可溶性聚苯乙烯系阴离子交换聚合物的制备及其均相成膜性能研究
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摘要
本文首先采用间接氯甲基化方法,在均相反应体系中实现了线型聚(苯乙烯-乙烯)嵌段共聚物(PSE)的氯甲基化,探索了PSE在氯甲基化过程中交联程度的测定方法。通过对聚苯乙烯系阴离子交换微球溶胀度的研究,筛选出适于制备可溶性聚苯乙烯系阴离子交换聚合物的胺化试剂与溶剂。考察了可溶性聚苯乙烯系阴离子交换聚合物合成过程中的各种影响因素,制备出4种完全可溶的聚苯乙烯系阴离子交换聚合物,即三甲胺型可溶性聚苯乙烯系阴离子交换聚合物(TMA-AEP)、三乙胺型可溶性聚苯乙烯系阴离子交换聚合物(TEA-AEP)、二甲基乙醇胺型可溶性聚苯乙烯系阴离子交换聚合物(DMEA-AEP)、二甲基异丙醇胺型可溶性聚苯乙烯系阴离子交换聚合物(DMIPA-AEP)。采用傅里叶红外光谱(FT-IR)、氢核磁共振(1H-NMR)、热失重(TGA)和差热扫描(DSC)等手段对合成材料进行组成、结构和耐热性能等表征,研究了不同种类的可溶性聚苯乙烯系阴离子交换聚合物在各种溶剂中的溶解性、在甲醇中的溶解度以及黏度数据,并对其成膜后的吸水率与溶胀度进行了初步探讨。
研究结果表明：通过溶剂抽提称重与氢核磁谱图计算相结合的方法,可准确测定不同氯甲基化线型聚苯乙烯系聚合物的交联程度；交联反应会使氯甲基化产物的玻璃化温度升高,但会导致氯甲基化产物的取代度降低,并使氯甲基基团更容易发生热分解；强碱性聚苯乙烯系阴离子交换微球在甲醇中的溶胀度最大,在乙醇中的溶胀度次之,而以三甲胺型聚苯乙烯系阴离子交换微球在甲醇中的溶胀度最大,可达11.18 mL/g；经过胺化反应4种可溶性阴离子交换聚合物的热稳定性降低,热稳定性依次为：DMEA-AEP> DMIPA-AEP> TMA-AEP> TEA-AEP;4种可溶性阴离子交换聚合物材料在甲醇中均可以完全溶解,TMA-AEP在甲醇中的溶解度先增大后减少,其中离子交换容量为2.53mmol/g时溶解度最大；4种可溶性阴离子交换聚合物材料,取代度越大,吸水率越大,TEA-AEP的吸水性最强,其吸水率最高达到10.0,且吸水溶胀后可达到原膜片面积的4.3倍。
An indirect chloromethylation of linear polystyrene-b-polyethylene(PSE) was carried out first in a homogeneous system in this work, and then the cross-linking degree of chloromethylated PSE was measured. After evaluating the swelling degree of cross-linked anion-exchange polymer, suitable amination reagents and solvents were selected for preparing soluble anion-exchange polymer based on polystyrene. Various factors influencing the preparation of soluble anion-exchange polymer were investigated. Four kinds of soluble anion-exchange polymer were prepared, including trimethylamine anion-exchange polymer(TMA-AEP), triethylamine anion-exchange polymer(TEA-AEP), dimethylethanolamine anion-exchange polymer(DMEA-AEP), dimethylisopropanol anion-exchange polymer(DMIPA-AEP). Fourier transform infrared spectroscopy(FT-IR), hydrogen nuclear magnetic resonance('H-NMR), thermogravimetry analysis(TGA), differential scanning calorimetry (DSC) and other analysis were used to characterize the composition, structure and thermal stability of the products. The solubility of different kinds of soluble anion-exchange polymer in various solvents as well as the viscosity in methanol were measured. Their water adsorption rates and swelling ratios after flim forming were determined.
The results showed that cross-linking degree of different chloromethylated PSE could be measured by solvent extraction combined with 1H-NMR spectroscopy. The cross-linking reaction led to the increase of the glass transition temperature of chloromethylated product, but the thermal decomposition of the chloromethyl groups occured more easily, resulting decrease of substitution degree. The cross-linked anion-exchange polymer swelled best in methanol, ethanol came second, among which, trimethylamine cross-linked anion-exchange polymer has the largest swelling degree,11.18 mL/g. Four prepared soluble anion-exchange polymer materials were totally soluble in methanol, but their thermal stability decreased after amination reaction, as in the following order:DMEA-AEP> DMIPA-AEP> TMA-AEP> TEA-AEP. The TMA-AEP had the largest solubility in methanol when ion-exchange capacity was 2.53 mmol/g. The higher substitution degree, the larger water adsorption ratio for the investigated soluble anion-exchange polymer materials. TEA-AEP had the largest water adsorption ratio as 10.0, and the film area could be 4.3 times larger after water adsorption.
研究结果表明：通过溶剂抽提称重与氢核磁谱图计算相结合的方法,可准确测定不同氯甲基化线型聚苯乙烯系聚合物的交联程度；交联反应会使氯甲基化产物的玻璃化温度升高,但会导致氯甲基化产物的取代度降低,并使氯甲基基团更容易发生热分解；强碱性聚苯乙烯系阴离子交换微球在甲醇中的溶胀度最大,在乙醇中的溶胀度次之,而以三甲胺型聚苯乙烯系阴离子交换微球在甲醇中的溶胀度最大,可达11.18 mL/g；经过胺化反应4种可溶性阴离子交换聚合物的热稳定性降低,热稳定性依次为：DMEA-AEP> DMIPA-AEP> TMA-AEP> TEA-AEP;4种可溶性阴离子交换聚合物材料在甲醇中均可以完全溶解,TMA-AEP在甲醇中的溶解度先增大后减少,其中离子交换容量为2.53mmol/g时溶解度最大；4种可溶性阴离子交换聚合物材料,取代度越大,吸水率越大,TEA-AEP的吸水性最强,其吸水率最高达到10.0,且吸水溶胀后可达到原膜片面积的4.3倍。
An indirect chloromethylation of linear polystyrene-b-polyethylene(PSE) was carried out first in a homogeneous system in this work, and then the cross-linking degree of chloromethylated PSE was measured. After evaluating the swelling degree of cross-linked anion-exchange polymer, suitable amination reagents and solvents were selected for preparing soluble anion-exchange polymer based on polystyrene. Various factors influencing the preparation of soluble anion-exchange polymer were investigated. Four kinds of soluble anion-exchange polymer were prepared, including trimethylamine anion-exchange polymer(TMA-AEP), triethylamine anion-exchange polymer(TEA-AEP), dimethylethanolamine anion-exchange polymer(DMEA-AEP), dimethylisopropanol anion-exchange polymer(DMIPA-AEP). Fourier transform infrared spectroscopy(FT-IR), hydrogen nuclear magnetic resonance('H-NMR), thermogravimetry analysis(TGA), differential scanning calorimetry (DSC) and other analysis were used to characterize the composition, structure and thermal stability of the products. The solubility of different kinds of soluble anion-exchange polymer in various solvents as well as the viscosity in methanol were measured. Their water adsorption rates and swelling ratios after flim forming were determined.
The results showed that cross-linking degree of different chloromethylated PSE could be measured by solvent extraction combined with 1H-NMR spectroscopy. The cross-linking reaction led to the increase of the glass transition temperature of chloromethylated product, but the thermal decomposition of the chloromethyl groups occured more easily, resulting decrease of substitution degree. The cross-linked anion-exchange polymer swelled best in methanol, ethanol came second, among which, trimethylamine cross-linked anion-exchange polymer has the largest swelling degree,11.18 mL/g. Four prepared soluble anion-exchange polymer materials were totally soluble in methanol, but their thermal stability decreased after amination reaction, as in the following order:DMEA-AEP> DMIPA-AEP> TMA-AEP> TEA-AEP. The TMA-AEP had the largest solubility in methanol when ion-exchange capacity was 2.53 mmol/g. The higher substitution degree, the larger water adsorption ratio for the investigated soluble anion-exchange polymer materials. TEA-AEP had the largest water adsorption ratio as 10.0, and the film area could be 4.3 times larger after water adsorption.
引文
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