Poly(arylether amides) and poly(aryletherketone amides) via aromatic nucleophilic substitution reactions of self‐polymerizable AB and AB₂ monomers

Abstract

Two new extended self-polymerizable AB monomers, N-(4-fluorobenzoyl)-4-amino-4Ј-hydroxydiphenylether and N-(4-fluorobenzoyl)-4-amino-4Ј-hydroxybiphenyl, were prepared. The monomers were homopolymerized and copolymerized to highmolecular-weight, linear poly(arylether amides) in N-methylpyrrolidone (NMP)/toluene in the presence of potassium carbonate at elevated temperature. The polymers retained NMP up to 200°C. Samples containing small amounts of the solvent (5-10 wt %) were soluble in polar aprotic solvents. However, after complete removal of the NMP, the polymers were only soluble in strong acids such as sulfuric acid and methanesulfonic acid (MSA). The polymers, which had intrinsic viscosities of 0.57-1.49 dL/g (30.1 Ϯ 0.1°C in MSA), were semicrystalline with melting temperatures above 400°C. Two new self-polymerizable AB 2 amide monomers, N,NЈ-bis(4-fluorobenzoyl)-3,4-diamino-4Ј-hydroxydiphenylether and N,NЈ-bis(4-fluorobenzoyl)-3,5-diamino-4Ј-hydroxybenzophenone, were also prepared and polymerized to give a hyperbranched poly(arylether amide) and a hyperbranched poly(aryletherketone) amide. The arylfluoride-terminated, amorphous polymers had intrinsic viscosities of 0.34 and 0.24 dL/g (30.0 Ϯ 0.1°C in m-cresol), glass-transition temperatures of 210 -269°C, and were soluble in a wide variety of organic solvents. Matrix-assisted laser desorption/ionization time-of-flight analysis indicated that the components of the low-molecular-weight fractions contained cyclic structures.

Dendritic homopolymers and block copolymers: Tuning the morphology and properties

“…The large number of end groups and the globular structure of dendritic polymers [15][16][17][18][19][20][21][22][23][24][25][26][27][28] are two factors that have stimulated research in such materials in areas ranging from drug delivery to nanofabrica-tion. 29 -32 By introducing chirality into dendritic structures, Denkewalter, Newkome, Seebach, McGrath, and others [33][34][35][36] have generated optically active polymers with targeted applications in areas of chemical separation and sensor technology.…”

Surface Wettability Controllable Polyimides Bearing Long-chain Alkyl Groups by UV Light Irradiation

“…2). 3,5-Dinitro-4-hydroxybenzophenone (1) were synthesized from 3,5-dinitrobenzoyl chloride and anisole by Friedel-Crafts acylation reaction using aluminum chloride as a catalyst, followed by demethylation using hydrogen bromide as the same manner previously reported [16]. 3,4,5-Tris(decyloxy) benzoic acid (2) were synthesized from gallic acid methyl ester followed by Williamson etherification reaction using decylbromide, then hydrolysis reaction in potassium hydroxide solution as the same manner described in previous literatures [17,18].…”

Novel Fluorine-containing Poly(aryl ether amide)s derived from 2,3,4,5,6-Pentafluorobenzoic Acid

“…It had been reported that the aryl fluoride containing an amide linkage reacted with phenoxides forming ether linkage without serious hydrolysis of amide linkage even at 180 . [10][11][12] On the basis of this consideration, the nucleophilic substitution reaction was chosen for the synthesis of F-PEAs.…”