Synthesis and characterization of polyaryleneetherketone triphenylphosphine oxides incorporating cycloaliphatic/cage hydrocarbon structural units

Abstract

New high temperature polyaryleneetherketone triphenylphosphine oxides incorporating trans-1,4-cyclohexane, 1,3-adamantane, and 4,9-diamantane structural units were synthesized by the base-promoted polymerization reaction between 4,4Јdifluorotriphenylphosphine oxide and the novel dihydroxy monomers trans-1,4-bis(4hydroxybenzoyl)cyclohexane, 1,3-bis(4-hydroxybenzoyl)adamantane, and 4,9-bis(4-hydroxybenzoyl)diamantane. The monomers were synthesized in a good yield by a twostep procedure involving the Friedel-Crafts acylation of anisole by the diacid chlorides trans-1,4-cyclohexanedicarbonyl chloride, 1,3-adamantanedicarbonyl chloride, and 4,9diamantanedicarbonyl chloride, followed by demethylation with pyridine hydrochloride. The polymers, which could be processed into tough, free standing films from organic solvents, exhibited high T g 's in the range of 192-239°as well as thermooxidative stabilities (5% weight loss in air) in the range of 445-490°. Preliminary results from a UV-visible spectroscopic study of dilute solutions of the polymers in chloroform showed absorption maxima in the 263-274 nm region and transparency to spectral radiation in the 300 -800 nm range, indicating that these triphenylphosphine oxide polymers could have potential applications for space thermal control coatings.

Synthesis of a polyoxadiazole containing the 4-hydroxypyridine group and photo-induced fluorescent imaging on the polymer film

“…The compositions calculated from the elemental analysis and 1 H NMR data were in reasonable agreement. During the polymerization reaction, the pyridone group was converted into a hydroxypyridine unit, with a chemical shift around 10 ppm (for hydroxyl group) in the NMR spectrum similar to the previous reports [33,34]. It is plausible that such a downfield-shifted peak of the hydroxyl group resulted from a weakening of OAH bond in the presence of intermolecular hydrogen bonding.…”

Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane

“…[94,122,125,127,132,133] In 2004, Dang et al synthesized polyarylenether ketones with 2 as the structural unit. [134] Diamantane polymers have been covered in a review by Meador. [135] Even though some of these polymers show very interesting features, such as high-subglass transition temperatures or low dielectric constants, none of them seems to have been used in practice.…”

Synthesis of disubstituted homodiamantanes by acylative ring expansion using benzoyl trifluoromethanesulfonate

“…Fusing two molecules of adamantane forms diamantane (2: pentacyclo[7.3.1.1 4,12 .0 2,7 .0 6,11 ]tetradecane). A hydrocarbon with additional CH 2 into adamantane is called homoadamantane (3: tricyclo[4.3.1.1 3,8 ]undecane).…”

“…A hydrocarbon with additional CH 2 into adamantane is called homoadamantane (3: tricyclo[4.3.1.1 3,8 ]undecane). In principle, ring enlargement of diamantane can derive two isomers, homodiamantane (4: pentacyclo[8.3.1.1 4,13 .0 2,7 .0 6,12 ]tetradecane) and isohomodiamantane (5: pentacyclo[8.3.1.1 4,13 .0 2,8 .0 6,12 ]tetradecane). The preparation and functionalization of elegant structures of these diamondoid hydrocarbons have fascinated chemists [1][2][3][4][5][6].…”

“…The preparation and functionalization of elegant structures of these diamondoid hydrocarbons have fascinated chemists [1][2][3][4][5][6]. Recently the interest in diamondoid structures has been renewed by application in material science [10,11], polymer science [12][13][14][15], and medicinal chemistry [16].…”