臺灣博碩士論文加值系統

本研究分別以熱及光化學法製備出兩種芳香族及一種脂肪族之活性雙官能基Bis-azetidine-2,4-dione的高分子中間體，其具備三項優點：（1）單體熱穩定性高，熱裂解溫度超過200℃。（2）可與脂肪族的一級胺在室溫迅速進行加成開環反應，產率極高且無副產物之生成。（3）單體具有高度的反應選擇性，若單體同時與脂肪族的一級胺、一級醇、苯胺及二級胺反應，單體對一級胺具有絕對的快速反應選擇活性。

本文使用此單體和脂肪族二元胺以快速一步驟的熱熔法製備多種Polymalonamide高分子，以及由快速二步驟的預聚合物方法製作Polymalonamide彈性體，預聚合物方法先利用Jeffamine D2000與Bis-azetidine-2,4-diones單體製備含軟鏈段之高分子預聚物，再加入鏈延長劑(己二胺)於高分子預聚物中，即完成高分子彈性體之製備。依Bis-azetidine-2,4-diones單體結構的不同，可分別製備出高結晶型、半結晶型與非結晶型的高分子彈性體。

合成之Polymalonamide高分子及Polymalonamide彈性體，以熱分析儀器(DSC、TGA)測量高分子產品的熱性質，並且以動態機械性質分析儀（DMA）與拉力測試瞭解高分子彈性體之基本機械性質，並將探討熱性質及機械性質的變化與高分子彈性體結構之間的關係；最後藉由原子力顯微鏡（AFM）、場發射掃瞄式電子顯微鏡（FE-SEM）去證實熱性質、機械性質與高分子彈性體結構之間的關係，並且觀察高分子彈性體的表面型態學與其原料結構間的關係。

Two methods of synthesizing bis-azetidiene-2, 4-dione intermediates have been accomplished in our lab for preparation of three bis-azetidine-2, 4-dione, PBAZ, MBAZ, and LBAZ for our study. Using a thermal process, diethylketene cyclo-adds to aromatic diisocyanates to form aromatic bis-azetidine-2, 4-diones. The yields of bis-aztidine-2, 4-diones from p-phenylene diisocyanate(PPDI) and 4, 4’-dipehnylene diisocyanate (4, 4’-MDI) were found to be 74％ (for PBAZ) and 82% (MBAZ) respectively. Whereas, N, N’-hexamethylene bis-azetidine-2, 4-dione(LBAZ) an aliphatic counterpart, was prepared differently by photolysis of hexamethylene-bis-N-formyl-N-methacrylamides in 71%. Melt-polymerization of bis-azetidine-2, 4-diones with hexamethylene diamine yielded polymalonamides.

Similar melt-polymerization has also been extended to synthesize polymolonamide elastomers using Jeffamine® D2000 as the soft-segment component and hexamethylene diamine as the extender with each of the prepared bis-azetidine-2, 4-diones. Elastomers of 35%, 45% and 55% hard-segment contents in each series were prepared. All syntheses were carried out by a two-step process by formation of pre-polymers between individual azetidine-2, 4-diones with Jeffamine* in the first step. The second step to the final product was done with hexamethylene diamine as the extender. Very rapid conversions to the final products were observed universally in less than 150 sec. The polymalonamide elastomers prepared were analyzed by TGA, DSC, DMA, AFM and FE-SEM to characterize morphology of the products.

All elastomers prepared from PBAZ and LBAZ are semi-crystalline in nature. Especially, three PBAZ derived elastomers crystallize readily to form distinctive oval island-shape domains as observed by AFM, and are characterized by their sharp Tg,s and Tg,h in DSC and DMA. The domain sizes are uniformly distributed between 200nm to 300nm with increasing larger sizes for higher hard-segment contents. Although semi-crystalline LBAZ-derived elastomers also showed similar phase-segregation in AFM, but their patterns were different and could be influenced greatly by processing techniques. Under high spinning rates of greater than 4000 rpm in spin-coating process, the morphology of LBAZ-elastomers turned into fibrous pattern. Our study indicated that only MBAZ-elastomers are amorphous and showed well mixing between hard and soft segments as indicated by the appearances of Tg,s and new Tg,m at -10~18℃ for the mixed phases in DSC. The physical properties of elastomers have been found to be greatly influenced by morphology and by the hard-segment contents but appeared to be in lesser degrees for the latters.

致謝 I
摘要 I
第1章 緒論 1
第2章 文獻回顧 3
2-1 Polymalonamides 3
2-2 微相分離與型態學(Morphology) 5
2-2-1 軟硬鏈段與相變化 5
2-2-2 高分子表面型態之研究 7
2-3 彈性體之簡介 10
第3章 實驗內容 12
3-1 實驗藥品 12
3-1-1 異氰酸鹽 12
3-1-2 醯氯 12
3-1-3 胺 13
3-1-4 酸 14
3-1-5 有機溶劑 14
3-2 實驗儀器 16
1.傅利葉紅外線光譜儀 16
2.核磁共振光譜儀 16
3.微差熱掃描分析儀 16
3-3 實驗裝置設備 18
1. 熱化學反應器裝置 18
2. 光化學反應器裝置 18
3-4 樣品製備與分析方法 19
3-4-1 拉伸力測試之樣品製備 19
3-4-2 AFM測試之樣品製備 20
3-4-3 FE-SEM測試之樣品製備 21
3-5 高分子樣品物性分析方法 22
3-5-1 以極限黏度法測量彈性體之分子量 22
3-5-2 動態機械性質分析儀（DMA）分析方法 23
3-5-3 原子力顯微鏡（AFM）之分析原理 25
3-5-4 場發射掃瞄式電子顯微鏡（FE-SEM） 26
第4章 Bis-azetidine-2,4-diones之合成 27
4-1 p-Phenylene-Bis-Azetidine-2,4-dione的合成 【PBAZ】 27
4-1-1 實驗步驟 27
4-1-2 實驗結果 30
4-2 其它高分子原料之合成 31
4-2-1 熱化學合成 4,4-Methylene-bis(phenyl Azetidine-2,4-dione)【MBAZ】 31
4-2-2 光化學合成 N,N’-Hexamethylene-bis-azetidine-2,4-dione【LBAZ】 31
4-3 Azetidine-2,4-dione之選擇性實驗 32
4-3-1 Phenyl-azetidine-2,4-dione的合成及反應 32
4-3-2 選擇性實驗結果與討論 33
4-4 合成BAZ之結果與討論 34
第5章 Polymalonamides和Elastomers的合成 35
5-1 Polymalonamide的合成 35
5-1-1 合成之實驗步驟 35
5-1-2 實驗結果與討論 36
5-2 彈性體的合成 39
5-2-1 彈性體實驗步驟 39
5-3 實驗結果與討論 41
第6章 彈性體性質分析之結果 43
6-1 以極限黏度法測量彈性體之平均分子量 43
6-1-1 實驗結果與討論 43
6-2 高分子彈性體之儀器分析結果與討論 45
6-2-1 熱性質分析結果與討論（TGA、DSC） 45
6-2-2 機械性質分析結果與討論（拉伸力測試、DMA測試、硬度測試） 55
6-3 結果與討論 65
第7章 彈性體之表面型態之研究 67
7-1 三種高分子材料結構與表面型態的差異分析 67
7-2 硬鏈段含量與表面型態關係之分析 76
7-3 硬鏈段含量與硬鏈段微區域大小之間的關係 84
7-4 利用FE-SEM證明AFM相分離結果 88
7-5 結果與討論 94
第8章 結論 96
參考文獻 99
附錄一 101

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