臺灣博碩士論文加值系統

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。

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.

目錄
摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 X
第一章 緒論 1
1-1 前言 1
1-2 COC材料發展近況 2
1-2-1 何謂COC材料 2
1-2-2 COC材料之聚合反應類型 2
1-2-3 COC材料之特性與應用 5
1-3 Metallocene/MAO觸媒系統之簡介 7
1-4 聚烯烴高分子之官能化 10
1-4-1合成前驅物poly[ethylene-co-(5-ethylidiene-2-norbornene)]： 11
1-4-2合成含氯p[E-co-ENB]接枝聚合PMMA 11
1-4-3合成含溴p[E-co-ENB]接枝聚合PMMA 14
1-4-4 p[E-co-ENB]利用硼烷化學接枝聚合PMMA 15
第二章 實驗部份 20
2-1 藥品 20
2-2 儀器 22
2-3合成 p[E-co-ENB] 23
2-4合成含氯p[E-co-ENB]接枝聚合PMMA 24
2-4-1環氧化反應 24
2-4-2 甲醇開環反應 24
2-4-3 酯化反應 24
2-4-4 利用ATRP反應接枝PMMA 25
2-5 合成含溴p[E-co-ENB]接枝聚合PMMA 26
2-5-1 溴化反應 26
2-5-2 利用ATRP反應接枝PMMA 26
2-6 p[E-co-ENB]利用硼烷化學接枝聚合PMMA 27
2-6-1 氫硼化反應 27
2-6-2 接枝聚合PMMA 27
第三章 結果與討論 29
3-1 合成p[E-co-ENB] 29
3-2 合成含氯p[E-co-ENB]接枝聚合PMMA 31
3-2-1 環氧化反應 31
3-2-2 甲醇開環反應 32
3-2-3 酯化反應 34
3-2-4 利用ATRP反應接枝PMMA 35
3-3 合成含溴p[E-co-ENB]接枝聚合PMMA 37
3-3-1 溴化反應 37
3-3-2 利用ATRP反應接枝PMMA 39
3-4 p[E-co-ENB]利用硼烷化學接枝聚合PMMA 40
3-4-1 氫硼化反應 40
3-4-2 接枝聚合PMMA 41
3-5 p[E-co-ENB]接枝聚合PMMA三種方法之比較 43
3-5-1 接枝聚合效率方面 43
3-5-2 微差掃描熱卡計之分析 44
3-5-3 成本與效率觀點 45
第四章 結論 46
第五章 參考文獻 48
自傳 79


圖目錄
Figure 1 p[E-co-(ENB)] 之 1H-NMR圖 50
Figure 2 p[E-co-(ENB)] 之 FT-IR圖 51
Figure 3 反應物ENB單體濃度影響共聚物組成關係圖 52
Figure 4 反應物乙烯氣體壓力影響共聚物組成關係圖 52
Figure 5 環氧化反應後：(a).含26mol％環氧官能基 (b).含5mol％環氧官能基 之p[E-co-(ENB)]1H-NMR圖， 53
環氧化反應前：(c). p[E-co-(ENB)]之1H-NMR圖 53
Figure 6 (a). 含5mol％環氧官能基p[E-co-(ENB)] 之FT-IR圖, (b). p[E-co-(ENB)] 之FT-IR圖 54
Figure 7 (a).(b).(c) 含環氧官能基p[E-co-(ENB)]利用三種不同反應條件進行甲醇開環反應之1H-NMR 圖 55
Figure 8 (a) 含5mol％羥基p[E-co-(ENB)] 56
(b)含5mol％環氧官能基p[E-co-(ENB)] 之FT-IR圖 56
Figure 9 含1.59mol％Cl官能基p[E-co-(ENB)]之1H-NMR 圖 57
Figure 10 (a).含1.59mol％Cl官能基p[E-co-(ENB)], (b). 含5mol％羥基p[E-co-(ENB)] 之FT-IR圖 58
Figure 11 PMMA接枝率為(a).12.6mol％,(b).15.9 mol％,(c).43.9 mol％ 之含Cl官能基p[E-co-(ENB)]接枝PMMA 1H-NMR 圖 59
Figure 12 (a).含Cl官能基p[E-co-(ENB)]接枝PMMA,(b).含Cl官能基p[E-co-(ENB)] 之FT-IR圖 60
Figure 13 溴化反應後：(a).含19.84mol％Br官能基 (b). 含7.72mol％Br官能基 之p[E-co-(ENB)]1H-NMR圖 61
溴化反應前： (c). p[E-co-(ENB)]1H-NMR圖 61
Figure 14 PMMA接枝率為(a).2.4mol％,(b).5.4 mol％,(c).8.2 mol％ 之含Br官能基p[E-co-(ENB)]接枝PMMA 1H-NMR 圖 62
Figure 15 (a).含Br官能基p[E-co-(ENB)]接枝PMMA,(b).含Br官能基p[E-co-(ENB)] 之FT-IR圖 63
Figure 16 含OH官能基之p[E-co-(ENB)]之1H-NMR圖 64
Figure 17 (a).含OH官能基之p[E-co-(ENB)]之FT-IR圖,(b). p[E-co-(ENB)]之FT-IR圖 65
Figure 18 PMMA接枝率為(a).29.7mol％,(b).13.8 mol％ 之含硼官能基p[E-co-(ENB)]接枝PMMA 1H-NMR 圖 66
Figure 19 (a).含硼官能基p[E-co-(ENB)]接枝PMMA,(b).含OH官能基p[E-co-(ENB)] 之FT-IR圖 67
Figure 20 p[E-co-(ENB)].含環氧基p[E-co-(ENB)].含羥基p[E-co-(ENB)]以及含氯官能基p[E-co-(ENB)]接枝PMMA之DSC圖 68
Figure 21 p[E-co-(ENB)].以及含溴官能基p[E-co-(ENB)]接枝PMMA之DSC圖 69
Figure 22 p[E-co-(ENB)].以及含硼官能基p[E-co-(ENB)]接枝PMMA之DSC圖 70

表目錄
Table 1-1 三種材料物性比較表 71
Table 3-1 ENB之添加量與乙烯壓力對於共聚物組成之影響 72
Table 3-2 mCPBA添加量對於環氧率之影響 73
Table 3-3 含氯官能基p[E-co-(ENB)]接枝PMMA之研究 74
Table 3-4 反應時間與溴化氫濃度對於溴化反應之影響 75
Table 3-5 含溴官能基p[E-co-(ENB)]接枝PMMA之研究 76
Table 3-6 利用硼烷化學接枝PMMA之研究 77
Table 3-7 p[E-co-(ENB)]接枝聚合PMMA三種方法之比較 78

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