The synthesis and properties of some aromatic polythioethers

Abstract

Polyarylene sulfides have been prepared from 4.4'-biphenyldithiol and 4.4'-biphenylether dithiol by reaction with 4.4'-dichlorodiphenylsulfone. These polymers were oxidized to the corresponding polysulfoxides using hydrogen peroxide. The thermal properties of the polysulfoxides prepared were investigated and compared with those of their polythioether precursors. ZUSAMMENFASSUNG: Polythiole aus 4.4'-Biphenyldithiol nnd 4.4'-Biphenylatherdithiol wurden durch Umsetzung mit 4.4'-Dichlordiphenylsulfon hergstellt. Die Polymeren wurden mit Wasserstoffperoxid zu den entsprechenden Polysulfoxiden oxidiert. Die thermischen Eigenschaften der hergestellten Pol ysulfoxide wurden untersucht und mit denen der Ausgangsstoffe (Polythioather) verglichen.

Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

“…Besides poly(phenylene sulfide), a number of other fully‐aromatic polysulfides have been studied, although none of them appears to have reached the stage of commercial application, for example: polysulfides containing fused54, 55 or heterocyclic56, 57 structures, or polymers based on more complex main chains, such as poly(thioether ketones)54, 58 and poly(thioether sulfones) 59. It is worth mentioning that poly(arylene thioethers), including also poly(thioether ketones), have higher hydrophobicity, flame resistance and refractive index than the corresponding poly(arylene ethers), for example, poly(phenylene oxide) or poly(ether ketones) (PEKs).…”

“…It is worth mentioning that, in contrast to the “monomer route” (i.e., the use of sulfone‐containing monomers), at the beginning of the '70s a “polymer route” to polysulfones was proposed (Figure 3), which allowed to convert preformed aromatic polysulfides into the corresponding polysulfones by the help of hydrogen peroxide 59. Literature offers a number of later examples of this approach, which has been applied to the oxidation of aliphatic [such as poly(thietane),75 poly(ethylene sulfide)153, 154 and poly(hexene sulfide)155] and aromatic55, 57, 156 polysulfides to polysulfones.…”

Cesium fluoride-mediated synthesis of aromatic polysulfides from aromatic dithiols and activated aromatic dihalides

“…of CsF at 130 8C for 4 h readily afforded aromatic polysulfide 3 b with high inherent viscosity of 0.67 dL/g (see Experimental part). The polycondensation proceeded under essentially neutral and milder conditions, compared with those for the conventional synthesis of aromatic polysulfides using potassium carbonate (for example, at 150 -160 8C for 3 -24 h) [3][4][5][6] . In addition, these polymerization conditions were milder than those for the CsF-assisted synthesis of aromatic polyethers with high molecular weights from bisphenols and activated aromatic dihalides (for example, at 160 8C for 4 h) 10) .…”

“…PPS is produced by the high-temperature solution polycondensation of p-dichlorobenzene with sodium sulfide, while a number of aromatic polysulfides are usually synthesized from monomer pairs of aromatic dithiols and activated aromatic dihalides 1,2) . The solution polycondensation using anhydrous potassium or sodium carbonate [3][4][5][6] and the phase-transfer-catalyzed polycondensation 7) have been reported as typical synthetic methods of aromatic polysulfides. Still another method using potassium fluoride as the base has been known as a more simple synthetic route 8,9) , because this method does not require the removal of water during the preparation of potassium salts of dithiols from the reaction system prior to the polycondensation.…”

Novel synthesis of macrocyclic disulfides from poly(phenylene sulfide) by depolymerization reaction

“…However, aromatic dithiols are rather difficult to synthesize because of the characteristic of easily being oxidized. Three different methodologies have been reported for the preparation of aromatic dithiols from various aromatic compounds, including (1) reduction reaction of aryldisulfonyl chlorides, (2) Newman‐Kwart rearrangement reaction of bis( N , N ‐dimethylthiocarbamate), and (3) nucleophilic substitution reaction of dichloride compounds with NaHS 4–9. The main disadvantages of above methods are: (1) low yield of (<30%) for the first method, and severely corrosive reagent of aryldisulfonyl chlorides used; (2) high cost of synthesis for the other two methods due to too many synthetic steps involved.…”