Linear and networked polymers formed by the near simultaneous occurrence of etherification and esterification under mild reaction conditions

Abstract

Despite the large difference in their nucleophilicity, phenoxide and carboxylate anions take part nearly simultaneously in the aliphatic nucleophilic substitution reaction with 1,4‐dibromo‐2‐butene. This leads to the formation of ether (O) and ester (COO) linkages simultaneously under mild reaction conditions when hydroxyl benzoic acids are employed as nucleophiles. The process yields a new class of polymer broadly classified as unsaturated poly(ether ester) which are potentially functionalizable. This methodology has also been extended for preparing networked polymers by making use of 3,5‐dihydroxybenzoic acid as A3 type monomer. Copyright © 2011 Society of Chemical Industry

A new addition to the family of polyesters—Synthesis and characterization of novel (alternating) poly(ether ester)s, poly(butylene 3-/4-hydoxy benzoate)s

“…Materials UPEE 1 (M n 022528, M w 033750, PD01.5) and 2 (M n 0 25554, M w 038079, PD01.49) were prepared as reported before by us by reacting 4-hydroxybenzoic acid and 3-hydroxybenzoic acid respectively with 1,4-dibromo-2-butene A. Parthiban (*) : F. M. Choo in dipolar aprotic solvents in the presence of mild base like potassium carbonate [6]. p-Toluenesulfonylhydrazide (TSH) (97%) was purchased from Aldrich Chemical Co. Tetrahydrofuran (THF) was purified in a solvent purification system (Glass Contour).…”

“…Unsaturated poly(ether ester)s (UPEE) were prepared by reacting hydroxybenzoic acids (HBA) with trans-1,4-dibromo-2-butene as reported before by us [6]. The reaction proceeded smoothly in dipolar aprotic solvents by using bases like potassium carbonate under mild conditions.…”

“…Ester bond is the only desired bond formed in these polymerization reactions. Recently we reported a new class of polymers broadly termed as unsaturated poly(ether ester)s which were obtained by the simultaneous formation of ether and ester bonds during polymerization reaction [5,6]. It is worthwhile to note here that such poly(ether ester)s are unknown.…”

Soluble, microporous ladder polymers formed by stepwise nucleophilic substitution of octafluorocyclopentene

“…9 Because of the absence of protons in OFCP, products formed by the substitution reaction with phenoxides generated in situ from phenols can be conveniently and conclusively analyzed by 19 F nuclear magnetic resonance ( 19 F-NMR) spectroscopy ( Fig. The ability to undergo such tetrasubstitution makes OFCP a suitable, non-aromatic monomer for producing ladder polymers as well as hyperbranched or networked polymers.…”

“…Polymers formed by a one step process, irrespective of the reaction temperature exhibited a similar surface area (Table 3, LAD P5 and LAD P6). 9 (ii) Uniformly smooth desorption curve. 1,11 However, it is comparable to bisnaphthalene based soluble polyimides of intrinsic microporosity.…”