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標題: 含胺酯及尿素官能基環型寡聚物之合成、鑑定與開環聚合
Synthesis, identification and ring-opening polymerization of cyclic urethane urea oligomer
作者: 羅偉舜
Lo, Wei-Shun
關鍵字: 環型寡聚物;cyclic oligomer;擬高稀技術;分子間環化反應;聚胺酯;開環聚合反應;pseudo high dilution;intermolecular cyclization;polyurethane urea;ring-opening polymerization;MALDI-ToF mass
出版社: 化學工程學系所
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本研究藉由2,4-甲苯二異氰酸鹽(2,4-toluene diisocyanate,2,4-TDI)與分子量700的聚丙烯醚二元醇(poly(oxypropylene),PPG700)以2.2:1的比例,成功合成產率達76%以上之單鏈段雙異氰酸鹽末端基的線型預聚物(2,2’-TDI700)。並在擬高稀(pseudo high dilution)的反應環境下,與乙二胺(ethylene diamine,EDA)進行雙分子環合反應,製備得含胺酯與尿素基的環型寡聚物EDA700,經丙酮(acetone)分離純化後,重量產率可達50%。


In this study, 2,2'-diisocyanate terminated TDI700 was obtained by reaction of 2,4-TDI and Mw.700 poly(oxypropylene) at a ratio of 2.2:1. GPC analysis showed us a good yield of low chain extended 2,2'-TDI700 around 76%.

In the model compound study, chemical shifts in the urethane and urea group derived from 2,4-TDI were clearly identified and widely used in our research.

Followed by reacting with ethylene diamine(EDA) at a pseudo high dilution condition, the ring closure of diisocyanate group on 2,2'-TDI700 was achieved with repeating unit of 1~2. The purified structure of cyclization product, EDA700, was confirmed by FTIR, NMR, MALDI-ToF mass analysis. However ,the GPC analysis of EDA700 did not agree with the mass analysis. By several indirect evidences, cyclic compound is considered to form aggregates.

In the ring opening polymerization of EDA700, effects of catalysts and temperature were studied. An unexpected release of EDA molecular during the reaction restricted the growth of molecular weight. The highest polymeric product was synthesized without any catalyst at 180℃ for 6 hours and showed only up to 8 repeating units with polydispersity of 1.31 in GPC analysis.
其他識別: U0005-2708200711264000
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