Adamantyl-substituted phenolic polymers

Abstract

4‐(1‐Adamantyl)phenol was synthesized via Friedel‐Crafts reaction of 1‐bromoadamantane and phenol. Substitution in the phenol para position forces polymerization to occur only in the ortho positions to give a linear polymer. Variations in formaldehyde amount, reaction time, and catalyst were evaluated. Increasing the amount of paraformaldehyde increased formation of cyclic octamer, an easily identified by‐product due to its insolubility in common organic solvents. The cyclic octamer was acetylated to give a soluble model compound for comparison to acetylated polymers by IR and NMR. All of the synthetic variations employed produced low molecular weight polymers as indicated by NMR end‐group analysis and SEC. The polymers showed number‐average molecular weights of ca. 3000 (versus polystyrene standards by SEC), and exhibited glass transition temperatures ranging from 175–230°C, an increase of ca. 100°C over unsubstituted and para‐alkyl substituted analogs. All of the samples exhibited a 10% weight loss at 400°C in nitrogen, indicating thermal stability much greater than the parent and alkyl‐substituted polymers. © 1996 John Wiley & Sons, Inc.

Preparation and characterization of para-tertiary-butylphenol formaldehyde resins using dual catalytic-extraction method

“…The tertiary butyl groups of the PTBP-FR resonate at 33.7 ppm (Peak g) and 31.2 ppm (Peak h). From the amplification spectrum, only ortho-ortho methylene linkages (Peak c, 30.8 ppm) are formed, which corresponds well with the fact that the PTBP possesses only two reactive sites on the ortho position of benzene ring [27]. On the other hand, the signal of acetone-d6 solvent at 30 ppm may overlap with the resonance of ortho-ortho bridge structures, which makes Peak c difficult to identify [23].…”

Benzyl ether polymers: Crystallinity and pendant adamantyl effects

“…Adamantyl phenol 11 and resorcinol 17 were obtained by reported procedures and gave spectral data consistent with their structures. The dibromo monomer 10 (Fig.…”

“…Adamantyl-substituted phenol was synthesized by alkylating phenol with 1-bromoadamantane as EXPERIMENTAL previously reported. 11 Phenol (150.0 g, 1.63 mol) and 1-bromoadamantane (30 g, 0.14 mol) were heated at 100ЊC under N 2 for 4 h. The exit gas All chemicals were purchased from Aldrich Chemical Company except 1-cyclohexyl-2-pyrrolidinone was bubbled into a 10% aqueous sodium hydroxide solution to trap the HBr formed. The excess (CHP) which was purchased from Lancaster Synthesis Inc. Reagents 6-amino m-cresol, p-tolyl phenol was removed by stirring the product in three 1000 mL portions of hot water.…”

Synthesis and properties of new aromatic polyisophthalamides with adamantylamide pendent groups

“…Aromatic condensation polymers containing adamantane groups in the backbone have repeatedly been reported in the past. Thus, polyamides,18 polyimides,19, 20 phenolic resins,21 polysulfones,22 and polycarbonates23 have been synthesized from monomers based on the adamantane ring. As a rule, the incorporation of these moieties into the polymer structure has brought about an increase of both solubility and glass transition temperatures, so that the incorporation of adamantyl pendent groups was foreseen as a suitable alternative to improve the properties of traditional PIPAs.…”