芳香单硫聚甲烷环状物的相转移催化合成及其开环聚合

Synthesis of Cyclic Aromatic Sulfide Oligoformals by Phase Transfer Catalysis and Its Ring-Opening Polymerization

以四丁基硫酸氢铵为相转移催化剂合成了一系列芳香单硫聚甲烷环状物(简称环状物),并采用凝胶渗透色谱、高效液相色谱、核磁共振、热重分析法对环状物的结构进行了表征。熔点测定表明,低相对分子质量环状物具有明显的熔点(204-268 ℃)。低相对分子质量环状物在2,2’-二硫代二苯并噻唑的引发下于(285±5)℃发生开环聚合,得到相应的不溶性的线型高相对分子质量的芳香单硫聚甲烷。示差扫描量热法分析表明,所得到的高相对分子质量的芳香单硫聚甲烷的玻璃化转变温度为 97．1-141．7℃。所合成的低相对分子质量环状物的潜在用途是作为高温黏合剂、高性能聚合物材料和纳米材料的基体。

A novel method for synthesis of cyclic aromatic sulfide oligoformals （ cyclic oligoformals） over tetrabutyl ammonium bisulfate as phase transfer catalyst was studied. This method took advantages of mild operating conditions and high product yield. The cyclic oligoformals were characterized by means of gel permeation chromatography （ GPC ）, high-pressure liquid chromatography （ HPLC ）, ^1H nuclear magnetic resonance （^1H NMR）and thermo-gravimetric analysis（TGA）. The cyclic oligoformals had melting temperatures ranging from 204℃ to 268℃. Ring-opening polymerizations of cyclic oligoformals could readily be carried out at（285 ± 5 ）℃ in presence of 2,2＇-dibenzothiazole disulfide as initiator. Linear aromatic sulfide polyformals with high relative molecular mass were obtained. These polyformals were insoluble in most solvents. According to differential scanning calorimetry （DSC） measurement,the glass transition temperature of obtained polymers ranged from 97.1℃ to 141.7℃. The prepared cyclic oligoformals could be used as hot-melt adhesive, and matrices for high-performance polymers and nano-composites.