Aryl-substd. poly-p-phenylene(s) - by anionic polymerisation of aryl-substd. cyclo-hexa-1,3-diene(s) and reaction of resulting poly-p-cyclo-hexa:di:ene with oxidising agent

摘要

New aryl-substd poly-p-phenylenes of formula (I) are produced by (a) anionic polymerisation of substd 1,3-cyclohexadienes of formula (II) in organic solvent in the presence of alkali metal alkyls, and (b) reaction of the resulting poly-p-cyclohexa-1,3-dienes (III) with an oxidising agent in organic solvent (opt after isolation of III); where Ar = 6-18C aryl; n = 1,2, 3 or 4; x = 10-5000. Pref, stage (a) is carried out in cyclohexane or toluene at 0-60 deg C using n-BuLi, and stage (b) is carried out at 70-200 deg C in xylene, naphthalene, etc, using chloranil, tetrachloro-p-benzoquinone (IV), etc as oxidising agent. USE/ADVANTAGE - (I) are useful for the prodn of moulded prods (claimed). The process enables the prodn of (I) in high yield; (I) have very high thermal stability (up to 650 deg C); eg poly(phenyl-1,4-phenylene) is completely soluble in boiling Ph0Ph, gives an anisotropic melt at 300 deg C and undergoes max decompsn at 650 deg C (60% residue at 1000 deg C); the precursor (III) decomposes at 350 deg C (99%).