Cyclic Ladder Polymers by Polycondensation of Silylated Tetrahydroxy-tetramethylspirobisindane with 1,4-Dicyanotetrafluorobenzene

Abstract Summary: 5,5′,6,6′‐Tetra(trimethylsiloxy)‐4,4,4,4′‐tetramethyl‐1,1‐spirobisindane was polycondensed with 1,4‐dicyanotetrafluorobenzene under variation of solvent temperature, time, and feed ratio. Under optimized reaction conditions, all products detectable by MALDI‐TOF mass spectrometry (up to masses around 8 000 Da) proved to be cyclic ladder oligomers and polymers. In N ‐methylpyrrolidone and dimethylsulfoxide odd‐numbered cycles were formed in addition to the prevailing even‐numbered ones. However, in sulfolane exclusively even‐numbered cycles were obtained (detectable up to masses around 10 000 Da), together with even‐numbered linear chains. Temperatures above 100 °C enhanced the molecular weights by side reactions. With the less reactive cyano‐2,3,5,6‐tetrafluorobenzene (CTB) again cycles were formed, but their content and the conversions were lower. Polycondensation of CTB up to 160 °C and all polycondensations of cyanopentafluorobenzene gave crosslinked products. Synthesis of cyclic ladder polymers. magnified image Synthesis of cyclic ladder polymers.