{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T14:46:25Z","timestamp":1790347585076,"version":"4.1.0"},"reference-count":36,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2022,12,15]],"date-time":"2022-12-15T00:00:00Z","timestamp":1671062400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Regional Development Fund, and the National Research, Development and Innovation Office, Hungary","award":["K135946"],"award-info":[{"award-number":["K135946"]}]},{"name":"European Regional Development Fund, and the National Research, Development and Innovation Office, Hungary","award":["PD128612"],"award-info":[{"award-number":["PD128612"]}]},{"name":"European Regional Development Fund, and the National Research, Development and Innovation Office, Hungary","award":["K124544"],"award-info":[{"award-number":["K124544"]}]},{"name":"European Regional Development Fund, and the National Research, Development and Innovation Office, Hungary","award":["VEKOP-2.3.2-16-2017-00013"],"award-info":[{"award-number":["VEKOP-2.3.2-16-2017-00013"]}]},{"name":"European Union and the State of Hungary","award":["K135946"],"award-info":[{"award-number":["K135946"]}]},{"name":"European Union and the State of Hungary","award":["PD128612"],"award-info":[{"award-number":["PD128612"]}]},{"name":"European Union and the State of Hungary","award":["K124544"],"award-info":[{"award-number":["K124544"]}]},{"name":"European Union and the State of Hungary","award":["VEKOP-2.3.2-16-2017-00013"],"award-info":[{"award-number":["VEKOP-2.3.2-16-2017-00013"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Novel poly(dithiophosphate)s (PDTPs) were successfully synthesized under mild conditions without any additive in the presence of THF or toluene diluents at 60 \u00b0C 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 \u22124 to \u221250 \u00b0C, 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.<\/jats:p>","DOI":"10.3390\/ijms232415963","type":"journal-article","created":{"date-parts":[[2022,12,15]],"date-time":"2022-12-15T04:25:26Z","timestamp":1671078326000},"page":"15963","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"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"],"prefix":"10.3390","volume":"23","author":[{"given":"\u00c1kos","family":"Szab\u00f3","sequence":"first","affiliation":[{"name":"Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gy\u00f6rgyi","family":"Szarka","sequence":"additional","affiliation":[{"name":"Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3960-1829","authenticated-orcid":false,"given":"L\u00e1szl\u00f3","family":"Trif","sequence":"additional","affiliation":[{"name":"Functional Nanoparticles Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Benj\u00e1min","family":"Gyarmati","sequence":"additional","affiliation":[{"name":"Soft Matters Group, Department of Physical Chemistry and Materials Science, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, M\u0171egyetem rkp. 3, H-1111 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0615-4361","authenticated-orcid":false,"given":"Laura","family":"Bereczki","sequence":"additional","affiliation":[{"name":"Plasma Chemistry Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"},{"name":"Chemical Crystallography Research Laboratory, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2475-6841","authenticated-orcid":false,"given":"B\u00e9la","family":"Iv\u00e1n","sequence":"additional","affiliation":[{"name":"Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3939-6925","authenticated-orcid":false,"given":"Ervin","family":"Kov\u00e1cs","sequence":"additional","affiliation":[{"name":"Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tud\u00f3sok krt. 2, H-1117 Budapest, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,12,15]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"101366","DOI":"10.1016\/j.progpolymsci.2021.101366","article-title":"Phosphorus-containing flame retardant epoxy thermosets: Recent advances and future perspectives","volume":"114","author":"Huo","year":"2021","journal-title":"Prog. Polym. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Liu, Y., and Zhang, P. (2022). Review of Phosphorus-Based Polymers for Mineral Scale and Corrosion Control in Oilfield. Polymers, 14.","DOI":"10.3390\/polym14132673"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"110151","DOI":"10.1016\/j.eurpolymj.2020.110151","article-title":"Phosphorus-containing star-shaped polymer conjugates for biomedical applications","volume":"142","author":"Todorova","year":"2021","journal-title":"Eur. Polym. J."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"6107","DOI":"10.1021\/jacs.2c02076","article-title":"Cross-Linked Polyphosphazene Nanospheres Boosting Long-Lived Organic Room-Temperature Phosphorescence","volume":"144","author":"Zhang","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"124761","DOI":"10.1016\/j.polymer.2022.124761","article-title":"Metallocene and other transition metal derivatives of phosphazene oligomers and polymers: A retrospective summary","volume":"249","author":"Allcock","year":"2022","journal-title":"Polymer"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2203006","DOI":"10.1002\/adfm.202203006","article-title":"Phosphorus-fixed stable interfacial nonflammable gel polymer electrolyte for safe flexible lithium-ion batteries","volume":"32","author":"Mu","year":"2022","journal-title":"Adv. Funct. Mater."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2100523","DOI":"10.1002\/mabi.202100523","article-title":"Phosphorus-Containing Polymeric Zwitterion: A Pioneering Bioresponsive Probe for 31P-Magnetic Resonance Imaging","volume":"22","author":"Pompach","year":"2022","journal-title":"Macromol. Biosci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5797","DOI":"10.1021\/jm020309o","article-title":"Immobilization of Aminothiols on Poly(oxyalkylene phosphates). Formation of Poly(oxyethylene phosphates)\/Cysteamine Complexes and Their Radioprotective Efficiency","volume":"45","author":"Georgieva","year":"2002","journal-title":"J. Med. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"16196","DOI":"10.1039\/D1NJ02480A","article-title":"Efficient removal of Pb(II) and Cr(VI) from acidic wastewater using porous thiophosphoryl polyethyleneimine","volume":"45","author":"Sun","year":"2021","journal-title":"New J. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"110931","DOI":"10.1016\/j.eurpolymj.2021.110931","article-title":"Ultrafast synthesis of phosphorus-containing polythioethers in the presence of TBD","volume":"162","author":"Daglar","year":"2022","journal-title":"Eur. Polym. J."},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Zhang, X.H., and Theato, P. (2021). Sulfur-Containing Polymers: From Synthesis to Functional Materials, John Wiley-VCH.","DOI":"10.1002\/9783527823819"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1021\/jacs.1c09329","article-title":"Polymerizations with elemental sulfur: From petroleum refining to polymeric materials","volume":"144","author":"Lee","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"110387","DOI":"10.1016\/j.eurpolymj.2021.110387","article-title":"Sulfur-based oxidation-responsive polymers. Chemistry, (chemically selective) responsiveness and biomedical applications","volume":"149","author":"Geven","year":"2021","journal-title":"Eur. Polym. J."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2000695","DOI":"10.1002\/marc.202000695","article-title":"Elemental Sulfur Mediated Novel Multicomponent Redox Polycondensation for the Synthesis of Alternating Copolymers Based on 2,4-Thiophene\/Arene Repeating Units","volume":"42","author":"Mutlu","year":"2021","journal-title":"Macromol. Rapid Commun."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5019","DOI":"10.1039\/D2PY00850E","article-title":"Polymers from S-vinyl monomers: Reactivities and properties","volume":"13","author":"Ziegenbalg","year":"2022","journal-title":"Polym. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"e202114896","DOI":"10.1002\/anie.202114896","article-title":"Inverse Vulcanization of Norbornenylsilanes: Soluble Polymers with Controllable Molecular Properties via Siloxane Bonds","volume":"61","author":"Scheiger","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Ceneviva, L.V.S., Mierzati, M., Miyahara, Y., Nomura, C.T., Taguchi, S., Abe, H., and Tsuge, T. (2022). Poly(3-mercapto-2-methylpropionate), a Novel \u03b1-Methylated Bio-Polythioester with Rubber-like Elasticity, and Its Copolymer with 3-hydroxybutyrate: Biosynthesis and Characterization. Bioengineering, 9.","DOI":"10.3390\/bioengineering9050228"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"e202202005","DOI":"10.1002\/anie.202202005","article-title":"Click Synthesis Enabled Sulfur Atom Strategy for Polymerization-Enhanced and Two-Photon Photosensitization","volume":"61","author":"Li","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"110202","DOI":"10.1016\/j.eurpolymj.2020.110202","article-title":"Preparation and characterization of sulfur-vinylbenzyl chloride polymer under optimized reaction conditions using inverse vulcanization","volume":"143","author":"Abbasi","year":"2021","journal-title":"Eur. Polym. J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"375","DOI":"10.1002\/prac.18600790154","article-title":"Die Ersetzung des Sauerstoffs durch Schwefel in organischen Verbindungen","volume":"79","author":"Carius","year":"1860","journal-title":"J. Prakt. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1662","DOI":"10.1021\/ja01226a014","article-title":"Chemistry of the Aliphatic Estersof Thiophosphoric acids. I","volume":"67","author":"Mastin","year":"1945","journal-title":"J. Am. Chem. Soc."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1007\/s00170-021-08614-x","article-title":"Extreme pressure and antiwear additives for lubricant: Academic insights and perspectives","volume":"120","author":"Li","year":"2022","journal-title":"Int. J. Adv. Manuf. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"469","DOI":"10.1023\/B:TRIL.0000044495.26882.b5","article-title":"The history and mechanisms of ZDDP","volume":"17","author":"Spikes","year":"2004","journal-title":"Tribol. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"177","DOI":"10.1002\/ls.1324","article-title":"A study on tribological behaviours of ZDDP in polymer thickened lubricating greases","volume":"28","author":"Dixena","year":"2016","journal-title":"Lubr. Sci."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"107466","DOI":"10.1016\/j.mineng.2022.107466","article-title":"A novel surfactant O,O\u2019-bis(2-butoxyethyl) ammonium dithiophosphate: Synthesis, selective flotation and adsorption mechanism towards galena","volume":"179","author":"Zou","year":"2022","journal-title":"Miner. Eng."},{"key":"ref_26","first-page":"778","article-title":"Chelation of heavy metals by potassium butyl dithiophosphate","volume":"23","author":"Xu","year":"2011","journal-title":"J. Environ. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3419","DOI":"10.1021\/cr900243d","article-title":"A Berzelius Reagent, Phosphorus Decasulfide (P4S10), in Organic Syntheses","volume":"110","author":"Ozturk","year":"2010","journal-title":"Chem. Rev."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"133166","DOI":"10.1016\/j.molstruc.2022.133166","article-title":"Synthesis, experimental and theoretical analyses of bis(2-ethylphenyl)phosphorodithioates of nickel(II)","volume":"1263","author":"Sharma","year":"2022","journal-title":"J. Mol. Struct."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1908","DOI":"10.1002\/ejic.201601541","article-title":"Mechanochemical Reactivity of Square-Planar Nickel Complexes and Pyridyl-Based Spacers for the Solid-State Preparation of Coordination Polymers: The Case of Nickel Diethyldithiophosphate and 4,4\u2032-Bipyridine","volume":"13","author":"Cabras","year":"2017","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_30","first-page":"1118","article-title":"Polyperesterification of diethyl ester of dithiophosphoric acid with glycols","volume":"9","author":"Pudovik","year":"1967","journal-title":"Vysokomol. Soyed."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"44","DOI":"10.1016\/j.progpolymsci.2015.01.001","article-title":"Reactions of H3PO4 forming polymers. Apparently simple reactions leading to sophisticated structures and applications","volume":"45","author":"Penczek","year":"2015","journal-title":"Prog. Polym. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"830","DOI":"10.1002\/pola.22427","article-title":"Formation of Poly(ethylene phosphates) in Polycondensation of H3PO4 with Ethylene Glycol. Kinetic and Mechanistic Study","volume":"46","author":"Pretula","year":"2008","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1016\/0584-8539(69)80170-4","article-title":"Vibrational spectroscopic study of organophosphorus compounds: P-S-H and P-H groups","volume":"25","author":"Nyquist","year":"1969","journal-title":"Spectrochim. Acta"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"11883","DOI":"10.1021\/acs.jafc.9b04398","article-title":"Characterization of Dialkyldithiophosphates as Slow Hydrogen Sulfide Releasing Chemicals and Their Effect on the Growth of Maize","volume":"67","author":"Carter","year":"2019","journal-title":"J. Agric. Food Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"265","DOI":"10.1039\/p29950000265","article-title":"Phosphorus-31 NMR Investigation of the Heterogeneous Hydrolytic Decomposition of Zinc(lI) Bis(O,O-Dialkyl Dithiophosphate) Lubricant Additives","volume":"2","author":"Burn","year":"1995","journal-title":"J. Chem. Soc. Perkin Trans."},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Rubinstein, M., and Colby, R.H. (2003). Polymer Physics, Oxford University Press. [1st ed.].","DOI":"10.1093\/oso\/9780198520597.001.0001"}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/24\/15963\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:41:49Z","timestamp":1760146909000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/24\/15963"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,12,15]]},"references-count":36,"journal-issue":{"issue":"24","published-online":{"date-parts":[[2022,12]]}},"alternative-id":["ijms232415963"],"URL":"https:\/\/doi.org\/10.3390\/ijms232415963","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,12,15]]}}}