金属铬配合物催化环氧烷烃与酸酐的共聚反应

Copolymerization of Epoxides With Anhydrides Catalyzed by Chromium Complex

合成了氨基双酚化合物,并制备了相应的金属铬配合物,作为引发剂考察其在环氧环己烷与丁二酸酐聚合反应中的催化行为。以2,4-二叔丁基苯酚,多聚甲醛以及N-二甲基乙二胺为原料合成了相应的氨基双酚化合物,并采用核磁共振氢谱对其进行了鉴定。将得到的氨基双酚化合物在无水无氧条件下与无水氯化铬(Cr Cl2)在四氢呋喃中反应后再在空气中氧化制备出相应的三价氨基双酚铬氯配合物。所得到的配合物用核磁共振氢谱以及高分辨质谱进行了表征。制备的氨基双酚氯化铬配合物在有机碱4-(N-二甲基)吡啶(DMAP),PPNCl,及N-Melm的作用下可以有效的引发环氧烷烃(环氧环己烷,环氧氯丙烷,环氧丙烷)与酸酐(邻苯二甲酸酐,丁二酸酐)的开环共聚。对聚合物采用核磁共振氢谱凝胶渗透色谱(GPC)进行表征。

Amino bisphenol compound was synthesized, and then its metal complex was prepared, catalysis behavior of prepared metal complex for the polymerization reaction of cyclohexene oxide and butanedioic anhydride was investigated. Amino bisphenol compound was synthesized from 2,4-di-tertbutylphenol, paraformaldehyde and N-dimethylethylenediamine, and it was characterized by ^1H NMR.The amino bisphenol compound reacted with anhydrous chromium chloride （CrCl2） in dry THF at room temperature to prepare corresponding divalent chromium complex, and then the divalent chromium complex was oxidize to the target trivalent chromium chloride complex, its structure was identified by ^1H NMR and MALDI-TOF-MS. The trivalent chromium complex was an efficient initiator for the copolymerization of cyclic acid anhydride with epoxides by assistance of organic base such as 4- （N-dimethyl） pyridine （DMAP）, a series of polyesters were produced from phthalic anhydride, succinic anhydride and eyclohexene oxide, they were structurally characterized by ^1H NMR and GPC.