臺灣博碩士論文加值系統

聚氧氮苯并環己烷(Polybenzoxazine)由於在硬化過程中具有良好尺寸安定性、低吸濕性、耐化學性等優點，因此在近年來被廣泛的研究。然而Benzoxazine本身交聯密度低，所以耐熱性及機械性質仍顯不足。因此，利用Benzoxazine良好的分子設計彈性，或是利用添加補強材形成複合材料，以提高其熱穩定性及機械性質。
本研究主要目的在製備不同側鏈氧氮苯并環己烷，並混摻多面體矽氧烷寡聚物(POSS)後形成奈米複合材料。首先利用無溶劑法選用不同的雙酚類與苯胺、三聚甲醛先行合成不同側鏈的Benzoxazine: 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) isopropane (Bz-A), 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) methylene (Bz-F), 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) thylbenzene(Bz-ap)，利用FTIR、1H-NMR進行結構鑑定，並利用微分掃描熱卡計(DSC)探討其熱硬化行為，經硬化後的Benzoxazine利用DMA、TGA探討其物性。實驗結果顯示，Benzoxazine在硬化過程中具有自催化的效果。熱機械性質與熱穩定性方面，Bz-F由於分子結構立體障礙小，具有較高的交聯密度，因此有較佳的機械性質與耐熱性質。
將不同含量的POSS分別加入Benzoxazine系統中形成奈米複合材料，探討奈米複合材料的熱硬化行為及其硬化物之物性。由結果顯示，添加POSS後會降低Benzoxazine硬化時的自催化效果。熱機械性質與熱穩定性方面，POSS添加量在5wt%時具有最佳的機械性質與耐熱性。

Polybenzoxazines have evinced significant interest as a class of high performance polymer. These novel materials gain attention because of low volumetric shrinkage upon curing, minimal moisture absorption, excellent resistance to chemicals. However, the low crosslinking densities of benzoxazine resins leaded to insufficient in mechanical properties and thermal stability. Therefore, for improve mechanical properties and thermal stability, the molecular design flexibility and added reinforcements would be employ.
The goal of this research is focused on the synthesis of different side chain benzoxazines and hybrid with polyhedral oligomeric silsesquioxane(POSS) to preparation for nanocomposites. 6,6-Bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) isopropane (Bz-A), 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) methylene (Bz-F) and 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) ethylbenzene (Bz-ap) can be use the bisphenols which contain different pendant group with aniline and paraformaldehyde through solventless method to synthesis. The structure of synthesized Benzoxazines will be confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and their thermal curing behavior of Benzoxazines was studied by differential scanning calorimetry (DSC). The properties of cured Benzoxazines were studied by dynamic mechanical analysis (DMA), thermal gravimetric analysis (TGA). The results show that Benzoxazines at curing process have high autocatalytic effect. In mechanical and thermal stability properties, Bz-F had excellent properties than Bz-A and Bz-ap, because of higher cross-linkes and it was attributed to lower steric hinderance.
Various contents of POSS were added into Bz-A, Bz-F and Bz-ap, respectively. The thermal curing behaviors of thermocurable nanpcomposites were investigated, and their cured network’s physical properties were also investigated. The results indicate that the autocatalytic effect of Benzoxazines would be decrease after added POSS. The mechanical and thermal stability properties of nanocomposites were increased with the increasing of POSS contents, whereas when POSS contents over 5wt%, the properties slightly decreased.

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 v
Scheme vii
表目錄 viii
圖目錄 ix
第一章 緒論 1
1-1 前 言 1
1-2 奈米複合材料 1
1-3氧氮苯并環己烷介紹 2
1-4多面體矽氧烷寡聚物的介紹 4
1-5 研究之目的 6
第二章 原理與文獻回顧 8
2-1 奈米複合材料文獻回顧 7
2-2 聚氧氮苯并環己烷文獻回顧 9
2-2-1聚氧氮苯并環己烷之合成與文獻回顧 9
2-2-2 Benzoxazine之改質與文獻回顧 18
2-3 POSS簡介與文獻回顧 28
2-3-1 POSS之T8 結構介紹 28
2-3-2 POSS與高分子共聚模式 29
2-3-3 POSS與其他奈米填充材料之比較 30
2-3-4 POSS 在高分子奈米複合材料的發展 32
第三章 實驗部份 33
3-1 實驗流程圖 33
3-2 材料與藥品 34
3-3 實驗裝置圖 35
3-4 儀器設備 36
3-5 實驗步驟 37
3-5-1 6,6-bis(3-phenyl-3,4dihydro-2H-1,3-benzoxazinyl) methylene (Bz-F)之合成.....37
3-5-2 Bz-F, Bz-A與Bz-ap硬化反應 39
3-5-3 Bz-F, Bz-A與Bz-ap與POSS形成奈米複合材料之配製 40
3-5-4硬化反應動力學之探討 40
3-5-5奈米複合材料之試片製作 40
3-6 結構鑑定與物性測試 41
第四章 不同側鏈Benzoxazine之合成與鑑定及其物性研究 42
4-1 Bz-F, Bz-A與Bz-ap之合成鑑定 42
4-2 不同側基Benzoxazine硬化動力學參數探討 43
4-3 硬化技術之探討 48
4-4 熱穩定性分析 49
4-5 動態機械分析 50
第五章 不同側鏈Benzoxazine奈米複合材料物性之研究 69
5-1 Benzoxazine奈米複材硬化動力學參數探討 69
5-2 Benzoxazine奈米複材熱穩定性分析 71
5-3 Benzoxazine奈米複材動態機械分析 71
5-4 Benzoxazine奈米複材的相形態之探討 72
第六章 總結 91
參考文獻 93

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