Synthesis and properties of multifunctional thiol crosslinked gels containing disulfide bond in the network structure
Synthesis and properties of multifunctional thiol crosslinked gels containing disulfide bond in the network structure
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DOI：
10.1002/pola.28760
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发表时间：
2017-11
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影响因子：
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通讯作者：
N. Naga;Kazumasa Moriyama;H. Furukawa
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文献类型：
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作者：
N. Naga;Kazumasa Moriyama;H. Furukawa
以二甲基亚砜（DMSO）为溶剂，通过氧化多官能团硫醇单体三（3-巯基丙酸）丙烷、三（3-巯基丙酰氧基乙基）异氰脲酸酯、季戊四醇四（3-巯基丙酸）酯和双（3-巯基丙酸）戊四醇六酯，合成了含二硫键的交联凝胶。在85 °C下与DMSO的氧化反应和在50 °C下在乙酸酐存在下的奥尔布赖特-戈德曼氧化反应都产生了相应的凝胶。DMSO氧化反应的转化率高于Albright-Goldman氧化反应。通过扫描显微光散射定量表征了凝胶的网络结构。反应产物在凝胶中形成了均匀的网状结构，网孔约为0.5nm。通过压缩试验研究了所得凝胶的力学性能。交联密度随单体浓度、单体巯基数或反应转化率的增加而增加，杨氏模量和凝胶断裂应力增大。三-、四-、六-硫醇单体和二硫醇单体的共辄产生柔软且柔性的凝胶。通过二硫苏糖醇还原凝胶中的二硫键，将凝胶转化为溶液。加热所得溶液通过二硫键的重整诱导再结晶。© 2017 Wiley Periodicals，Inc. J.波利姆科学，A部分：聚合物2017，55，3749-3756
Joint crosslinked gels containing disulfide linkage have been synthesized by oxidation reaction of multi-functional thiol monomers, trimethylolpropane tris(3-mercaptopropionate), tris-[3-mercaptopropionyloxy-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), and dipenta-erythritol hexakis (3-mercaptopropionate) in dimethyl sulfoxide (DMSO). Both the oxidation reactions with DMSO at 85 °C and Albright-Goldman oxidation in the presence of acetic anhydride at 50 °C yielded the corresponding gels. The oxidation reaction with DMSO showed higher reaction conversion than that with Albright-Goldman oxidation. Network structure of the gels was quantitatively characterized by means of a scanning microscopic light scattering. The reactions formed homogeneous network structure with about 0.5 nm of mesh in the gels. Mechanical properties of the obtained gels were investigated by compression test. Increasing of the crosslinking density with increasing of the monomer concentration, number of thiol group of the monomer or reaction conversion, raised Young's modulus, and breaking stress of the gels. Cogelation of the tri-, tetra-, of hexa-thiol monomer and dithiol monomers yielded soft and flexible gels. Reduction of the disulfide bonds in the gels by dithiothreitol turned the gel into solution. Heating of the resulting solution induced the regelation by reforming of the disulfide bonds. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3749–3756