Synthesis of New Aprotic Polar Polymers

N， N-二甲基乙酰胺（DMAc）、二甲基亚砜（DMSO）和六甲基磷酸三酰胺（HMPA）是有机合成中独特而有用的非质子极性溶剂。在本研究项目中，合成了这些极性溶剂的聚合物同源物。首先，制备了DMSO的聚合物同系物。以相应的脂肪族聚硫化物为原料，用双氧水氧化合成了脂肪族聚亚砜。所制得的聚亚砜作为氧化试剂用于Swern氧化。通过对聚硫乙烯的选择性氧化，制备了一种真正的DMSO聚合物同系物——聚亚砜。在DBU的存在下，采用线性聚乙亚胺与二（二甲胺）磷酸氯酯的聚合反应合成了HMPA。所制得的HMPA与聚苯乙烯等商品聚合物具有良好的混相性。采用开环聚合法制备了双（二甲胺）磷酸丙胺聚合物。以聚富马酸为例，成功制备了主链上全酰胺基团的聚（N， N-二甲基氨基甲酰亚甲基）。

N, N-Dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and hexamethyl-phosphoric triamide (HMPA) are unique and useful aprotic polar solvents in organic synthesis. In this research project, the polymer homologues of these polar solvents were synthesized.First, the polymer homologue of DMSO was prepared. Aliphatic polysulfoxides were successfully synthesized from the corresponding aliphatic polysulfides by the oxidation using hydrogen peroxide. The polysulfoxides obtained were used as oxidizing reagents in Swern oxidation. A real polymer homologue of DMSO, poly-(ethylene sulfoxide) was prepared by selective oxidation of poly (ethylene sulfide).The poly (HMPA) was synthesized by the polymer reaction of linear poly (ethyleneimine) with bis (dimethylamino) phosphoryl chloride in the presence of DBU.The poly (HMPA) obtained showed good miscibility with commodity polymers such as polystyrene. The poly (HMPA) was also prepared by ring-opening polymerization of bis (dimethylamino) phosphorylpropylenimine.As an example of poly (DMAc), poly (N, N-dimethylcarbamoylmethylene) having amide groups on all main chain carbons was successfully prepared by the polymer reaction of poly (fumaric acid).