親疏水雙性共聚三成分彈性高分子之合成與研究

Synthesis and Characterization of Amphiphilic Elastomeric Copolymer Poly(PIMA-co-MMA-co-PEGMA)

徐彩婷(Tsai-Ting Hsu)

指導教授 ： 蔣見超

國立中正大學/工學院/化學工程學系/碩士(2015年)

摘要

研究以陰離子聚合法製備polyisoprene(PI)，並將PI尾端官能化上一壓克力官能基，以進行後續之自由基反應。選取methyl methacrylate(MMA)以及poly(ethylene glycol) methyl ether methacrylate (PEGMA)為自由基的共聚單體，希望可以增加polyisoprene的黏性以及親水性，製備出Poly(PIMA-co-MMA-co-PEGMA)具彈性的親疏水雙性高分子。
　　首先以陰離子聚合法合成polyisoprene並且利用尾端具有活性的特色接上環氧丙烷(propylene oxide)，使polyisoprene的尾端變成帶有活性的氧(PIO-)，再加入methacryloyl chloride，使此高分子變為一巨單體polyisoprenyl methacrylate(PI-MA)；接著再使用自由基法，以AIBN作為起始劑並導入PEGMA和MMA，並以THF為溶劑加熱至70℃，便可得到三成分的共聚高分子。
　　所得到的高分子分別以1H-NMR、FT-IR進行結構鑑定，分子量Mn由GPC檢測並可量測其PDI，熱性質由TGA和DSC分析，並由DSR測量高分子的黏度、黏彈性和由接觸角量測其親水性。

關鍵字

甲基丙烯醯氯 ； 自由基聚合 ； 陰離子聚合法

並列摘要

The work is mainly to use anionic polymerization to prepare polyisoprene, and then functionalized the end of polyisoprene as a methacryl functional group which can be initiated by radical polymerization. We choose methyl methacrylate(MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomers in radical polymerization, expect to add viscosity and hydrophilicity of polyisoprene, leading to an amphiphilic polymer of Poly(PIMA-co-MMA-co-PEGMA).
　　First, polyisoprene is prepared via anionic polymerization. Because the living anionic chain end can react with propylene oxide, it forms a living oxygen ion at polymer chain end. After adding methacryloyl chloride, it forms a double bond at the end of the polymer, then we get PI-MA and this polymer will be served as a macromonomer. Next we heat to 70℃ to polymerize copolymer, using PI-MA、MMA and PEGMA as monomers, AIBN as initiator and THF as solvent.
　　Synthesis and characterization data of the copolymers have been collected from GPC、1H-NMR 、FTIR、TGA and DSC. Next, we also measure viscosity and viscoelasticity of the copolymers by DSR. Finally, we measure contact angle of the copolymers to presume the hydrophilicity.

並列關鍵字

methacryloyl chloride ； radical polymerization ； anionic polymerization

參考文獻

[21]Chen, D., Shao, H., Yao, W., & Huang, B. (2013). Fourier Transform Infrared Spectral Analysis of Polyisoprene of a Different Microstructure. International Journal of Polymer Science.

[1]Billouard, C., Carlotti, S., Desbois, P., & Deffieux, A. (2004). “Controlled” high-speed anionic polymerization of propylene oxide initiated by alkali metal alkoxide/trialkylaluminum systems. Macromolecules, 37(11), 4038-4043.

[2]Cao, T., Munk, P., Ramireddy, C., Tuzar, Z., & Webber, S. E. (1991). Fluorescence studies of amphiphilic poly (methacrylic acid)-block-polystyrene-block-poly (methacrylic acid) micelles. Macromolecules, 24(23), 6300-6305.

[3]Balazs, A. C., Zhou, Z., & Yeung, C. (1992). Behavior of amphiphilic comb copolymers in oil/water mixtures: a molecular dynamics study. Langmuir, 8(9), 2295-2300.

[4]Gref, R., Minamitake, Y., Peracchia, M. T., Trubetskoy, V., Torchilin, V., & Langer, R. (1994). Biodegradable long-circulating polymeric nanospheres.Science, 263(5153), 1600-1603.