Synthesis of Polymers with Ultra High Molecular Weight by Solid Phase Ring-opening Polymerization of Novel Macrocyclic Sulfides

研究了含均三嗪结构的大环硫代芳酯、硫醚的合成及固相开环聚合反应。以1-二丁氨基-3，5-二巯基均三嗪（BADMT）为原料，在稀溶液（0.01mol/L）中与溴代（邻、间、对）苯二甲撑反应，合成了大环硫醚。所得产物经循环制备HPLC分离，分别以中等产率分离出大环二聚体[（o-，m-，p-）CS-2]、三聚体[（o-，m-，p-）CS-3]和四聚体[（o-，m-，p-）CS-4]，并考察了它们在N2气氛下的本体开环聚合反应。各大环硫醚在300℃以上无催化剂开环聚合，所得聚合物的分子量不高。另一方面，通过使用催化剂如季鎓卤化物有效地增强聚合。当o-CS-2与四苯基氯化膦在250℃下聚合10 min时，在较低的聚合温度下，可得到分子量为180000的聚硫醚。的23%。研究了大环硫醚的无溶剂开环聚合行为，发现开环聚合反应发生迅速，生成高分子量聚合物。

Synthesis and solid phase ring-opening polymerization of macrocyclic S-aryl thioesters, macrocyclic sulfides containing s-triazine structure were studied. The macrocyclic sulfides were prepared by the reaction of 1-dibutylamino-3, 5-dimercapto-s-triazine (BADMT) with (o-, m-, p-) xylylene dibromide using bases at a dilute condition (0.01 mol/L) in various solvents. The obtained products were worked up using recycle preparative HPLC to isolate macrocyclic dimmers [(o-, m-, p-) CS-2], trimers [(o-, m-, p-) CS-3], tetramers [(o-, m-, p-) CS-4], with moderate yields, respectively.The ring-opening polymerizations of the obtained macrocyclic sulfides in bulk were examined under N_2 atmosphere. Although the ring-opening polymerization of each macrocyclic sulfide without catalysts proceeded over 300℃, the molecular weights of the resulted polymers were not relatively high. On the other hand, the polymerizations were enhanced efficiently by using catalysts such as quaternary onium halides. When the polymerization of o-CS-2 was conducted with tetraphenyphosphonium chloride at 250℃ for 10min, a poly (sulfide) with Mw of 180000 was obtained at a conv. of 23%. The behavior of the solvent free ring-opening polymerization of the macrocyclic sulfides was investigated to found that the ring-opening polymerization occurred rapidly to produce high molecular weight polymers.