Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide
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 (P<sub>4</sub>S<sub>10</sub>) and...
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MDPI AG
2022-12-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/23/24/15963 |
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| author | Ákos Szabó Györgyi Szarka László Trif Benjámin Gyarmati Laura Bereczki Béla Iván Ervin Kovács |
| author_facet | Ákos Szabó Györgyi Szarka László Trif Benjámin Gyarmati Laura Bereczki Béla Iván Ervin Kovács |
| author_sort | Ákos Szabó |
| collection | DOAJ |
| description | 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 (P<sub>4</sub>S<sub>10</sub>) and glycols such as ethylene glycol (EG), 1,6-hexanediol (HD) and poly(ethylene glycol) (PEG). GPC, FTIR, <sup>1</sup>H and <sup>31</sup>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. <sup>31</sup>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 <i>T</i><sub>g</sub>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. |
| first_indexed | 2024-03-09T16:19:10Z |
| format | Article |
| id | doaj.art-d4f2818851474e6eabb1ee248288ef6e |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T16:19:10Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-d4f2818851474e6eabb1ee248288ef6e2023-11-24T15:30:31ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-12-0123241596310.3390/ijms232415963Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus PentasulfideÁkos Szabó0Györgyi Szarka1László Trif2Benjámin Gyarmati3Laura Bereczki4Béla Iván5Ervin Kovács6Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungaryPolymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungaryFunctional Nanoparticles Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungarySoft Matters Group, Department of Physical Chemistry and Materials Science, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, H-1111 Budapest, HungaryPlasma Chemistry Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungaryPolymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungaryPolymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok krt. 2, H-1117 Budapest, HungaryNovel 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 (P<sub>4</sub>S<sub>10</sub>) and glycols such as ethylene glycol (EG), 1,6-hexanediol (HD) and poly(ethylene glycol) (PEG). GPC, FTIR, <sup>1</sup>H and <sup>31</sup>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. <sup>31</sup>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 <i>T</i><sub>g</sub>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.https://www.mdpi.com/1422-0067/23/24/15963poly(dithiophosphate)phosphorus pentasulfidediolsTHF incorporationpolythiophosphatephosphorus-containing polymer |
| spellingShingle | Ákos Szabó Györgyi Szarka László Trif Benjámin Gyarmati Laura Bereczki Béla Iván Ervin Kovács Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide International Journal of Molecular Sciences poly(dithiophosphate) phosphorus pentasulfide diols THF incorporation polythiophosphate phosphorus-containing polymer |
| title | Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide |
| title_full | Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide |
| title_fullStr | Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide |
| title_full_unstemmed | Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide |
| title_short | Poly(dithiophosphate)s, a New Class of Phosphorus- and Sulfur-Containing Functional Polymers by a Catalyst-Free Facile Reaction between Diols and Phosphorus Pentasulfide |
| title_sort | poly dithiophosphate s a new class of phosphorus and sulfur containing functional polymers by a catalyst free facile reaction between diols and phosphorus pentasulfide |
| topic | poly(dithiophosphate) phosphorus pentasulfide diols THF incorporation polythiophosphate phosphorus-containing polymer |
| url | https://www.mdpi.com/1422-0067/23/24/15963 |
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