聚醚砜阴离子内毒素过滤膜的制备

发布时间：2018-04-25 22:26

本文选题：氯甲基化 + 季铵化　；参考：《东华大学》2017年硕士论文

【摘要】：小剂量的内毒素就能够引起广泛的生理病理反应,如机体发热、白细胞反应、糖代谢紊乱、血管舒缩机制紊乱等,严重者可导致死亡。内毒素广泛存在于各种环境中,因此,在医用领域中(如:医用过滤装置),亟待寻找一种高效去除内毒素、适合大批量工业生产的方法。本课题针对国内外内毒素的滤除情况做了大量的调查研究,寻找了一种高效去除内毒素的方法,将特异性去除内毒素方法—阴离子交换法和非特异性去除内毒素方法—过滤法进行结合,探究其内毒素去除效果。本课题选用制膜普遍采用的聚醚砜,先进行氯甲基化反应、再进行季铵化反应,希望得到聚醚砜阴离子内毒素过滤膜。本课题首先选择在聚醚砜的侧链上引入氯甲基基团(-CH_2Cl)作为反应跳板,寻找了反应活性高、反应时间短、反应效果好、环境友好的1、4-二氯甲氧基丁烷作为氯甲基化反应的试剂,路易斯酸-氯化锌作为反应催化剂。并设计三因子三水平正交试验来比较聚醚砜氯甲基化反应中反应时间、反应温度、氯甲基化试剂用量对聚醚砜氯甲基化程度的影响,通过核磁共振图谱来表征其氯甲基化程度,实验结果发现聚醚砜氯甲基化程度随着反应温度的升高而升高,最优的反应温度为90度;随着氯甲基化试剂用量的增多也随之变高,最优的氯甲基化试剂用量为14.4g;随着反应时间的增加,反应速度由快变慢,最佳的反应时间为6h。随后选取氯甲基化程度最高的聚醚砜作为反应物进行聚醚砜季铵化反应。聚醚砜的季铵化是以三级铵R3N和卤代烷R-X为反应物,生成季铵盐[R_4N~+][X-]的反应。选取反应活性高的三甲胺作为季铵化试剂,常温反应制备聚醚砜阴离子内毒素过滤膜。通过化学手段表征,红外光谱图显示聚醚砜阴离子内毒素过滤膜表面有季铵基团的特征峰;zeta电位显示聚醚砜阴离子内毒素过滤膜表面带有正电荷,与季铵基团为强碱性基团,在水中显示正电性理论相符。通过物理手段表征,接触角显示聚醚砜阴离子内毒素过滤膜接触角变小,亲水性变好,与季铵基团为亲水性基团理论相符;电镜结果显示,氯甲基化聚醚砜膜表面在进行季铵化反应之后变得坑洼;阻水透气性能显示,由于反应过程中基布纤维的溶胀,使得相比较氯甲基化的聚醚砜,季铵化聚醚砜透气性能稍变差,阻水性能稍变好。本课题进一步选用0.25EU/ml灵敏度的鲎试剂进行内毒素检验,根据鲎试剂与内毒素反应产生凝胶的原理,通过翻转试管观察凝胶的形态来判断结果,发现通过聚醚砜阴离子内毒素过滤膜滤除前的溶液为凝胶态,滤除后溶液为液态,进一步显示聚醚砜阴离子内毒素过滤膜能够成功滤除内毒素。综上所述,通过以1、4-二氯甲氧基丁烷为氯甲基化试剂在反应温度为90度,反应时间为6h,氯甲基化试剂为14.4g时成功制备氯甲基化聚醚砜程度最高;以三甲胺为季铵化试剂常温反应15天,能够成功制备聚醚砜阴离子内毒素过滤膜并能有效滤除内毒素。
[Abstract]:A small dose of endotoxin can cause a wide range of physiological and pathological reactions, such as body fever, leukocyte reaction, disorder of sugar metabolism, and disorder of vasoconstriction, and so on. Serious people can cause death. Endotoxin is widely found in various environments. Therefore, in medical field (such as medical filter device), it is urgent to find a kind of efficient endotoxin removal. In accordance with the method of mass production in large quantities, this subject has done a lot of investigations and studies on the filtration of endotoxin at home and abroad, and found a method of efficient removal of endotoxin. It combines the specific removal of endotoxin method and the nonspecific removal endotoxin method - filtration method to explore the effect of endotoxin removal. This topic selects the Polyethersulfone anionic endotoxin ultrafiltration membrane. The first choice is to introduce the chloromethyl group (-CH_2Cl) on the side chain of polyethersulfone as the reaction springboard, and find the reaction activity is high, the reaction time is short, and the reaction effect is found. Good, environmentally friendly 1,4- two chloromethyl butane as a reagent for chloromethylation, Lewis acid and zinc chloride as a reaction catalyst. And a three factor three level orthogonal test was designed to compare the reaction time, reaction temperature, and the effect of the amount of chloromethylation reagents on the degree of chloromethylation of polyethersulfone. The results show that the degree of chloromethylation of polyethersulfone increases with the increase of reaction temperature, and the optimum reaction temperature is 90 degrees. With the increase of the amount of chloromethylation reagents, the optimal dosage of chloromethylation reagents is 14.4g. With the increase of reaction time, the reaction speed is increased. The optimum reaction time is 6h. and then the Polyethersulfone is then selected as the reactant with the highest chloromethylated polyethersulfone as the reactant. The quaternatization of polyethersulfone is based on the reaction of three ammonium R3N and halogenated R-X to produce quaternary ammonium salt [R_4N~+][X-]. The Polyethersulfone anionic endotoxin membrane should be prepared. By chemical means, the infrared spectrum shows the characteristic peak of the quaternary ammonium group on the surface of the Polyethersulfone anionic endotoxin membrane, and the zeta potential shows that the surface of the Polyethersulfone anionic endotoxin membrane has positive charge, and the Ji Anji group is a strong basic group, and the positive electricity is displayed in the water. According to the physical means, the contact angle shows that the contact angle of the Polyethersulfone anionic endotoxin membrane is smaller, the hydrophilicity is better and the quaternary ammonium group is the hydrophilic group theory; the electron microscope results show that the surface of the chloromethyl polyethersulfone membrane becomes potholed after the quaternizing reaction; the water resistance and permeability performance shows, the reaction process is due to the reaction process. The swelling of the medium fabric fiber makes the Polyethersulfone with chloromethylation, and the permeability of quaternated polyethersulfone is slightly worse, and the water resistance performance is slightly better. This subject further selects the endotoxin test by the 0.25EU/ml sensitivity limulus reagent. According to the principle of condensing of the limulus reagent and the endotoxin reaction, the morphology of the gel is observed by the reversal test tube. To determine the results, it is found that the solution of the filtration membrane of the Polyethersulfone anionic endotoxin filter membrane is a gelation state and the filtrate is filtrated into liquid, which further shows that the Polyethersulfone anionic endotoxin filter membrane can successfully filter the endotoxin. In summary, the reaction temperature is 90 degrees by the reaction temperature of 1,4- two chloromethyl butane as the chloromethylated reagent. The successful preparation of chloromethylated polyethersulfone at the time of 6h and chloromethylation of 14.4g is the highest. With trimethylamine as a quaternated reagent at normal temperature for 15 days, the Polyethersulfone anionic endotoxin filter membrane can be successfully prepared and the endotoxin can be effectively filtered out.

【学位授予单位】：东华大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ051.893

【参考文献】