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Quantitative analysis of hydrogen bonding in poly(4-vinylphenol) blends using near infrared spectroscopy

机译:聚(4-乙烯基苯酚)共混物中氢键的近红外光谱定量分析

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Quantitative evaluation of hydrogen bonding of poly(4-vinyl phenol)/poly(ethylene oxide) PVPh/PEO blends was conducted using Fourier transform near infrared (FT-NIR) spectroscopy. Absorption coefficients of the free (a{sub}F), intra- (PVPh-PVPh) (a{sub}A) and inter-associated (PVPh-PEO) hydroxyl groups (a1) were estimated. Two sets of approximations were tested, including adopting a least-squares refinement method to calculate absorption coefficients from all NIR spectra or using a literature value for a{sub}F. Each set of absorption coefficients thus estimated were used to determine hydroxyl concentration for the free and hydrogen-bonded hydroxyl overtone bands in the blends. A comparison is made among the resultant concentrations of the free, intra- and inter-associated hydroxyl groups. The concentration of free hydroxyl groups markedly decreases with PEO percentage, and that of intra-associated hydroxyl remains almost constant. Concentration for the inter-associated hydroxyl groups in the blends increases very slowly above 0.2 PEO weight fraction. When concentration of OH groups is reported per PVPh chain, FT-NIR measurements show a broad maximum in the number of interchain hydrogen bonds. This result can be used to explain partially previous orientation behaviour observed for PVPh/PEO blends.
机译:使用傅立叶变换近红外(FT-NIR)光谱对聚(4-乙烯基苯酚)/聚(环氧乙烷)PVPh / PEO共混物的氢键进行定量评估。估计了游离(a {sub} F),内部(PVPh-PVPh)(a {sub} A)和相互关联的(PVPh-PEO)羟基(a1)的吸收系数。测试了两组近似值,包括采用最小二乘法改进方法从所有NIR光谱计算吸收系数,或使用文献值的{sub} F。如此估算的每组吸收系数用于确定共混物中的游离键和氢键键合的羟基泛音带的羟基浓度。在所得的游离,内和内缔合羟基的浓度之间进行比较。游离羟基的浓度随PEO百分比显着降低,而内部缔合羟基的浓度几乎保持恒定。在0.2 PEO重量分数以上时,共混物中相互缔合的羟基的浓度非常缓慢地增加。当报告每个PVPh链的OH基团浓度时,FT-NIR测量显示链间氢键数的最大值最大。该结果可用于部分解释先前对PVPh / PEO共混物的取向行为。

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