Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, Hungary.
Functional Nanoparticles Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, Hungary.
Int J Mol Sci. 2022 Dec 15;23(24):15963. doi: 10.3390/ijms232415963.
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 (PS) and glycols such as ethylene glycol (EG), 1,6-hexanediol (HD) and poly(ethylene glycol) (PEG). GPC, FTIR, H and P 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. P 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 s 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.
新型聚二硫代磷酸酯（PDTPs）在温和条件下成功合成，无需添加任何添加剂，在 60°C 下，在四氢呋喃或甲苯稀释剂的存在下，通过丰富的五硫化二磷（PS）与乙二醇（EG）、1,6-己二醇（HD）和聚乙二醇（PEG）等二醇之间的直接、无催化剂反应来实现。GPC、FTIR、H 和 P NMR 分析证明了具有二硫代磷酸酯偶联基团的大分子的形成，这些基团具有 P=S 和 P-SH 侧基功能。令人惊讶的是，P-SH 基团打开 THF 的环并将其作为支化点并入聚合过程中。该过程在甲苯中不存在，为获得线性链提供了条件。P NMR 测量表明长时间部分水解和酯化，导致形成硫代磷酸部分和支化点。共聚，即使用 EG 或 HD 与 PEG 的混合物，导致具有广泛变化的粘弹性质的聚合物。TGA 表明 PDTPs 的热稳定性低于 PEG，因为 P-O-C 部分的热稳定性相对较低。这些聚合物的低玻璃化转变温度（Tg）为-4 至-50°C，通过 DSC 发现缺乏 PEG 结晶。这种聚合过程和由此产生的新型 PDTPs 为聚合物合成和应用可能性开辟了各种新途径。
