuo)

指導教授 ： 汪昆立

國立臺北科技大學/工程學院/化學工程研究所/碩士(2008年)

https://doi.org/10.6841/NTUT.2008.00053

摘要

本實驗合成新型含吡啶結構之星狀起始劑，利用親水單體磺酸丙基甲基丙烯酸鉀鹽(SPMA)；親油單體苯乙烯(Styrene) 及甲基丙烯酸甲酯(MMA)進行原子轉移自由基聚合(ATRP)形成兩性共聚合物。起始劑與聚合體經由IR、NMR、及GPC鑑定其結構及分析其聚合動力，轉化率與數目平均分子量呈線性分佈，且聚合體之分子量呈狹窄分佈，證明ATRP的活性聚合現象。結果證實，可以成功從本次合成的星狀起始劑聚合，以ATRP方法進行高分子聚合且為可控制的活性聚合反應。
使用ATRP法合成之聚合體PMMA，經由UV-Vis分析得知未加酸前UV吸收為294 nm及328 nm，加酸後UV吸收改變為306 nm及382 nm；其PL分析得知在382 nm的激發波長下，螢光為500 nm，螢光強度隨著酸濃度的增加而變強。星狀兩性聚合體PMMA-b-PSPMA經由NMR光譜可以得知PSPMA確實接上，此聚合體在溶劑中形成粒子，粒子大小隨溶劑改變而不同，利用DLS測得粒子大小範圍在0.25~10 μm，且使用SEM觀察粒子在玻璃上所呈現的表面型態，經SEM來證明此聚合體形貌有柱狀、圓形平板狀、不規則平板狀、樹枝狀、葡萄狀及球狀。

關鍵字

原子轉移自由基聚合 ； 星狀起始劑 ； 兩性聚合體

並列摘要

A star initiator containing two amide bromides and one ester bromide units was synthesized and used in ATRP polymerization. Four monomers including one hydrophilic monomer - potassium 3-sulfopropyl methacrylate (SPMA) and two hydrophobic monomers - methyl methacrylate (MMA), styrene, were used in the ATRP polymerization. Amphiplilic polymers were prepared from the hydrophilic and hydrophobic monomers. The structures of the initiator and prepared polymers were confirmed by IR and NMR. The polydispersity indexs (PDIs) of prepared polymers were below 1.4 and the experimental results showed the polymerizations by the initiator were living polymerizations.
The PMMA polymer was synthesized by ATRP polymerization, and analyzed by UV spectra. This compound absorbed at 294 nm and 328 nm, the absorption changed to 306 nm and 382 nm after protic acid was added. The protonated polymer possessed strong fluorescence (around 500 nm) after protic acid was added as excited at 382 nm. The fluorescent intensity at 500 nm increased as acid concentration. Amphiphilic block copolymers of poly(MMA-b-SPMA) were prepared and confirmed by NMR. The amphiphilic block polymer aggregated to form particles (0.25~10 μm) in different solvents measured by DLS. The shape of particles had pillar, round-shaped flat, non-regularity flat, tree-shape, grapes, sphere to be measured by SEM on the glass.

並列關鍵字

ATRP ； Star Initiator ； Amphiphilic block copolymers

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