臺灣博碩士論文加值系統

本研究以不同比例的進料Bis-phenol A Diglycidyl Methacrylate（BisGMA）(50~80 mol%)及Triethylene Glycol Dimethacrylate (TEGDMA) (20~50 mol%)，使用Camphorquinone (CQ) 與 Diphenylphosphine oxide為光起始劑，以不同照光時間(2~6 mins)與不同照光強度(600~1800 mW/cm2)，並以可見光固化聚合，討論BisGMA/TEGDMA進料比、照光時間及照光強度對雙鍵反應轉化率的影響，以及交聯密度與轉化率如何影響到膨潤交聯產物的水與高分子之交互作用，及影響乾交聯產物的動態機械性質。
藉由FTIR傅立葉紅外線光譜儀測高分子的轉化率得知，隨著BisGMA含量增加、照光時間增長或照光強度增強時，轉化率都會上升。而轉化率與照光強度有冪次關係，其指數為0.226~0.371之間。利用雙鍵轉化率與照光時間可計算出增長反應級數(n)與反應速率常數(k)，n值與k值皆隨著BisGMA進料量增加或照光強度增強而降低。壓縮模數隨BisGMA進料量增加而上升，交聯密度會增加，且網路中物理纏結的密度（Ns）和網路中化學交聯的密度（Nc）都會增加，表示BisGMA進料量增加有助於物理性及化學性的交聯。而增加照光時間或照光強度時，亦會得到上述類似之結果。此外，利用交聯密度與高分子吸水率可計算得出水和高分子間交互作用參數（χ），隨著BisGMA含量增加、照光時間增長或照光強度增強時，χ值會上升，平衡含水率越低。固化體積收縮率隨BisGMA進料量增加或照光強度增強而下降，因為BisGMA有苯環結構，會降低其固化體積收縮率。但隨照光時間增長時，固化體積收縮率則上升。由動態機械分析發現，隨著BisGMA進料量增加、照光時間增長或照光強度增強時，儲存模數與玻璃轉移溫度(Tg)皆會增加。玻璃轉移溫度(Tg)隨著交聯密度增加而上升，為線性關係。而儲存模數與交聯密度各取自然對數後，儲存模數正比於交聯密度的1.918次方。
實驗結果得知當改變BisGMA/TEGDMA進料比、照光時間或照光強度，均會影響高分子的網路結構、雙鍵轉化率與交聯密度，進而影響到膨潤交聯產物的水與高分子之交互作用，及影響乾交聯產物的動態機械性質。

　Adhesives were prepared by using various mole ratios of bis-phenol A diglycidyl methacrylate（BisGMA）(50~80 mol%) and triethylene glycol dimethacrylate (TEGDMA) (20~50 mol%) in feed, with camphorquinone (CQ) and diphenylphosphine oxide as the photoinitiators. We use the different photocuring times (2~6 mins) and different light intensities (600~1800 mW/cm2) of visible light. We examine the effects of BisGMA/TEGDMA mole ratios in feed, photocuring times and light intensities on conversion of reaction, and how crosslink density and conversion of reaction affect the interactions between water and polymers in swollen resins and dynamic mechanical properties of dry resins.
According to FTIR analysis, as the contents of BisGMA increase, the photocuring times increase or the light intensity increases, the conversions of double bonds increase. There is a power raw relationship between the conversion and light intensity with an exponent equal to 0.226~0.371. The order of propagation reaction (n) and reaction rate constant (k) are calculated by the conversions of double bonds versus photocuring times. As the contents of BisGMA increase or the light intensity increases, both of the n values and k values decrease. Compressive modulus and crosslinking density increase with increasing the contents of BisGMA in feed. Both of the density of physical entanglement（Ns）and the density of chemical crosslinking in network（Nc） increase with increasing the contents of BisGMA in feed, showing that adding BisGMA is favorable for physical and chemical crosslinking. And increasing the photocuring times or the light intensities, leads to similar results to the above. In addition, the interaction parameters of water and polymers in adhesives (χ) were calculated by crosslinking densities and equilibrium water contents. As the contents of BisGMA increase, the photocuring times increase or the light intensity increases, the χ values increase and the equilibrium water contents decrease. Curing volume shrinkages decrease with increasing the contents of BisGMA in feed or increasing the light intensity because of BisGMA with benzene structure offering the less shrinkage than TEGDMA. But increasing the photocuring times, the curing volume shrinkages increase. According to DMA analysis, as the contents of BisGMA increase, the photocuring times increase or the light intensity increases, the storage modulus and the glass transition temperature (Tg) will increase. The glass transition temperature is increased by increasing crosslink density, there is a linear relationship between them. And there is a power raw relationship between the storage modulus and crosslink density with an exponent equal to 1.918.

Experimental results show that we vary BisGMA/TEGDMA ratios in feed, photocuring times or light intensities, that will influence the conversions of double bonds, network structure of polymer and crosslink density, thereby affecting the interactions between water and polymers in swollen resins, as well as affecting dynamic mechanical properties of dry resins.

一、前言…………………………………………………………………..1
二、實驗方法…………………………………………………………….8
2.1 BisGMA/TEGDMA高分子的製備 8
2.2　測定反應後產物中殘留溶劑量達到平衡的時間 9
2.3　雙鍵反應轉化率測試 9
2.4　平衡膨潤測定 9
2.5　壓縮變形率測試 10
2.6　固化體積收縮率測試 10
2.7 動態機械性質分析 11
三、結果與討論 12
3.1　測定反應後產物中殘留溶劑量達到平衡的時間 12
3.2　傅立葉轉換紅外線光譜（FTIR）分析 12
3.2.1　BisGMA進料量與照光時間對雙鍵轉化率之影響 13
3.2.2　照光強度對雙鍵轉化率的影響 14
3.3　雙鍵轉化率與照光時間及光固化動力學模型 15
3.4　平衡含水率分析 16
3.4.1 BisGMA/TEGDMA比例與照光時間對平衡含水率之影響 16
3.4.2 照光強度對平衡含水率的影響 17
3.5　材料之壓縮測試 17
3.5.1　壓縮模數測定 17
3.5.2　含水率與交聯密度及Flory-Huggins交互作用參數 19
3.5.3　膨潤交聯網絡結構對黏彈性質之影響分析 21
3.6　固化體積收縮率分析 23
3.6.1　BisGMA/TEGDMA比例與照光時間對固化體積收縮率之影響 23
3.6.2　照光強度對固化體積收縮率之影響 24
3.7　材料之動態機械性質分析 24
3.7.1　BisGMA/TEGDMA比例對動態機械性質之影響 24
3.7.2　照光時間對動態機械性質之影響 25
3.7.3　照光強度對動態機械性質之影響 26
3.7.4 動態機械性質與交聯密度的關係…………………………26
四、結論 28
五、參考文獻 30
附錄 A 環化反應示意圖.....................................................................72
附錄 B 考慮反應機構之光固化動力學.............................................73
附錄 C 水和高分子間交互作用參數（χ）與交聯密度的關係……74

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