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  • 學位論文

磺酸化尼龍6之結晶動力學研究

A Study of Crystallization Kinetics in Sulfonate Nylon 6

指導教授 : 芮祥鵬
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摘要


本實驗改變尼龍6分子鏈的結構合成不同比例之磺酸化尼龍6,合成出不同比例的苯磺酸鈉(0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%)之聚合物,並與尼龍6(Nylon 6)比較在不同等溫結晶溫度結晶與不同速率完成樣品之結晶熱力學、動力學性質。 首先利用微差掃描熱卡計(DSC)將含有不同比例(0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%)苯磺酸鈉之磺酸化尼龍6於不同等溫結晶溫度(Tc)結晶,根據Hoffman-Weeks方程式得到樣品之平衡熔點(Tm0),發現到分子鏈上含不同比例苯磺酸鈉之磺酸化尼龍6,其平衡熔點(Tm0)皆略不相同。而利用樣品於各等溫結晶溫度(Tc)下結晶之熔融曲線,可計算出樣品於該結晶溫度的結晶度,發現到樣品於中過冷度時,因遠離樣品的玻璃轉換溫度(Tg)與熔點(Tm),故結晶度會到一極大值,再利用樣品的結晶放熱曲線計算出樣品完成比例與結晶時間的關係,將此曲線利用Avrami方程式加以分析,可得到樣品之結晶速率(k)及Avrami指數(n),而由結晶速率(k)可得知含有不同比例(0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%)苯磺酸鈉之磺酸化尼龍6會隨著等溫結晶溫度(Tc)的上升,其結晶速率(k)的值會下降,由此可證明結晶的成核成長機制,且可得知隨著含不同比例(0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%)苯磺酸鈉之磺酸化尼龍6,其結晶速率(k)的值也會隨之下降,且由合成不同比例苯磺酸鈉之磺酸化尼龍6,比較在相同結晶溫度(130℃~180℃)下之結晶速率(k),發現到,結晶速率(k)增加趨於平緩,且其隨著不同比例(0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%)苯磺酸鈉增加之磺酸化尼龍6亦然。接著利用Lauritizen-Hoffman方程式可得到樣品之RegimeIII轉換成RegimeII臨界溫度,發現到隨著分子鏈中苯磺酸比例的增加,其磺酸化尼龍6臨界溫度比尼龍6約略下降,並在廣角度X光散射實驗中,可得知磺酸化尼龍6中含有二種結晶晶格型態。

並列摘要


In this study, the kinetic analysis on melt crystallization of Nylon 6 copolymer containing sulfonate was conducted through measuring their spherulite growth rates. A multiple melting behavior of Nylon 6 copolymer containing sulfonate was found through differential scanning calorimetry (DSC) and corresponding crystalline microstructure of were studied by wide-angle X-ray diffraction(WAXD). With Avrami analysis, the crystallization rate constant for Nylon 6 copolymer containing sulfonate were evaluated. The equilibrium melting point was obtained using the Hoffman-Weeks method. It was found that the equilibrium melting point of Nylon 6 copolymer containing sulfonate was the same with that of Nylon 6 respectively. The crystallization rate (k) increased when the temperature increased. The synthesis of sulfonic acid sodium of different proportions (0.8 wt%、1.4 wt%、3.0 wt%、5.1 wt%) showed a significant enhancement to the increase of crystallization rate and the downward shift of the optimum crystallization temperature. Finally, the transition temperature between Regime III and Regime II, obtained using the Lauritizen-Hoffman method, was found to be lower for Nylon 6 copolymer containing sulfonate than those of Nylon 6 systems. With WAXD, the model specimens was found to contain α form and γ form.

參考文獻


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