臺灣博碩士論文加值系統

摘 要
本論文以硫醇、醯胺當作雙成分起始劑活性聚合乙烯係單體，探討其起始反應機制、共聚合反應行為與熱裂解動力等等。在聚合反應過程當中，硫醇、醯胺雙成分起始劑缺一不可，硫醇會經由鏈轉移反應將氫原子轉移到醯胺上形成一過渡狀態錯化合物，在經由適當的重排反應形成thiolamide結構，單體經由這不穩定結構進行活性聚合反應。聚合過程當中，分子量的大小可由單體與硫醇的比例來控制，醯胺在此系統當中扮演著capping agent的功能。由於amide的結構存在於高分子尾端基團上，因此進行聚合反應時會有一定程度的立體效應，不同極性的溶劑會影響capping agent和高分子末端自由基的距離，影響反應速率、分子量分佈係數等等。由於立體效應的存在，所得到的高分子具有較高的玻璃轉移點溫度，高分子末端不存在終止反應造成的不飽和雙鍵，因此具有相當高的熱安定性，搭配不同種類的硫醇、醯胺所得到的末端基團也會影響高分子材料的熱安定性。在共聚合反應時，由於尾端基團的存在會影響共聚單體的反應活性，而產生不同r1、r2的值，加入少量拉電子基團的共單體會加快共聚合反應速率。利用這種活性聚合方法成功地合成團鏈共聚合物高分子。

Abstract
Living radical polymerization of vinyl monomer by thiol and lactam as initiator was investigated in this thesis, including the mechanism, reactivity of copolymerization, and thermal degradation behavior. Proton is transferred from thiol to lactam group and forms the inter-medium structure, thiolamide, as the active specie during the initiation step. Propagation reaction, thereby, occurs via monomer insertion from the terminal group of the polymer chain end. Molecular weight can be controlled by the monomer-to-thiol ratio. Lactam in this system acts as a capping agent, which in terms to control the tactility and the dynamic equilibrium of activation/deactivation process. In addition, polymers prepared by this route have high glassy transition temperatures due to the high proportion of syndiotactic conformation produced. Solvent effects were also examined to reveal the evidence of capping agent on the polymerization rate, tactility, and molecular weight distribution. Since the absence of termination reaction in the system, polymers without vinyl-bond are generated, which causes the high thermal stability. For copolymerization, the polymerization rate enhanced by adding a few mole ratio of comonomer bearing with electron withdraw group, meanwhile the reactivity will also vary accordingly. Finally, well-defined block copolymers were successfully synthesized by this novel approach.

目 錄
中文摘要…………………………………………………………………………I
英文摘要………………………………………………………………………II
誌謝……………………………………………………………………III
目錄……………………………………………………………………IV
表目錄…………………………………………………………………IX
圖目錄…………………………………………………………………XI
反應機構目錄…………………………………………………………………XVIII

第一章 序論……………………………………………………………………………….1
第二章 文獻回顧………………………………………………………………………….3
2-1 簡介…………………………………………………………………………………3
2-2 陰離子聚合法………………………………………………………………………5
2-3 基團轉移聚合法……………………………………………………………………7
2-4 Iniferter………………………………………………………………………………9
2-4.1 Iniferter之結構與特性…………………………………………………………..10
2-5 活性自由基聚合系統 SFRP、ATRP、RAFT的比較………………………….12
2-5.1 穩定自由基聚合反應 (Stable Free Radical Polymerization)……………….13
2-5.2 原子轉移自由基聚合反應 (Atom Transfer Radical Polymerization)………17
2-5.3 可逆鏈轉移聚合反應 (Reversible Addition Chain Transfer Polymerization).19
2-6 活性自由基聚合的基本要求……………………………………………………...22
2-6.1 起始反應………………………………………………………………………22
2-6.2 自由基和休眠物種交換之影響………………………………………………23
2-6.3 終止反應之影響……………………………………………………………....26
2-7 活性自由基聚合反應機構……………………………………………………….29
2-7.1 分子交換……………………………………………………………………..33
2-7.2 觸媒活化休眠物種…………………………………………………………..33
2-7.3 永久自由基的影響………………………………………………………….34
2-7.4 平衡反應機制……………………………………………………………….34
2-7.5 休眠物種的結構…………………………………………………………….36
2-8 活性自由基聚合反應動力之探討………………………………………………37
2-8.1 活性反應速率機構和活化反應速率常數………………………………….39
2-8.2 聚合反應速率……………………………………………………………….44
第三章 研究動機……………………………………………………………………….48
第四章 實驗內容……………………………………………………………………….49
4-1 藥品………………………………………………………………………………49
4-2 儀器設備…………………………………………………………………………50
4-3 實驗步驟………………………………………………………………………….50
4-4 產物鑑定………………………………………………………………………….51
4-5 理論計算Hartree-Fock Self-Consistent-Field……………………………………52
4-5.1 Gaussian 98……………………………………………………………………52
4-5.2 Basis set 基底函數組…………………………………………………………52
4-5.3 6-31G Basis set……………………………………………………………...…53
4-5.4 Polarized Basis set 極化基底函數組…………………………………………53
4-6 ESR研究自由基存在的型式………………………………….………………..53
第五章 聚合反應動力學之探討…………………………………………………………54
5-1 以12-硫醇和己內醯胺當作雙成分起始劑活性聚合苯乙烯單體……………….54
5-1.1 鑑定研究………………………………………………………………………54
5-1.1A FT-IR………………………………………………………………………54
5-1.1B NMR………………………………………………………………………54
5-1.1C ESR……………………………………………………….……………….59
5-1.1D 理論計算………………………………………………………………….59
5-1.2 反應機構………………………………………………………………………60
5-1.3 分子量的行為特徵……………………………………………………………67
5-1.4 團鏈共聚合物…………………………………………………………………68
5-1.5 聚合動力學探討………………………………………………………………71
5-1.5A 己內醯胺的反應動力研究……………………………………………….71
5-1.5B 12-硫醇的反應動力研究………………………………………………….71
5-1.5C 活化能…………………………………………………………………….71
5-1.6 結論……………………………………………………………………………76
5-2 以12-硫醇和己內醯胺聚合MMA之研究……………………………………….77
5-2.1 結構鑑定………………………………………………………………………77
5-2.2 動力學探討……………………………………………………………………85
5-2.2A 己內醯胺對於聚合動力的影響………………………………………….85
5-2.2B 12-硫醇對於聚合動力的影響…………………………………………….85
5-2.2C 活化能…………………………………………………………………….86
5-2.3 反應機構………………………………………………………………………95
5-2.4 溶劑效應………………………………………………………………………95
5-2.5 膠凝效應………………………………………………………………………95
5-2.6 結論……………………………………………………….………….………100
第六章 共聚合反應探討……………………………………………………….……….101
6-1 MMA-AN共聚合反應探討………………………………………………………102
6-1.1 反應動力學探討…………………………………………………………..…102
6-1.2 共聚合反應性的探討………………………………………………………..103
6-2 MMA-VAc共聚合反應探討…………………………………………………….107
6-2.1 反應動力學探討……………………………………………………………107
6-2.2 共聚合反應性的探討……………………………………………………….107
6-3 MMA-MAn共聚合反應探討…………………………………………………….112
6-3.1 反應動力學探討……………………………………………………………..112
6-3.2 共聚合反應性的探討………………………………………………………..112
6-4 MMA-St共聚合反應探討……………………………………………………..…117
6-4.1 反應動力學探討………………………………………………………..……117
6-4.2 共聚合反應性的探討………………………………………………………..118
6-6結論………………………………………………………………………………..122
第七章 研究以硫醇/醯胺當作起始劑合成之高分子熱性質探討…………………….123
7-1 相同醯胺條件下改變不同硫醇種類對於PMMA的熱性質分析……………...123
7-1.1 實驗代號……………………………………………………………………..124
7-1.2 產物之鑑定…………………………………………………………………..124
7-1.3 裂解行為比較………………………………………………………………..125
7-1.4 尾端基團對於PMMA的熱穩定性影響……………………………………131
7-1.5 熱裂解動力分析……………………………………………………………..132
7-1.5A Flynn method……………………………………………………………..132
7-1.5B Flynn-Ozawa method…………………………………………………….133
7-1.5C Kissinger method…………………………………………………………133
7-1.6 結論…………………………………………………………………………..138
7-2 相同12-硫醇條件下改變不同醯安類對於PMMA的熱性質分析…………….139
7-2.1 實驗代號說明………………………………………………………………..139
7-2.2 TGA圖形的比較與尾端基對其熱穩定性的影響…………………………..139
7-2.3 熱裂解動力…………………………………………………………………..142
7-2.3A Flynn method……………………………………………………………142
7-2.3B Flynn-Ozawa method……………………………………………………142
7-2.3C Kissinger method………………………………………………………..142
7-2.4 結論………………………………………………………………………….147
7-3 相同醯胺條件下改變不同硫醇種類對於PBA的熱性質分析………………..148
7-3.1 實驗代號…………………………………………………………………….148
7-3.2 結構鑑定……………………………………………………………………..148
7-3.3 比較PBA的熱裂解行為…………………………………………………….149
7-3.4 研究可能的熱裂解機構……………………………………………………..154
7-3.5 尾端基團對於PBA熱穩定性的影響……………………………………….155
7-3.6 熱裂解動力學探討…………………………………………………………..158
7-3.6A 恆溫裂解實驗…………………………………………………………...158
7-3.6B Flynn method……………………………………………………………..161
7-3.6C Flynn-Ozawa method…………………………………………………….161
7-3.6D Kissinger method………………………………………………………...162
7-3.7 結論…………………………………………………………………………166
第八章 總結……………………………………………………………………………..167
參考文獻…………………………………………………………………………………168
自述………………………………………………………………………………………176
著作………………………………………………………………………………………177

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