Abstract：
New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2\',3\'-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61-82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by 1H, 19F, and 13C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs.
摘要：
通过氟化远爪双（环碳酸酯）（bis-CC）与二胺的加聚反应，合成了具有各种摩尔重量的新型氟化聚羟基聚氨酯（FPHU）。氟化双CC最初是通过氟化二环氧化物的羰基化合成的，1,4-之二（2\'，3'-环氧丙基)全氟丁烷，在LiBr催化剂存在下，在高产量。然后，通过氟化双CC与己胺的模型反应优化了几种反应条件。随后，通过使bis-CC与不同的六亚甲基二胺在80°C和催化剂的存在下在本体中反应来制备带有羟基氨基甲酸酯部分(FPHU)的氟化聚合物。化学选择性聚合反应产生了三种带有伯羟基和仲羟基的异构体，产率为61-82％。合成的氟化CC和相应的FPHU通过1H，19F,和13CNMR光谱。将它们与在相似条件下合成的它们的氢化同系物进行比较。凝胶渗透色谱(GPC),差示扫描量热法(DSC),FPHU的热重分析（TGA）数据显示，与PHU相比，摩尔质量更高，玻璃化转变和分解温度略有增加。
