本論文探討改質聚苯醚(PPO)之反應方法與性質，以製備官能化工程塑料並應用於物質分離與電氣等領域。首先利用原子轉移自由基反應及沃爾–齊格勒反應使PPO溴化，提出新的溴化反應方法radical and atom transfer halogenation (RATH)及其反應機制，相較於傳統溴化方法，RATH反應可在較低溫中進行，並可應用於多種溶劑之中。以溴化PPO為起始反應物，進行原子轉移自由基加成反應及雙原子親核取代反應，分別將TEMPO及米氏酸化合物(MA-M)導入PPO中，合成官能化的PPO-TEMPO及PPO-MAM，利用紅外光光譜儀(FTIR)、核磁共振光譜儀(NMR)、微差掃描卡計(DSC)和熱重分析儀(TGA)確認高分子之結構與熱性質。PPO-TEMPO可進行氮氧自由基控制聚合反應，且可利用TEMPO基團進行自由基交聯反應；而PPO-MAM之米氏酸基團進行熱裂解反應後可生成高反應性的烯酮官能基(ketene)，可接續進行[2+2]自身加成反應。因此，PPO-TEMPO和PPO-MAM都是具有可自身交聯特性的熱塑性高分子。將PPO-TEMPO和PPO-MAM製成膜材後並進行熱交聯反應，藉由熱重分析儀(TGA)、動態熱機械分析儀(DMA)及拉伸實驗確認膜材之性質。交聯後之PPO膜材保有良好的熱性質且具有更好的耐溶劑性、成膜性及機械強度。

This study explores multiple ways to functionalize poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and investigates the properties of the functionalized PPO. First, brominated PPO is prepared by atom transfer radical reaction and Wohl-Ziegler reaction. A new bromination method, radical and atom transfer halogenation (RATH), and its reaction mechanism has been demonsatrted. Compared to the conventional bromination methods, RATH can be performed at lower temperatures with less solvent restriction. Then, crosslinkable thermalplastic polymers, PPO-TEMPO and PPO-MAM, have been synthesized through bromination of PPO followed by atom transfer radical addition and nucleophilic substitution reaction, respectively. Structural and thermal analysis are carried out with FTIR, NMR, DSC and TGA. PPO-TEMPO could serve as a macroinitiator for nitroxide-mediated polymerization. Moreover, PPO-TEMPO and PPO-MAM are casted into films and thermally crosslinked to form crosslinked membranes with high gel fractions. The cured membranes exhibit excellent thermal properties, mechanical properties and solvent resistance as well as film formability.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VII
表目錄 XI
第一章 緒論 1
1-1 Poly(phenylene oxide) (PPO)結構與特性 1
1-2 PPO應用領域 2
1-3 PPO改質方法 3
1-4研究動機 6
第二章 文獻回顧 7
2-1 PPO溴化反應機制 7
2-2溴化PPO之改質反應 9
2-3含可交聯官能基之熱固性PPO 13
2-4帶米氏酸衍生物及Ketene官能基之高分子 15
2-5研究方法 19
第三章 實驗部分 20
3-1實驗藥品 20
3-2分析方法及使用儀器 22
3-3實驗步驟 25
3-3-1利用兩種機制溴化PPO，合成PPO-Br及NBS_PPO-Br 25
3-3-2利用兩種機制改質及官能化NBS_PPO-Br 28
3-3-3官能化PPO之熱交聯反應 30
第四章 結果與討論 32
4-1利用兩種機制溴化PPO 32
4-1-1 PPO-Br之合成鑑定 32
4-1-2 NBS_PPO-Br之合成鑑定 39
4-2利用兩種機制改質及官能化溴化PPO 44
4-2-1 PPO-TEMPO之合成鑑定 44
4-2-2 PPO-MAM之合成鑑定 51
4-3 官能化PPO之熱交聯反應 56
4-3-1 PPO-TEMPO之熱交聯反應 56
4-3-2 PPO-MAM之熱交聯反應 60
第五章 結論 66
第六章 參考文獻 67

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