钯催化胺化反应合成高性能材料——聚亚胺砜

SYNTHESIS OF HIGH-PERFORMANCE POLY(IMINO SULFONE) VIA PALLADIUM-CATALYZED AMINATION REACTION

利用三(二亚苄基丙酮)二钯(Pd2(dba)3)与1.1′-联萘-2.2′-二苯膦(BINAP)组成的催化体系,高效地催化4,4′-二氯二苯砜和芳香二胺的Buchwald-Hartwig交叉偶联反应,制备出新型聚亚胺砜.聚合物结构通过核磁氢谱、红外谱图、凝胶渗透色谱和元素分析等方法进行表征,表征结果与目标产物相吻合,并具有较高的分子量(Mw>2.5×104).利用DSC、TG和XRD等对其性能进行测试,结果表明,该类聚合物为无定形态,具有较高的玻璃化转变温度(Tg>200℃)、良好的热稳定性(Td>400℃)和溶解性能.其中含异丙基的PIS-3不仅可溶解在强极性溶剂中,并且在室温条件下(25℃)可溶于四氢呋喃中.

A series of novel high-performance polymers poly（imino sulfone）s （PISs） have been obtained by the aryl amination reaction of 4,4＇-dichlorodiphenyl sulfone and a series of aromatic diamines,using the catalytic system generated from tris（ dibenzylideneaeetone ） -dipalladium （0） （ Pd2 （dba） 3 ） and 2,2＇-bis （ diphenyl phosphino） - 1,1 ＇- binaphthyl （BINAP）. The structures and general properties of PISs are characterized by means of FTIR, 1H-NMR spectroscopy, DSC, TG, XRD, etc. The results confirm the proposed molecular structure and show that PISs possess high molecular weight （ Mw 〉 2.5 × 10^4 ） ,high glass transition temperature （ Ts 〉 200℃ ） and good thermal stability with high decomposition temperatures （Td 〉 400℃ ）. PISs possess amorphous structures and also exhibit the excellent solubility. PIS-3 and PIS-4 can be dissolved not only in high polar solvents, but also in common organic solvent THF at room temperature （25℃）.