利用接枝型團連共聚物製備功能性微粒

Synthesis and Characterization of Functional Particles by Block Copolymers

吳孟松(Meng-Sung Wu)

指導教授 ： 莊祖煌 ； 鄭國忠

國立臺北科技大學/工程學院/化學工程所/碩士(2005年)

摘要

本研究利用活性自由基法合成聚4-氯甲基苯乙烯(polychloromethylstyrene, PCMS)與其團連共聚物，並利用不同鏈長之直鏈型双胺類三級胺的改質技術，合成出具親水-疏水段之外部交連微粒(micelle)結構的雙性團連共聚物，並分析其特性。首先，利用自由基起始劑((Benzoyl peroxide,BPO)、穩定自由基(2,2,6,6-tetramethylpiperidinooxy, TEMPO)及4-氯甲基苯乙烯單體(CMS)反應合成聚4-氯甲基苯乙烯(PCMS)，再加入苯乙烯單體(St)合成具有polychloromethylstyrene-block- polystyrene(PCMS-b-PS)，進一步分別利用不同長短之直鏈型双胺類三級胺進行四級胺化改質，使其形成核部份(core)為疏水性鏈段，殼部份(shell)為親水性之外部交連的微粒結構。並利用GPC、NMR、EA、SEM、UV及動態雷射光散射儀(DLS)等，來探討在不同pH值、NaCl濃度與THF/H2O比例的溶液中對於雙性團連共聚物形態之影響。
結果顯示，PCMS-b-PS團連共聚物的分子量分佈皆能控制在約1.3以下，而改質過後之雙性微粒結構的平均粒徑皆會隨著pH值、NaCl濃度及酸化的影響。此外發現以較短鏈之直鏈型双胺類三級胺改質下所形成之微粒粒徑有明顯的較小，約為130nm~150nm。此外，在改質交連中引入發色團(甲基橙)，粒子在pH值約小於2時形成紅色；且更進一步引入螢光團，使其團連共聚物為帶有顏色或螢光之功能性高分子。

關鍵字

活性自由基聚合反應 ； 四級胺化 ； 外部交連 ； 微粒

並列摘要

Polychloromethylstyrene, PCMS, macro-initiators were synthesized by a stable free radical polymerizations in the presence of 2,2’,6,6’-teramethyl-1-piperidinyloxy (TEMPO) and benzoyl peroxide initiator; then the TEMPO-capped PCMS were extended by polymerization with styrene monomers to synthesize PCMS-b-PS block copolymers. The block copolymers were further modified by tertiary diamines with different lengths of chains; then shell cross-linked, sub-micro micelles will be formed. Well-defined amphiphilic copolymers can be synthesized and the behaviors of such copolymers in various solvents will be studied in relation to the respective structures by the GPC, NMR, SEM, EA, and DLS etc. The diameters particle can be formed as about 150nm, which can be changed with pH value, salt concentration, and H2O/THF ratio. The particles grafted with dye and fluorescent groups were also synthesized, and they will be well discussed in the further work.

並列關鍵字

living free-radical polymerization ； shell cross-linked ； micelle

參考文獻

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