Synthesis of thermosetting polyetherimide‐containing allyl groups

Abstract An allyl‐containing diphenol, 1‐(3‐allyl‐4‐hydroxyphenyl)‐1‐(4‐hydoxyphenyl)‐1‐(6‐oxido‐6H ‐dibenz[c,e][1,2]oxaphosphorin‐6‐yl)ethane (1) , was prepared from a one‐pot reaction of 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide, 4‐hydroxyacetophenone, and 2‐allylphenol in the presence of p ‐toluenesulfonic acid monohydrate. Then, an allyl‐containing dietheramine, 1‐(4‐(4‐aminophenoxy)phenyl)‐1‐(3‐allyl 4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenz[c,e][1,2] oxaphosphorin‐6‐yl)ethane (3) , was prepared from the nucleophilic substitution of (1) with 4‐fluoronitrobenzene, followed by the reduction of the dinitro groups by Fe/HCl. A flexible polyetherimide (PEI) (4) with a curable characteristic was prepared from the condensation of (3) and 4,4′‐oxydiphthalic anhydride (ODPA) in m ‐cresol in the presence of isoquinoline. Curing PEI (4) at 300 °C leads to PEI (5) , which exhibits much a higher T g value (307 °C) and a lower coefficient of thermal expansion (CTE) (29 ppm/°C) than PEI (4) ( T g = 253 °C, CTE 52 ppm/°C). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013