臺灣博碩士論文加值系統

隨著時代的進步，傳統的電視或螢幕已漸漸地被輕薄、省電且無輻射的液晶螢幕所取代，然而液晶螢幕的重要組成配件中的導光板及面板皆為易燃的壓克力樹脂。因此，如何改善壓克力樹脂難燃性已被各界所重視。近年來DOPO衍生物難燃劑皆應用於印刷電路板及半導體構裝材料上，目前尚無報導將DOPO衍生物應用於壓克力樹脂的難燃劑上，因此本研究主要目的為發展新穎反應型的乙烯系DOPO衍生物之難燃劑，期望改善壓克力樹脂的難燃性。首先將9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)分別與Glycidyl methacrylate (GMA)、Allyl bromide合成出兩種反應型乙烯系含磷難燃劑。合成的含磷難燃劑DOPO-GMA及Allyl-DOPO，分別利用FTIR、MS、EA、DSC、1H-NMR及31P-NMR加以鑑定其結構。
將此合成的含磷乙烯系難燃劑分別配製不同比例的含磷量與methyl methacrylate (MMA)進行共聚合反應，得到不同含磷量的壓克力樹脂。另外再加入不同比例的交鏈劑triallyl isocyanurate (TAIC)，以比較氮-磷共乘效應對物性之影響。利用DSC探討各單體混合物的熱硬化行為；利用TGA及DMA探討共聚物之熱性質；利用UV-vis.測試共聚物之透明度；利用LOI探討共聚物之難燃性。實驗結果顯示，DOPO-GMA與Allyl-DOPO作為難燃劑，由於燃燒時所形成聚磷酸凝縮相的保護層，可提高壓克力樹脂之熱穩定性及難燃性。添加交鏈劑TAIC，由於氮-磷共乘效應明顯地提升含磷難燃壓克力樹脂的熱穩定性及難燃性，LOI值由23提升到29。雖然含磷難燃壓克力樹脂的Tg會隨含磷量的增加而有顯著地降低，但TAIC的添加，除了因氮磷共乘效應提升難燃性外，也可減緩Tg的降低。在透光度測試結果顯示，本研究的含磷難燃壓克力樹脂仍可保持良好的透光度。

Along with the times progress, the television or the traditional screen gradually have been replaced by the liquid crystal screen with the advantages of light, thin, province electricity and non-radiation. However the important light-guide plate and plane in the liquid crystal screen almost are the flammable PMMA resin. Hence, how to improve the flame retardancy of the PMMA resin has already been investigated. In recent years the series of DOPO derivative almost applied to the printed circuit board and the encapsulation material for the semiconductor devices, not yet applied to PMMA resin at present Therefore the goal of this research is focused on the preparation of the novel DOPO derivative flame-retardants with reactive vinyl group to improve the flame retardancy of the PMMA resin.
Two kinds of phosphorus-containing flame retardant DOPO derivatives: DOPO-GMA and Allyl-DOPO were synthesized from the 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO) with Glycidyl methacrylate (GMA) and allylbromide, respectively. The structure of the synthesized flame retardant was confirmed by Mass, NMR, EA and FTIR spectra. The resulting flame retardant of DOPO-GMA and Allyl-DOPO were copolymerized with methyl methacrylate (MMA) and triallyl isocyanurate (TAIC), respectively. The thermal behavior of the mixtures was evaluated by differential scanning calorimetry (DSC). The thermal stability and thermal mechanical property of the copolymers were investigated by thermal gravimetric analysis (TGA) and dynamic (thermal) mechanical analysis (DTMA), respectively. The results show that the flame retardancy of DOPO-modified PMMA increased with phosphorus content, while the glass transition temperature (Tg) was depressed and the CTE was increased. The generation of nitrogen-phosphorus synergism to excellently increase flame retardancy with the TAIC added, besides decreasing the reducing of Tg. With the transmittance testing, the good transparency was kept in the phosphorus-containing PMMA resins with flame retardancy.

中文摘要 ------------------------------------------------------- i
英文摘要 ------------------------------------------------------- ii
誌謝 ------------------------------------------------------- iv
目錄 ------------------------------------------------------- v
Scheme ------------------------------------------------------- viii
表目錄 ------------------------------------------------------- ix
圖目錄 ------------------------------------------------------- xi
第一章、 緒論---------------------------------------------------- 1
1-1 前言---------------------------------------------------- 1
1-2 甲基丙烯酸甲酯(MMA)概述及應用----------------------------- 2
1-3 導光板簡介----------------------------------------------- 2
1-4 本研究之目的--------------------------------------------- 4
第二章、 高分子燃燒、耐燃相關理論與文獻回顧-------------------------- 5
2-1 燃燒基本理論--------------------------------------------- 5
2-1-1 燃燒三角理論--------------------------------------------- 5
2-1-2 高分子巨觀燃燒機構---------------------------------------- 5
2-1-3 高分子微觀燃燒機構---------------------------------------- 8
2-1-4 高分子材料燃燒特性---------------------------------------- 9
2-2 高分子難燃化原理----------------------------------------- 11
2-2-1 影響高分子燃燒的因素-------------------------------------- 11
2-2-2 難燃方法------------------------------------------------ 12
2-3 難燃劑與難燃機構的種類-------------------------------------14
2-3-1 無機金屬系難燃劑----------------------------------------- 15
2-3-2 鹵素系難燃劑--------------------------------------------- 16
2-3-3 磷系難燃劑及難燃原理------------------------------------ 19
2-4 協同作用------------------------------------------------ 23
2-5 難燃劑的選擇--------------------------------------------- 24
2-6 難燃材料之測試方法---------------------------------------- 25
2-7 含磷難燃劑之文獻回顧-------------------------------------- 26
2-7-1 含磷難燃劑DOPO衍生物之應用---------------------------------26
2-7-2 含磷難燃劑在壓克力上之應用------------------------------------34

第三章、 實驗部份---------------------------------------------------38
3-1 實驗流程圖----------------------------------------------- 38
3-2 材料與藥品---------------------------------------------------39
3-3 實驗裝置圖---------------------------------------------------40
3-4 儀器設備----------------------------------------------------41
3-5 實驗步驟----------------------------------------------------42
3-5-1 DOPO-GMA之合成----------------------------------------------42
3-5-2 Allyl-DOPO之合成--------------------------------------------43
3-6 試片製備----------------------------------------------------44
3-6-1 DOPO-GMA系列之試片製備-------------------------------------44
3-6-2 Allyl-DOPO系列之試片製備------------------------------------46
3-7 物性測試----------------------------------------------------50
第四章、 以DOPO-GMA改質壓克力--------------------------------------54
4-1 DOPO-GMA之合成鑑定-------------------------------------------54
4-2 示差掃描熱分析-----------------------------------------------55
4-3 動態黏彈性質分析---------------------------------------------56
4-4 膨脹係數分析-------------------------------------------------57
4-5 熱穩定性分析-------------------------------------------------57
4-5-1 氮氣環境下的熱穩定性分析--------------------------------------58
4-5-2 空氣環境下的熱穩定性分析--------------------------------------58
4-6 LOI測試-----------------------------------------------------59
4-7 透明度測試---------------------------------------------------59
4-8 結論--------------------------------------------------------60
第五章、 以Allyl-DOPO改質壓克力---------------------------------------86
5-1 Allyl-DOPO之合成鑑定-----------------------------------------86
5-2 示差掃描熱分析-----------------------------------------------87
5-3 動態黏彈性質分析---------------------------------------------87
5-4 膨脹係數分析-------------------------------------------------88
5-5 熱穩定性分析-------------------------------------------------88
5-5-1 氮氣環境下的熱穩定性分析--------------------------------------88
5-5-2 空氣環境下的熱穩定性分析--------------------------------------88
5-6 LOI測試-----------------------------------------------------89
5-7 透明度測試---------------------------------------------------89
5-8 結論--------------------------------------------------------90
第六章、 總結-------------------------------------------------------115
6-1 示差掃描熱分析----------------------------------------------115
6-2 動態黏彈性質分析--------------------------------------------115
6-3 膨脹係數分析------------------------------------------------116
6-4 熱穩定性分析------------------------------------------------116
6-5 LOI測試----------------------------------------------------116
6-6 透明度測試-------------------------------------------------117
6-7 結論-------------------------------------------------------117
參考文獻 ----------------------------------------------------------124

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