Synthesis, structure and ring-opening polymerization of phenolphthalein macrocyclic polyarylates

Abstract

Phenolphthalein based polyarylate macrocyclic oligomers were selectively synthesized by an interfacial polycondensation reaction of o‐phthaloyl dichloride with phenolphthalein. The high selectivity benefits from the role of phenolphthalein as a color indicator, an efficient phase transfer catalyst, and a preferred conformation of the starting materials as indicated by analyzing a single‐crystal X‐ray structure of an analogous macrocycle. The melt ROP of phenolphthalein polyarylate cyclic dimer was studied using nucleophilic initiators. The molecular weight of the resulting polymers builds up very rapidly at the very early stage of polymerization but decreases with time. During the ROP of cyclic dimer, analogous macrocycles with higher degree of polymerization (n ≥ 3) and linear oligomers were produced by backbiting reaction especially at later stage of polymerization. Conversion of cyclic dimer is very fast at the earlier stage of polymerization and then increases slowly with time as analyzed by gel permeation chromatography. However, the total amount of cyclic oligomers in the ROP system increases with time at the later stage of polymerization because of the formation of larger macrocycles. The resulting polymers are amorphous. Glass transition temperatures (Tgs) of these polymers are influenced by the polymerization time, type of initiator, and initiator concentration.

Cyclic polymers: Synthetic strategies and physical properties

“…The driving force is based on a gain in entropy resulting from broadening of the molecular weight distribution and from a gain in segmental mobility. Numerous research groups studied ROPs of aliphatic cyclic oligocarbonates, [189][190][191][192] aromatic cyclic oligocarbonates, [193][194][195] aromatic cyclic oligoesters, 129,[199][200][201][202] aromatic cyclic oligoethers, 203,204 cyclic oligoaramides, 205 and cyclic arylene disulfides. 206 Most of these ROPs were summarized in recent review articles.…”

“…194,195,199 Other authors presented their polymerizations as kinetically-controlled ROPs despite higher temperatures (up to 340 C). [196][197][198][199][200][201][202][203] For most entropy-driven ROPs, the question of kinetic or thermodynamic control was not discussed. MT mass spectra are missing and information on the content of cyclic oligomers and polymers in the reaction product is totally absent.…”

High‐performance soluble copolyarylate based on phenolphthalein: synthesis, characterization and properties

“…Phenolphthalein (PP) has bulky pendent groups and an asymmetric structure. Many high‐performance polymers with PP‐based cardo groups have been synthesized, including poly(arylene ether sulfone)s, poly(arylene ether ketone)s, poly(arylene ether nitrile)s and PARs . Among them, PP‐based cardo PARs are the most widely studied.…”

“…reported macrocyclic arylate dimers synthesized through the interfacial polycondensation of o ‐phthaloyl dichloride with PP. PP‐based cardo PARs were obtained through the ring‐opening polymerization of macrocyclic precursors, which are particularly valuable for the manufacturing of advanced composite materials . Moreover, Ma and co‐workers prepared a new series of electrochromic PARs from triphenylamine‐based dicarboxylic acid monomer with a pendent phenothiazine group, PP and diphenol compounds.…”

Chemically Amplified Photolithography of a Copolymer Containing Phenolphthalein

“…[2] Thermally stable polymers based on a phenolphthalein backbone such as poly(aryl ether ketone), [3,4] poly(aryl ether sulfone), [5][6][7] and polyarylates exhibit high softening temperature and good solubility characteristics. [8] Recently, phenolphthaleins have also been known to create a photovoltage/ photocurrent when embedded in a photoelectrochemical cell. [9] The dyes in aqueous PVA show similar photocurrent kinetics to those observed for porphyrins and phthalocyanines.…”