优化双端氨基聚乙二醇的合成条件及其表征  

Optimization and Characterization of Synthesis Conditions of Amino-terminated Polyethylene Glycol

作　　者：赵鹏慧 庞策 张金虎 王婷 张晨阳 王永利[1] ZHAO Peng-hui;PANG Ce;ZHANG Jin-hu;WANG Ting;ZHANG Chen-yang;WANG Yong-li(Institute of Appiled Chemistry,Hebei North University,Zhangjiakou,Hebei 075000,China;ZHangjiakou City No.1 Middle School,Zhangjiakou,Hebei 075000,China)

机构地区：[1]河北北方学院应用化学研究所,河北张家口075000 [2]张家口市第一中学,河北张家口075000

出　　处：《河北北方学院学报（自然科学版）》2020年第9期1-7,19,共8页Journal of Hebei North University:Natural Science Edition

基　　金：河北省教育厅研究生创新资助项目(CXZZSS2019148);张家口市科学技术研究与发展计划项目(1811019A);河北北方学院一般项目(YB2018019)。

摘　　要：目的通过优化合成条件,提高双端氨基聚乙二醇(PEG-(NH 2)2)的产率。方法以聚乙二醇2000和对甲苯磺酰氯为原料,通过酯化反应生成聚乙二醇对甲苯磺酸酯(PEG-OTs),通过水热法与过量浓氨水反应,合成PEG-(NH 2)2。利用傅里叶变换红外光谱仪、超导核磁共振仪、紫外分光光度计和X-射线光电子能谱仪,对中间产物PEG-OTs和最终产物PEG-(NH 2)2进行表征,并对制备条件进行单因素考察和正交优化试验。结果与PEG和PEG-OTs比较,PEG-(NH 2)2的红外光谱中出现了氨基的3个特征吸收峰,分别为1953、1640和1060 cm-1;在核磁共振氢谱中存在-O-CH 2-CH 2-NH 2中与氨基相连的亚甲基质子和与氧相连的亚甲基质子的化学位移,分别是δ2.87 s和δ3.52 t,以及氨基上H的化学位移δ2.44 s;在紫外光谱中,存在由末端氨基产生的吸收峰292 nm;同时,XPS图显示有C-N键生成。正交优化后,最佳合成条件为n(PEG)∶n(TsCl)=1∶3,酯化温度为20℃,PEG-OTs与浓氨水反应时温度为140℃,PEG-OTs与浓氨水反应时间为4 h。最优条件下,3次平行试验的平均产率为78.49%。结论制备的双端氨基聚乙二醇产率高,且合成条件简单易行。Objective To improve the yield of amino-terminated polyethylene glycol(PEG-(NH2)2)by optimizing the preparation method.Methods PEG 2000 and p-toluenesulfonyl chloride were taken as the raw materials to synthesize PEG-p-toluenesulfonate(PEG-OTs)by esterification.PEG-(NH2)2 was synthesized by hydrothermal method with PEG-OTs and excessive NH4OH.Intermediate product PEG-OTs and the final product PEG-(NH2)2 were characterized by Fourier transform infrared spectrometer,superconducting nuclear magnetic resonance,ultraviolet spectrophotometer and X-ray photoelectron spectrometer.Then the preparation conditions were investigated by single factor and optimized by orthogonal test.Results Compared with PEG and PEG-OTs,three characteristic absorption peaks of amino group in PEG-(NH2)2 infrared spectrum,1953 cm-1,1640 cm-1 and 1060 cm-1,were found in this process.There were two chemical shifts of methylene proton connected with amino group and oxygen in-O-CH2-CH2-NH2 bond,which wereδ2.87 s andδ3.52 t,andδ2.44 s of chemical shifts was H on amino group in the NMR hydrogen spectrum.In the UV spectrum,an absorption peak of 292 nm was produced by terminal amino group.At the same time,the XPS showed the formation of C-N bonds.After orthogonal optimization,the optimum conditions were n(PEG)∶n(TsCl)=1∶3,esterification temperature at 20℃,reaction temperature of PEG-OTs with concentrated ammonia at 140℃,and reaction time of PEG-OTs with concentrated ammonia for 4 h.The average yield of three parallel experiments was 78.49%under the optimal conditions.Conclusion The polymer of PEG-(NH2)2 prepared in this study has high yield and simple synthesis conditions.

关 键 词：聚乙二醇2000 对甲苯磺酰氯 双端氨基聚乙二醇 

分 类 号：TQ316.3[化学工程—高聚物工业]