合成新型掌性雙嵌段高分子聚合物

Synthesis of the Novel Chiral Diblock Copolymer

黃建評(JIAN PING HUANG)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/碩士(2014年)

摘要

掌性高分子材料因為具備特殊的物理化學性質是學術、工業研究的重要課題，本研究為使用掌性杏仁酸(Mandelic acid)及其衍生物為單體以開發新型掌性高分子聚合物及團鏈共聚物所進行之合成研究。
在合成步驟上主要應用如下三個步驟加以合成:
1. 使用原子轉移自由基聚合反應，以溴化亞銅(Copper(I) bromide)與N,N,N',N,'N''-五甲基二亞乙基三胺(PMDETA)進行觸媒活化並加入甲基丙烯酸苯基酯(Benzyl methacrylate)與雙起始劑已進行聚甲基丙烯酸苯基酯的反應，並藉由雙起始劑之特點(一頭帶有溴酯基(-Br)，另一頭帶有氫氧(-OH)，使得在原子轉移自由基聚合的過程中可得到末端具有氫氧基的聚甲基丙烯酸苯基酯之高分子(PBnMA-OH)。
2. 將不同旋性之扁桃酸單體(D,L/D/L -mandelic acid)進行氫化反應，之後將氫化過後的單體D,L/D/L -2 - 環己基 - 2 - 羥基乙酸(D,L/D/L -hexahydromandelic acid)在對甲苯磺酸(p-toluenesulfonic acid)的存在下，可成功合成環化過後之D,D/L,L/D,L二聚體。
3. 使用開環聚合方式，利用異辛酸亞錫(Tin(II) 2-ethylhexanoate)作為起始劑，將PBnMA-OH轉換成PBnMA-O -(Oct)2之macroinitiator，並利用成功合成出之二聚體以進行第二段嵌段高分子的鏈成長反應，成功合成出PBnMA-b-PLCG (poly(Benzyl methacrylate)-block-poly(L-Dicyclohexylglycolide))和PBnMA-b-PDCG (poly(Benzyl methacrylate)-block-poly(D-Dicyclohexylglycolide))嵌段共聚高分子。
　　本實驗可有效地控制雙嵌段共聚物之高分子分子量與分子量分佈，另外藉由GPC、NMR、圓極化雙色光譜之實驗結果確認本研究成功的合成出具有掌性鏈段之嵌段共聚高分子。

關鍵字

開環聚合 ； 自由基聚合 ； 掌性高分子 ； 嵌段共聚高分子

並列摘要

Chiral Polymers possess unique physical, chemical and biochemical properties, and hence have been the focus of academy and industrial research because of their potential applications. To date, only a few synthetic main-chain chiral polymers are known because of the difficulty in the syntheses of chiral monomers.
This paper reports the first syntheses of a series of new chiral diblock copolymers of the PBnMA-b-PLCG (poly(Benzyl methacrylate)-block-poly(L-Dicyclohexylglycolide)), which were synthesized from ring-opening-polymerization of a chiral diglycolide ester generated by hydrogenation of mandelic acid. The chiral diblock copolymer of PBnMA-b-PLCG (poly(Benzyl methacrylate) -block-poly(L-Dicyclohexylglycolide)) was prepared via the following synthetic steps:　　
1. The chiral monomer (dicyclohexylglycolide) was synthesized from the dimerization of hexahydromandelic acid, which was prepared by hydrogenation of the phenyl ring of the mandelic acid, using p-toluenesulfonic acid as the acid catalyst.
2. The OH-capped PBnMA was prepared by atom transfer radical polymerization of benzyl methacrylate using the hydroxyl-containing a-bromoester as the initiator.
3. The PBnMA-b-PLCG diblock copolymer was prepared by living ring opening polymerization of the chiral cyclic ester (dicyclohexylglycolide) using OH-capped PBnMA as the macroinitiator.
The resulting chiral PBnMA-PLCG diblock copolymer was found to have a well-defined chemical structure as revealed by NMR and GPC and TEM analyses.

並列關鍵字

ring opening polymerization ； atom transfer radical polymerization ； chiral polymer ； diblock copolymer

參考文獻

2. R. M. Ho, Y. W. Chiang, C. C. Tsai, C. C. Lin, B. T. Ko and B. H. Huang, J. Am. Chem. Soc., 126, 2704 (2004)

4. G. L. Cheng, C. P. Hu, S. K. Ying, Macromol. Rapid Commun., 20, 303-307 (1999)

5. G. L. Cheng, C. P. Hu, S. K. Ying, Journal of Molecular Catalysis A: Chemical, 144, 357-362 (1999)

6. K. Matyjaszewski, Macromolecules., 32, 9051-9053 (1999)

7. K. Matyjaszewski, J. Xia, Chem. Rev., 101, 2921-2990 (2001)