臺灣博碩士論文加值系統

具有特殊功能的高分子材料為相關產業所急需，而高分子材料性能的掌握與控制高分子結構，我們設計合成了以有機金屬為主體的有機金屬可逆性加成裂解鏈轉移劑 (a) [TpRuS2C-R, R = PPh3, OMe, OEt, Ph], (b) [TpRuS2P(OEt)2] { Tp = hydridotripyrazolylborate, BH[(C3H3N2)3]}，為新穎有機金屬可逆性加成裂解鏈轉移劑，進行活性自由基聚合反應，包括在至少一種之起始劑(initiator)及至少一種之有(TpRuS2C-R)存在的狀況下，將一種或一種以上之單體進行聚合反應，可得到具有較低聚合度分佈性指數及具有高分子鏈末端金屬官能基化之聚合物。另一方面，所得之聚合物可更進一步進行金屬脫去反應，以得到同樣具有較低聚合度分佈性指數之有機聚合物。所得到的聚合物其PDI介於1.1~1.7之間。

Synthetic polymers have Living/controlled radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) can be achieved with the use of novel organometallic ruthenium complex (a) [TpRuS2C-R, R = PPh3, OMe, OEt, Ph], (b) [TpRuS2P(OEt)2] {where Tp is hydridotripyrazolylborate, BH[(C3H3N2)3]}. Electron with drawing organometallic substituents can enhance the activity of RAFT reagents. In addition, the terminal organometallic functional group may be removed by subjecting the obtained polymer to elimination to provide the corresponding organic polymer. In this study, organometallic reagents bearing dithiocarbonyl group is synthesized and applied to RAFT polymerization of styrene with conventional initiator, azobisisobutyronitril (AIBN) at 60℃. Monomer conversion, molecular weight evolution, and polydispersity index (PDI) are measured. The PDI of the formed polymer is between 1.1 and 1.7 in the presence of RAFT reagents.

LIST of CONTENTS
中文摘要 I
ABSTRACT II
LIST of CONTENTS III
LIST of FIGURE V
LIST of SCHEME VII
LIST of TABLE VIII
NUMBER and PAGE of COMPLEX IX
REACTION SCHEME X

Chapter 1. Introduction. 1
1-1 What is controlled/living free radical polymerization. 1
1-2 Controlled/living free radical polymerization. 5
1-3 Organometaiilc RAFT Polymerization. 15
1-4 Motivation. 18
Chapter 2. Result and discussion. 21
2-1 Synthesis the complex TpRuS2C-PPh3. 22
2-2 Synthesis the complex TpRuS2C-OCH3. 30
2-3 Synthesis the complex TpRuS2C-OCH2CH3. 35
2-4 Synthesis the complex TpRu(PPh3)(S2C-Ph). 38
2-5 Synthesis the complex PhS(S)CCH2C(S)SPh. 42
2-6 Synthesis the complex TpRu(PPh3)(S2P(OCH2CH3)¬2). 44

Chapter 3. Organometallic RAFT polymerization. 51
3-1 RAFT polymerization 51
3-2 Styrene polymerization with agents TpRu(PPh3)(S2C-R) (R = PPh3, OCH3, OCH2CH3, Ph), TpRu(PPh3)(S2P(OCH2CH3)2), PhS(S)CCH2C(S)SPh. 56
3-3 Discussion 61

Chapter 4. Experimental 65
4-1 Materials 65
4-2 Synthesis ruthenium complexes 68
References 80
Appendix 85

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