Well‐Controlled Synthesis of Poly (phenylene sulfide) (PPS) Starting from Cyclic Oligomers

Abstract

Summary The mixture of cyclic PPS oligomers (c‐PPS) with more than 99% of purity, less than 15 ppm of metal content and more than 4 of repeating units was prepared by the nucleophilic substitution reaction between dichlorobenzene (DCB) and sodium sulfide (Na2S) in relatively dilute solution. Melt polymerization of the c‐PPS in the absence of initiator at high temperature resulted in P(c‐PPS) having high molecular weight, relatively narrow molecular weight distribution and extremely low weight loss at high temperature. Results from MALDI‐TOF‐MS, GPC and in‐situ ESR analysis of the polymerization intermediates suggested that the polymerization of c‐PPS proceeded by a sulfide exchanging polymerization. In addition, the sulfide exchanging polymerization of c‐PPS in the presence of bis(4‐substituted phenyl) sulfides (BPS‐X) such as bis(4‐aminopheny) sulfide (BPS‐NH2), bis(4‐carboxyphenyl) sulfide (BPS‐COOH), and bis(4‐chlorophenyl) sulfide (BPS‐Cl) produced end‐group modified and ring‐opened P(c‐PPS)s. Comparison of polymerization rate in the presence of BPS‐X suggested that the BPS‐X acted as both initiator and chain transfer agent, and the sulfide exchanging polymerization was accelerated by the addition of BPS‐NH2 and BPS‐COOH due to the activation of sulfide linkage through the substitution effect.

Tribological properties of cyclic phenylene sulfide heat‐treated carbon fiber/polyphenylene sulfide composites

“…Illuminated by the research, we were convinced that the in-situ formation of a coating on the CF surface matching the matrix polymer and possessing high temperature resistance may be beneficial for reinforcing the specified matrix resin. Indeed, as a soluble precursor for PPS preparation, cyclic phenylene sulfide oligomers (CPS) [34,35] have been confirmed as an effective sizing agent for CF used in CF reinforced polyetheretherketone (PEEK) composite previously. [36] The good enhancement in mechanical (tensile, compressive, impact) strength and tribological properties of CF/PEEK composites was deduced to the chemical structural similarity of heat-treated CPS ( Ar-, S O) with PEEK ( Ar , C O), which significantly enhances the interface compatibility.…”

Preparation of Recyclable and Versatile Porous Poly(aryl thioether)s by Reversible Pd-Catalyzed C–S/C–S Metathesis

“…Sulfur-containing 1D-polymers like poly­(phenylene sulfide) (PPS) have seen widespread use in industry as insulators and replacements for metal parts due to their extremely high chemical, thermal, and mechanical resistance, as illustrated by the large number of patents (>100000) in this area . However, the harsh conditions required for the synthesis of PPS (Scheme a, polycondensation >250 °C, Na 2 S, autogenous pressure) , and the extreme stability of the aryl thioether bonds make it difficult to fine-tune PPS’s properties (e.g., M w , cross-linking, and polydispersity), although branched analogues of PPS have been occasionally reported following the polycondensation approach . This dramatically limits the possibility to access more complex poly­(aryl thioether)-based structures with 2D or 3D cores, despite their potential to exhibit advanced features such as porosity, metal-binding ability, or optoelectronic properties, among others.…”

Preparation of Recyclable and Versatile Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

“…16 Sulphur containing 1D-polymers like polyphenylene sulphide (PPS) have seen widespread use in industry as insulators and replacements for metal parts due to their extremely high chemical, thermal and mechanical resistance, as illustrated by the large number of patents (>100'000) in this area. 17,18 However, the harsh conditions required for their synthesis (Scheme 1a, polycondensation > 250 °C, Na2S, autogenous pressure) 17,19 and the extreme stability of the thioether bonds, make it difficult to fine-tune PPS's properties (Mw, cross-linking, polydispersity, etc.). Moreover, this dramatically limits the possibility to access more complex poly-arylthioetherbased structures with 2D or 3D cores, despite their potential to exhibit advanced features such as porosity, metalbinding ability or optoelectronic properties, among others.…”