Use of 4-piperidones in one-pot syntheses of novel, high-molecular-weight linear and virtually 100%-hyperbranched polymers

Abstract

4-Piperidone and 4-alkyl piperidones react selectively with aromatic hydrocarbons in a mixture of trifluoromethanesulfonic acid (TFSA) and CH(2)Cl(2) to give linear polymers, while N-(2-phenethyl)piperidone undergoes self-polymerization to yield virtually 100%-hyperbranched polymer.

Non‐Stoichiometric Polycondensations and the Synthesis of High Molar Mass Polycondensates

“…Afterwards, numerous authors contributed papers and patents to this field of work and, in 1907, Baekeland patented a procedure suitable for the technical production of Bakelite based on the polycondensation of phenol and formaldehyde 63, 64. Over the last ten years, Zolotukhin et al have reported several times on trifluoromethane sulfonic acid (triflic acid) catalyzed polycondensations of fluorinated ketones with various aromatic monomers, such as biphenyl, diphenyl ether or 4,4‐diphenoxybenzophenone 65–72. This process may yield high molar mass polymers when catalyzed by triflic acid and when the ketone is used in excess.…”

Effects of the N-alicyclic cation and backbone structures on the performance of poly(terphenyl)-based hydroxide exchange membranes

“…Friedel-Cras type polycondensation of arenes (such as biphenyl, terphenyl and uorene) and suitable ketones via hydroxyalkylation reactions in superacidic media is an attractive route to thermochemically and mechanically robust etherfree polymers suitable for the preparation of alkali-stable HEMs. [24][25][26][41][42][43][44][45] In order to prepare the polymer structures depicted in Scheme 1 by this method, we initially synthesized two monomers: one m-terphenyl and one tri-uoroacetophenone, each functionalized with a piperidine ring (Scheme 2). The piperidine ring can subsequently be quaternized by dimethylation to form the monocyclic DMP cation, or by cycloquaternization with 1,5-dibromopentane to form the Scheme 1 Overview of the variations in the molecular design of the cationic polymers synthesized and investigated as HEMs.…”

Fully branched hyperbranched polymers with a focal point: analogous to dendrimers

“…A number of such studies have been reported. 11,[21][22][23][24][25][26][27][28][29][30] Among them, the polymerization of AB 2 monomers by superelectrophilic arylation of particular carbonyl groups in strongly acidic environments is the mostly used method. 21,23,26,28,29 The superelectrophilic reaction between the reactive carbonyl group and an aromatic ring can exclusively yield a disubstituted product due to the high reactivity of the monosubstitued intermediate (Scheme 1).…”