- 學位論文
官能化(乙烯/5-亞乙基-2-降冰片烯)共聚物之合成研究
Study on the synthesis of functional poly﹝ethylene-co-﹙5-ethylidene-2-Study on the synthesis of functional poly﹝ethylene-co-﹙5-ethylidene-2-norbornene) ﹞
摘要
COC材料是目前新興高分子材料之一種，它擁有多項優點，例如高成膜性，高透光性，熱穩定性佳，良好機械性質，但其材料屬於非極性，藉由接枝聚合親水性單體（PMMA），可加強與極性材料之間的作用力，使COC材料可應用於更寬廣之領域。 本研究以柔軟之線性烯烴－乙烯與剛硬之環烯烴－5-ethylidiene-2-norbornene以metallocene/MAO觸媒系統共聚合成COC前驅物材料，藉由調整兩種烯烴單體進料組成，可得到不同組成的前驅物，前驅物玻璃轉換溫度(Tg)也可控制。接著，前驅物主要以5-ethylidiene-2-norbornene中未參與共聚合的ethylidiene雙鍵為改質點，以三種方法進行接枝聚合PMMA，第一部份將雙鍵改質經環氧化反應、甲醇開環反應，以及酯化反應接上具有－Cl官能基，再進行原子轉換自由基聚合反應接枝聚合PMMA。第二部份將前驅物之雙鍵與溴化氫水溶液進行溴化反應，可得到含－Br官能基之COC高分子，同樣也是進行原子轉換自由基聚合反應接枝聚合PMMA。第三部份則是利用硼烷化學在氧氣存在下進行自由基聚合反應接枝聚合PMMA。使用核磁共振光譜儀、傅立葉紅外線光譜儀，以及微差掃描熱卡計鑑定分析三大部份之反應，並探討各反應之反應機制、控制條件。
並列摘要
Cyclic olefin copolymers are important in polymer material due to their high transparency, good thermal stability, mechanical strength and easy to make film. The hydrophobic cyclic olefin copolymers were not compatible with hydrophilic material and have less chemical attraction each other. They could be changed to more polar by grafting PMMA and increase their application. Precursor was synthesized from soft linear olefin-ethylene and rigid cyclic olefin-5-ethylidiene-2-norbornene via Et(Ind)2ZrCl2/MAO catalyst system. The glass transition temperature of the copolymers could be controlled by different ratio of the two copolymers. Furthermore, grafted copolymerization was made from the double bond of the ethylidiene in the copolymers by three routes. First, the double bond of the ethylidiene in the copolymers convert to the copolymers containing chloride functional group via epoxidation, ring-opening reation by methanol, and esterification. The grafting PMMA can be carried by atom transfer radical polymerization. Second, the copolymers containing bromide functional group can be obtained by the copolymers containing ethylidiene group react with hydrobromic acid, and then grafting PMMA by atom transfer radical polymerization. Third, the material can be achieved by the free radical polymerization by borane chemistry procedures to graft PMMA. The mechanism of the three methods and the reaction parameter’s effect will be discussed. At the same time, the product could be identified by 1H-NMR, FT-IR, and DSC.
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