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標題: Novel Reactive Cyclic-Polymer Intermediates:Synthesis, Reaction and Application of Macrocyclic Poly(propylene oxide) Carbodiimides (MC-CDI).
作者: Cheng, Chih-Chia
關鍵字: ring-opening polymerization;巨環形碳二亞胺;macrocyclic CDI;macro-cyclic acylurea;prepolymers with narrow-molecular weights;high-dilution synthesis;intramolecular cyclization;開環聚合反應;巨環型醯基尿素;窄分子量分佈PU預聚物;高度稀釋合成;分子內環化反應
出版社: 化學工程學系所
巨環形高分子中間體的合成與開環聚合反應是高分子合成中最受矚目的發展重點之一。至目前為止,有效合成巨環形高分子中間體的方法仍充滿挑戰,但相較於一般線性結構,環狀結構潛在可提供優越物性及加工便利之優點。由於本實驗室近年來致力於碳二亞胺化學(carbodiimide chemistry)及合成異氰酸鹽預聚物(isocyanate prepolymer)之研究,由延伸其領域而發現快速又簡易的方法可製備反應型巨環狀高分子中間體。
本研究率先以窄分子量分佈預聚物進行分子內環化反應,進而成功合成出具高反應性的巨環形碳二亞胺(Macrocyclic CDIs,MC-CDI)。二異氰酸鹽中間體(diisocyanate intermediates)可以簡易地藉由2,4-TDI加入至聚異丙二醇中反應製備而得,並在高度稀釋(high dilution)合成法及1,3-Dmethyl-3-phospholene oxide(DMPO)催化劑下,完成MC-CDI之製備。單純之MC-CDI可藉由液相管柱層析(LC)進行純化分離,純化後可得MC-CDI產率約為40~70%,視巨環之分子量而定。MC-CDI更能進一步合成出高產率的衍生物巨環形醯基尿素(Macrocyclic Acylureas,MC-Acylureas)、末端帶有酸基的巨環形醯基尿素(Acid-Functionalized MC-Acylureas)及巨環形尿素(Macrocyclic Ureas,MC-Ureas)。開環模式反應也證實可經MC-Acylurea之熱反應而轉化成線形產物。
由於巨環形醯基尿素具有熱裂解開環之特性,我們成功地運用末端帶有酸基的巨環形醯基尿素進行開環聚合反應(Ring-Opening Polymerization,ROP),且簡易地製備出具高分子量的線形共聚合物。藉由本次於MC-CDI之研究及新發現,巨環形功能性中間體的性質及應用有更多新的瞭解,也使它們在高分子製程上具有嶄新的應用價值。

Synthesis and ring-opening polymerization of macrocyclic polymeric intermediates are one of the most highly sought-after targets in polymer synthesis. Synthesis of viable macrocyclic intermediates has been very challenging so far, but potentially the cyclic approach could provide many advantages over linear counterparts in areas of superior physical properties and simplicity in processing. Because of recent research in our laboratory on carbodiimide chemistry and isocyanate prepolymer synthesis, we have found a versatile facile approach of making macro-ring compounds.
We like to report the first successful synthesis of reactive macrocyclic carbodiimide (MC-CDI) through intramolecular cyclization of toluene diisocyanate prepolymer as the intermediate. The diisocyanate intermediates were prepared readily by addition 2,4-TDI to polypropylene diols. MC-CDIs were then obtained by cyclization of the prepolymer diisocyanate under high-dilution synthesis using DMPO as the catalyst. MC-CDIs could be purified by LC column and isolated in 40~70% yield for different molecular weight. MC-CDIs were converted into macrocyclic acylureas (MC-Acylureas), acid-functionalized MC-Acylureas and macrocyclic ureas (MC-Ureas) in high yield. The ring-opening reaction of macrocyclic polymer intermediates have also been demonstrated through heating of the MC-Acylurea.
The MC-Acylureas have shown to possess ring-opening properties through thermotysis. We have successfully applied their reaction to effect ring-opening polymerization (ROP) of acid-functionalized MC-Aculurea to synthesize for linear copolymers of high molecular-weight. Through our first MC-CDI research and discovery, we not only have advanced new fundamental understandings on these macrocyclic functional intermediates but also have found their novel applications in polymer processing.
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