本實驗是由DHBP (4,4''-Dihydroxybenzophenone)與DFDPS (4,4`-Difluorodiphenyl Sulfone)藉由親核取代反應縮合聚合成poly(ether sulfone)s (DHBP-PES)。再藉由DOPO、Phenol對DHBP-PES進行親核加成反應及親電子取代反應而成功得到P1，我們利用相同的方式加入 DOPO、Aniline對DHBP-PES來合成P2，然而在P2的和結果由NMR圖譜看到有反應不完全的現象，顯示高分子P2是不容易聚合的。另外本實驗亦從單體合成方向而製備高分子(P2),實驗藉由DHBP 與 DOPO、Aniline 先合成為單體(1)在與4,4`-Difluorodiphenyl Sulfone 進行親核性取代反應縮合聚合成，成功合成反應型聚醚碸 (P2)。由實驗結果顯示，導入DOPO結構的聚醚碸具有相當優異的熱穩定性，及玻璃轉移溫度，亦有相當優異的溶解特性，對日後業界加工提供新的應用方向。
將反應型聚醚碸(P1、P2)與環氧樹脂(DGEBA、CNE)進行部分交聯反應，以及(P2)與ODPA (Oxydiphthalicanhydride)進而製備出可塗佈易加工的交聯型聚醚碸，透過交聯反應可大幅提昇聚醚碸對有機溶劑的耐受性與提高熱穩定性。

Linear poly(ether sulfones) are generally prepared from equal molar of bisphenols and dihalides of diphenyl sulfone in the presence of base. Therefore, poly(ethers sulfones) with a residual phenol group in the repea ting unit are difficult to control. In this work, a phosphinate poly(ether su- lfone) (P1) with a phenol group in the repeating unit was prepared from a one-pot reaction of a 4,4''-dihydroxybenzophenone (DHBP)-based poly(e- ther sulfone), poly(oxy-1,4-phenylenecarbonyl-1,4-phenyleneoxy-1,4-ph- enylene-sulfonyl-1,4-phenylene (DHBP-PEEK), with 9,10-dihydro-oxa- 10-phosph aphenanthrene-10-oxide (DOPO) and phenol in the presence of H2SO4. The phenol linkages provide reacting cites with epoxy resins. Therefore, flexible and transparent films of epoxy thermosets can be pre- pared from the curing of P1 with epoxy resins, cresol novolac epoxy (C- NE) and diglycidyl ether of bisphenol A(DGEBA). A phosphinated pol- y(ether sulfone) (P2) with an amino group in the repeating unit was ate- mpted to prepare in a similar procedure except for the phenol is replaced by aniline. However, the reaction was not successfully. To achieve the go- al, a DOPO-diphenolaniline, 1,1-bis(4-hydroxyphenyl)-1-(4-aminopheny- l)-1-(6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane, was prepared from the one-pot reaction of DOPO, DHBP and aniline in the presence of H2SO4 . P2 can successfully be prepared from the nucleophi- lic substitution of DOPO-diphenolaniline and difluorodiphenylsulfone (DFDPS) in the presence of K2CO3. P1/CNE, P1/DGEBA, P2/CNE, P2/DGEBA thermosets all show flexibility. The moderate-to-high mole- cular weight of P1 might be responsible for the flexibility (toughness), which is rarely seen in the low molecular weight curing agent/epoxy thermosets. P2 is brittle, but flexible film can be achieved by reacting the amine with dianhydride ODPA. After imidization at 300 oC (1h), the resulting P2/ODPA displays a Tg value as high as 340 oC by dynamic mechanical mechanical analysis. The data show the power of crosslinking.

總目錄

中文摘要 I
Abstract II
總目錄 IV
主目錄 V
表目錄 VII
圖目錄 VIII

主目錄
第1章 文獻回顧 1
1.1聚碸高分子簡介 1
1.2應用於環氧樹脂的增韌改質劑 2
1.3聚醚碸的合成與功能 3
1.4新型聚醚碸的合成與功能 7
1.5研究動機 8
第2章 實驗 9
2.1實驗藥品 9
2.2儀器設備 10
2.3單體之合成 12
2.4聚合物之合成 13
2.4.1聚合物DHBP-PES之合成 13
2.4.2聚合物P1之合成 14
2.4.3聚合物P1-aceto之合成 14
2.4.4聚合物P2之合成(Method:1) 15
2.4.5聚合物P2之合成(Method:2) 16
第3章 單體的合成特性與分析 17
3.1單體(1)合成特性 17
3.2單體(1)鑑定與分析 18
3.2.1單體(1)DSC鑑定 18
3.2.2單體FTIR鑑定 19
3.2.3單體(1)NMR鑑定 20
第4章 聚合物合成討論與性質分析 22
4.1聚合物DHBP-PES合成與特性 22
4.1.1聚合物P1 FTIR鑑定 23
4.1.2聚合物DHBP-PES NMR鑑定 24
4.2聚合物P1合成與特性 25
4.2.1聚合物 P2 FTIR鑑定 26
4.2.2聚合物P1 NMR鑑定 27
4.3聚合物P2合成與分析(方法一) 34
4.4聚合物P2合成與分析(方法二) 39
4.4.1聚合物P2 NMR鑑定 40
4.5聚合物熱性質測試 43
第5章 反應型聚醚碸交聯反應 47
5.1聚合物P1與Epoxy進行交聯反應 47
5.1.1聚合物P1與Epoxy交聯之熱性質分析 48
5.2聚合物P2與Epoxy進行交聯反應 52
5.2.1聚合物P2與epoxy交聯之熱性質分析 53
5.3聚合物P2與ODPA進行交聯反應 57
5.3.1聚合物P2與ODPA交聯FTIR監測 58
5.3.2聚合物P2與ODPA交聯之熱性質分析分析 60
第6章 結論 64
第7章 參考文獻 65

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