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New cardo poly(aryl ether ketone)s containing side phthalide groups and aryl ether ketones in different lengths have been synthesized and characterized in terms of their thermal, volumetric and gas transport properties to H 2 , O 2 , N 2 , CH 4 and CO 2 . The polymers show high glass transition temperature (218–420 °C), good solubility in chlorinated solvents and strong acids as well as excellent thermal stability (decomposition temperatures above 510 °C). The most permeable membrane studied shows permeability coefficients of 11 to O 2 and 72 to CO 2 , with ideal selectivity factors of 4.6 for the pair O 2 /N 2 and 25 for CO 2 /CH 4 . The results, interpreted in terms of chain rigidity and chain packing ability, show that decreasing the length of the connector moieties between the cardo groups increases the fractional free volume, the glass transition temperature and the gas permeability coefficients.

High molecular weight, linear aromatic poly(ether ketone ketone)s with different iso-/tere-isomer repeating unit ratio ( 100 0 , 50 50 , 0 100 ) have been studied by 1 H and 13 C n.m.r. spectroscopy. The polymers were obtained in particle form by precipitation electrophilic Friedel-Crafts acylation condensation of iso- and terephthaloyl chlorides with diphenyl ether, 1,4- and 1,3-bis(4-phenoxybenzoyl)benzenes. Conventional 1 H and 13 C n.m.r. spectroscopy shows para -substitution in the diphenyl ether fragments of the main chain. Analysis of the expanded 1 H n.m.r. spectra for the ring proton resonances reveals defect meta - and ortho -structures. The amount and isomer ratio of these defect structures depend on the polymer structure and preparation path. The low field of 1 H n.m.r. spectra of polyketones based on ‘small monomers’ (diphenyl ether and iso- and terephthaloyl chlorides) were found to show additional minor signals corresponding to a different type of defect structure. A possible mechanism of formation of these defect structures is discussed. © 1997 Elsevier Science Ltd.

High molecular weight film-forming semicrystalline aromatic polyketones with a regular structure were obtained by precipitation electrophilic Friedel-Crafts polycondensation of 2,6-naphthalenedicarboxylic acid chloride with diphenyl ether, 1,4-bis(p-phenoxy) benzophenone and 1,4-bis(p-phenoxybenzoyl) benzene. Using 1H and 13C n.m.r. spectroscopy, the polyketones obtained were shown to be linear with para-substituted arylene fragments in the main chain. These polymers are soluble in strong protic acids and in common organic solvents, such as dichloroacetic acid and CHCl3/CF3CO2H mixtures. Depending on the chemical structure, these ‘as-made’ polyketones were found to show multiple melting behaviour on heating.

High molecular weight aromatic poly(ether ketone ketone)s were synthesized by the Friedel-Crafts polyacylation condensation of iso- and terephthaloyl chlorides with diphenyl ether, 1,4- and 1,3-bis(4- phenoxybenzoyl)benzenes. Depending on the monomers used for polycondensation, polyketones of regular structure with different iso-/tereisomer repeating unit ratio (100/0, 50/50, 0/100) in the main chain were obtained. Polymers of each repeating isomer unit were prepared in two different ways. All the polymer syntheses were performed as precipitation polycondensations and the resulting polymers were obtained in particle form. The influence of reaction conditions and preparation route on the polymer properties were examined. The monomer concentration and monomer stoichiometric ratio were found to affect the polymer viscosity. The size and shape of the polyketone particles obtained were also found to be governed by reaction conditions and preparation route.

8 pags, 5 pags, High molecular weight m-substituted poly(ether ketone-ketone) has been synthesized by electrophilic precipitation polycondensation via two different ways: reaction of isophthaloyl chloride with diphenyl ether and reaction of isophthaloyl chloride with 1,3-bis(4-phenoxybenzoyl)benzene. The second way of synthesis was found to give structurally more perfect polymers with higher molecular weights. In both cases polycondensation proceeded with precipitation of the polymers formed as uniform particles. The influence of reaction conditions has been studied. Monomer concentration and monomer stoichiometric ratio were shown to affect the polymer properties., Grateful acknowledgement is due to CICYT, Spain, for the support of this investigation (grant MAT 94/740E). One of us (M.G.Z.) also thanks CICYT for the tenure of a sabbatical grant during his research work in Madrid