侧基为磺酸根基团的聚丁二酸丁二醇酯共聚物的合成及应用研究

Preparation and Applications of Poly( butylene succinate)Copolymers Bearing Sulfonate Pendent Groups

以丁二酸,富马酸和1,4-丁二醇为原料,通过溶液聚合的方法合成了一系列主链含有碳碳双键的不饱和脂肪族聚酯,聚(丁二酸丁二醇酯-共-富马酸丁二醇酯)P(BS-co-BF)s.以过量的Na HSO3为磺化试剂,合成了侧基为磺酸根基团的聚丁二酸丁二醇酯PBS共聚物P(BS-co-SBS)s.运用核磁共振氢谱(1HNMR),红外光谱(IR)和凝胶渗透色谱(GPC)表征了共聚物的化学结构及分子量.结合溶剂挥发和透析法研究了系列共聚物P(BS-co-SBS)s在水中的自组装行为.动态光散射(DLS)和透射电镜(TEM)的研究发现,系列共聚物P(BS-co-SBS)s均可自组装形成稳定的、具有核壳结构,表面带有负电荷的胶束(尺寸:103~165nm,PDI:0.187~0.264,zeta电位-35^-51 m V).载药和释药的结果显示,胶束对疏水药物阿霉素具有一定的缓释效果.

A novel amphiphilic poly（ butylene succinate） PBS copolymer bearing sulfonate pendent groups was synthesized via a two-step synthetic strategy. First,unsaturated copolyester poly（ butylene succinate-cobutylene fumarate）,P（ BS-co-BF） was prepared via the solution polymerization of the succinic acid,fumaric acid and 1,4-butanediol in the presence of titanium tetraisopropoxide as the catalyst. Second,sulfonation of P（ BS-co-BF） was carried out by the reaction with slight excess of Na HSO3 in 2-methoxyethanol / water mixture（ 120 ℃ for 12 ~ 26 h）,resulting in 100% sulfonation,and PBS copolymers bearing sulfonate groups,P（ BSco-SBS） s,were obtained. To establish structure-function relationships,three copolymers,P（ BS-co-SBS） s with different SBS molar contents were synthesized,and the SBS molar content in the P（ BS-co-SBF） s was 18%,27% and 40%,respectively. The chemical structures of copolymers were characterized by1H-NMR,FTIR and gel permeation chromatography（ GPC）. Moreover,self-assemblies behavior of these amphiphilic copolymers P（ BS-co-SBS） s in water was investigated by means of UV spectrometer,and the sizes and morphologies of them were examined by dynamic light scattering（ DLS） and transmission electron microscopy（ TEM）,respectively. The results showed that the copolymers P（ BS-co-SBS） s can self-assembly into stable,core-shell spherical,small-sized（ 103 ~ 165 nm,PDI： 0. 187 ~ 0. 264） nanomicelles with negative surface charges（- 35^- 51 m V）. In vitro drug release showed that copolymers P（ BS-co-SBS） s have certain p H-responsive function.