Room temperature, simple and efficient synthesis and functionalization of aromatic poly(arylene sulfide)s, poly(arylene sulfoxide)s and poly(arylene sulfone)s. (7th February 2023)

• Record Type: Journal Article
• Authors: Cetina-Mancilla, Enoc; Reyes-García, Germán A.; Rodríguez-Molina, Manuel; Zolotukhin, Mikhail G.; Vivaldo-Lima, Eduardo; Ortencia González-Díaz, María; Ramos-Ortiz, Gabriel
• Is Part Of: European polymer journal. Volume 184(2023)
• Publication Date: 2023-02-07
• Subjects: Poly(arylene sulfide)s -- Poly(arylene sulfoxide)s -- Poly(arylene sulfone)s -- Superacid -- Non-stoichiometric -- Polyhydroxyalkylation; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2022.111800
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: Phenyl sulfide reacts with trifluoroacetone and isatin to give polyarylene sulfides. One-pot, room temperature polyhydroxyalkylations proceed with high regioselectivity. Room temperature oxidation affords polyarylene sulfoxides and polyarylene sulfones. Heating the polyarylene sulfoxides produce nanofoams. Controlled incorporation of various functionalities is achieved at room temperature. Abstract: Aromatic polysulfides and polysulfones are a large group of sulfur-containing polymers representing an important class of materials with diverse applications, ranging from high performance engineering plastics, gas separation, ultrafiltration, nanofiltration, ion-exchange membranes, and materials for biomedical applications. All these polymers are produced by high temperature nucleophilic substitution reactions of dichlorobenzene with sodium sulfide (PPS) and dichlorodiphenyl sulfone with bis-phenols in the presence of basic catalysts (PAES). In the present work, novel poly(arylene sulfide)s were obtained in nearly quantitative yields, by one-pot, room temperature, metal-free, highly regioselective, non-stoichiometric step-polymerizations of diphenyl sulfide (DPS) with 1, 1, 1-trifluoroacetone and isatin, in a mixture of trifluoromethanesulfonic acid (TFSA) with CH2 Cl2 . The polymers obtained were soluble in common solvents. The oxidation of the poly(arylene sulfide)s with H2 O2 at room temperature afforded poly(arylene sulfoxide)s and poly(arylene sulfones) with high oxidation selectivity. On heating, sulfoxide groups of the poly(arylene sulfoxide)s are converted into sulfide groups and oxygen, which acts as an expanding agent, is released in the process to form nanofoams with homogeneous pore distribution. Controlled incorporation of hydroxymethyl-, carboxy-, and "click" able allyl- and propargyl- functionalities is carried out by room temperature, post-modification reactions of the polymers bearing reactive oxindole groups.