Development of Synthesis and Preparation Methods of the Membranes Capable of Recognizing Chiral Structure for the Separation of Optical Isomers

为了开发一种制备超滤膜的技术，以有效分离光学异构体，如能够识别手性立体结构的高功能化聚合物和酶，对膜进行了光学分辨率研究，并获得了以下发现。氨基酸固定膜：将戊二醛与l -苯甘氨酸反应生成的凝聚物通过相转化法引入聚砜基质中制备氨基酸固定膜。结果表明，不同条件下制备的膜类型对分离因子的影响较大。在溶剂蒸发时间= 65分钟的条件下，温度为60℃。C，对苯甘氨酸外消旋体的分离系数为9.1。同时发现l -苯基甘氨酸固定膜可用于具有氨基酸基团的芳香族化合物的光学分辨。等离子体聚合l-薄荷醇膜：通过等离子体聚合将l-薄荷醇固定在不同孔径的醋酸纤维素多孔支撑膜上。对孔径分别为0.2、0.45和0.8 μ m的醋酸纤维素膜，在等离子体照射60、75和150 min时，l-薄荷醇的固定率不变，在此时间内制备的膜的纯水渗透率与孔半径的平方成正比。然而，我们看到，超过这些等离子体照射时间，l-薄荷醇在各膜上的固定率下降。在外消旋色氨酸、苯丙氨酸和酪氨酸的光学分辨中，外消旋色氨酸的分离因子最大。发现立体构型对分离因子有一定的影响。萜烯固定膜：采用等离子体聚合法将l-薄荷醇、s -香茅醇、r -柠檬烯、s -冰片等旋光性萜烯固定在孔径为0.2 μ m的醋酸纤维素膜上。在不同的等离子体聚合条件下制备了不同的膜。结果表明，随着等离子体辐照时间的延长，固定在膜上的萜烯量增加，分离系数大导致渗透通量降低。结果表明，无论所用的膜类型如何，氨基酸的光学分离都是可行的，其中s -香茅醇固定膜的分离因子最大。少

For the purpose of developing a technology in the preparation of ultrafiltration membranes for the effective separation of optical isomers such as the highly functionalized polymers and enzymes that are capable of recognizing chiral stereostructures, studies on membranes for optical resolution were performed and the following findings were obtained.1. Amino acid fixed membrane : Amino acid fixed membranes were prepared by introducing the condensate derived from the reaction of glutaraldehyde and L-phenylglycine into the polysulfone matrix by phase inversion method. It was found that the separation factor changed significantly with the types of membrane prepared under different conditions. Under the conditions of solvent evaporation period = 65 minutes at 60。C, a separation factor of 9.1 was obtained for the phenylglycine racemate. It was also found that the L-phenylglycine fixed membrane could be applied to the optical resolution of aromatic compounds with amino acid moiety.2. Plasma p … More olymerized l-menthol membrane : l-Menthol was fixed on the porous support membranes of cellulose acetate with different pore diameters by plasma polymerization. Constant fixation rates of l-menthol were obtained up to 60, 75 and 150 min of plasma irradiation time for cellulose acetate membranes with pore diameter = 0.2, 0.45 and 0.8 mum, respectively, and the pure water permeability of each membrane prepared over those times was proportionally related to the square of pore radii. However, it was seen that beyond these indicated times of plasma irradiation, the fixation rate of l-menthol on each membrane decreased. The separation factor of racemic tryptophan was the largest in the optical resolution of racemic tryptophan, phenylalanine and tyrosine. It was found that the steric configuration contributed to the separation factor.3. Terpene-fixed membranes : The fixation of optically active terpenes such as l-menthol, S-citronellol, R-limonene and S-borneol on the cellulose acetate membrane with pore diameter = 0.2 mum was performed by plasma polymerization. Different membranes were prepared under various conditions of plasma polymerization. It was revealed that the amount of terpene fixed on the membrane increased with increasing time of plasma irradiation, and the large separation factor resulted in a decrease in permeation flux. Further, it was shown that the optical resolution of amino acid was feasible irrespective of the types of membrane used, and the separation factor of S-citronellol fixed membrane was the largest among the prepared membranes. Less