Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide

Abstract

Novel poly(dithiophosphate)s (PDTPs) were successfully synthesized under mild conditions without any additive in the presence of THF or toluene diluents at 60 °C by a direct, catalyst-free reaction between the abundant phosphorus pentasulfide (P4S10) and glycols such as ethylene glycol (EG), 1,6-hexanediol (HD) and poly(ethylene glycol) (PEG). GPC, FTIR, 1H and 31P NMR analyses proved the formation of macromolecules with dithiophosphate coupling groups having P=S and P-SH pendant functionalities. Surprisingly, the ring-opening of THF by the P-SH group and its pendant incorporation as a branching point occur during polymerization. This process is absent with toluene, providing conditions to obtain linear chains. 31P NMR measurements indicate long-time partial hydrolysis and esterification, resulting in the formation of a thiophosphoric acid moiety and branching points. Copolymerization, i.e., using mixtures of EG or HD with PEG, results in polymers with broadly varying viscoelastic properties. TGA shows the lower thermal stability of PDTPs than that of PEG due to the relatively low thermal stability of the P-O-C moieties. The low Tgs of these polymers, from −4 to −50 °C, and a lack of PEG crystallites were found by DSC. This polymerization process and the resulting novel PDTPs enable various new routes for polymer synthesis and application possibilities.

Additive-free aerobic oxidative difunctionalization of alkenes with P4S10 and alcohols to access β-hydroxy phosphorodithioates

“…On the basis of the above experiments and referring to previous reports, 13,[17][18][19] a possible reaction mechanism was proposed as shown in Scheme 4. First, the reaction of P 4 S 10 with EtOH gave the O,O-diethyl S-hydrogen phosphorodithioate 5a.…”

“…First, the reaction of P 4 S 10 with EtOH gave the O,O-diethyl S-hydrogen phosphorodithioate 5a. 13,17 Subsequently, 5a was oxidized by dioxygen in air to afford the thiyl radical 6a along with the generation of hydroperoxide radical species. 18 Then, the selective addition of radical 6a to styrene 1a produced alkyl radical 7a, which was trapped by the hydroperoxide radical to form the hydroperoxide intermediate 8a.…”

Construction of β-Oximino Phosphorodithioates via (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl-Promoted Difunctionalization of Alkenes with tert-Butyl Nitrite, P4S10, and Alcohols

“…On the basis of the above experiments and previous reports, − ,, a possible reaction mechanism was demonstrated in Scheme . First, O , O -diethyl S -hydrogen phosphorodithioate 6a was formed through the reaction of P 4 S 10 with EtOH.…”