Preparation of Poly(thioarylene)s from Cyclic Disulfide Oligomers

Abstract

A series of poly(thioarylene)s, including fluorinated poly(thioarylene)s, was prepared from cyclic disulfide oligomers and diiodo or dibromo aromatic compounds in diphenyl ether solution at 270 °C. The cyclic disulfide oligomers were derived from 4,4‘-thiobis(benzenethiol) and 4,4‘-biphenyldithiol, respectively. Diiodo monomers had to be used in excess (∼4%) to obtain the highest molecular weight polymers, while equivalent amounts of dibromo monomers could be used. 1,4-Diiodobenzene gave poly(thio-1,4-phenylene) (PPS) with a T g of 88 °C and a T m of 286 °C, and 1,4-dibromobenzene gave PPS with a T g of 92 °C and a T m of 275 °C by reacting with the cyclic disulfide oligomers derived from 4,4‘-thiobis(benzene thiol). Poly(thiobiphenylene) obtained from cyclic disulfide oligomers derived from 4,4‘-biphenyldithiol had a melting point of 454 °C. Fluorinated diiodo or dibromo monomers have much lower reactivities toward the thiyl radical substitution reaction, and only low molecular weight polymers were obtained. All of the poly(thioarylene)s prepared have very high thermal stabilities as indicated by TGA.

Poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s derived from a dihydroxy(imidoarylene) monomer

“…The low viscosity ide anion becomes very serious at temperatures higher than 250ЊC, and high molecular weight of polymer 6d might be due to the side reaction between the sulfone group and thiophenoxide polymer could not be obtained. 21 We have pointed out earlier that solvents containing actianion. Poly(arylene thioether)s containing the penvated hydrogens could not be used for the polymerization because they react with cesium cardent imido group have high solubility in CHCl 3 except polymer 6c, which is insoluble in CHCl 3 .…”

Characterization of novel poly(aromatic amine‐2,3‐pyridinedione) oligomers by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry

“…The technique has also been applied to the investigation of synthetic polymers and oligomers, for which MALDI‐TOFMS can provide information of the absolute molecular mass, polydispersity, and structures of polymeric chains and end‐groups. A variety of synthetic polymers and oligomers have now been characterized using MALDI‐TOFMS 8–13. In this article we demonstrate the structural characterization of three kinds of novel synthetic poly(aromatic amino‐2,3‐pyridinedione) oligomers by MALDI‐TOFMS.…”

Palladium‐Catalyzed Polycondensation for the Synthesis of Poly(Aryl)Sulfides

“…[ 11–16 ] However, the synthesis of poly(phenyl)sulfide derivatives is still a challenging task, which is usually achieved under drastic reaction conditions by radical reactions, [ 6,17–21 ] nucleophilic substitution of fluoroarenes [ 22–24 ] or via sulfonium cations. [ 18,25–28 ] Only recently transformations under milder reaction conditions were realized involving Michael‐type addition [ 29,30 ] or transition metal mediated carbon–sulfur bond forming reactions. [ 24,31,32 ] All of these transformations require the synthesis of thiophenol derivatives prior to the transition metal mediated reaction with the corresponding halo arene.…”