{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T16:33:59Z","timestamp":1789662839521,"version":"4.0.1"},"reference-count":40,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2020,5,28]],"date-time":"2020-05-28T00:00:00Z","timestamp":1590624000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["19-73-10204"],"award-info":[{"award-number":["19-73-10204"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>With the aim of obtaining halogen-free polybenzoxazazines with reduced flammability, phosphazene-containing benzoxazines (PhBZ) were synthesized in a two-stage method. In the first stage of the reaction of hexachlorocycotriphosphazene with bisphenol A at molar ratios of 1:12, 1:16, and 1:24, respectively, mixtures of bisphenol and hydroxyaryloxycyclotriphosphazenes were obtained, which mainly contained P3N3[OC6H4C(CH3)3C6H4OH]6. In the second stage, when these mixtures interacted with aniline and an excess of paraformaldehyde in toluene at 80\u201390 \u00b0C, PhBZ containing 20\u201350% of the phosphazene component with Mw 1200\u20135800 were formed. According to 1H and 13C NMR spectroscopy, PhBZ contain a small amount of oligomeric compounds with Mannich aminomethylene bridges. With an increase of the content of the phosphazene component, the curing temperature of PhBZ decreases from 242 \u00b0C to 215 \u00b0C. Cured PhBZ samples with a phosphorus content of more than 1.5% have increased flammability resistance according to UL-94.<\/jats:p>","DOI":"10.3390\/polym12061225","type":"journal-article","created":{"date-parts":[[2020,5,29]],"date-time":"2020-05-29T02:16:27Z","timestamp":1590718587000},"page":"1225","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Synthesis of Phosphazene-Containing, Bisphenol A-Based Benzoxazines and Properties of Corresponding Polybenzoxazines"],"prefix":"10.3390","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1442-2039","authenticated-orcid":false,"given":"Igor S.","family":"Sirotin","sequence":"first","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9495-3416","authenticated-orcid":false,"given":"Igor A.","family":"Sarychev","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Viktoria V.","family":"Vorobyeva","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anastasia A.","family":"Kuzmich","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalia V.","family":"Bornosuz","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Denis V.","family":"Onuchin","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Irina Yu.","family":"Gorbunova","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vyacheslav V.","family":"Kireev","sequence":"additional","affiliation":[{"name":"Mendeleev University of Chemical Technology of Russia, 125047, Miusskaya sq. 9, Moscow 125047, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,5,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1413","DOI":"10.1002\/(SICI)1097-4628(19981114)70:7<1413::AID-APP16>3.0.CO;2-0","article-title":"Study of the characterization and curing of benzoxazines using 13C solid-state nuclear magnetic resonance","volume":"70","author":"Russell","year":"1998","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3271","DOI":"10.1021\/jp010606p","article-title":"A study on hydrogen-bonded network structure of polybenzoxazines","volume":"106","author":"Kim","year":"2002","journal-title":"J. Phys. Chem. A"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1002\/marc.200500779","article-title":"Fabrication of Biomimetic Super-Amphiphobic Surfaces Through Plasma Modification of Benzoxazine Films","volume":"27","author":"Wang","year":"2006","journal-title":"Macromol. Rapid Commun."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1121","DOI":"10.1295\/polymj.PJ2008072","article-title":"High Performance Polybenzoxazines as a Novel Type of Phenolic Resin","volume":"40","author":"Takeichi","year":"2008","journal-title":"Polym. J."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"58821","DOI":"10.1039\/C5RA07606D","article-title":"The effect of bis allyl benzoxazine on the thermal, mechanical and dielectric properties of bismaleimide\u2013cyanate blend polymers","volume":"5","author":"Wang","year":"2015","journal-title":"RSC Adv."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"354","DOI":"10.1016\/j.eurpolymj.2009.09.013","article-title":"Bis(benzoxazine-maleimide)s as a novel class of high performance resin: Synthesis and properties","volume":"46","author":"Jin","year":"2010","journal-title":"Eur. Polym. J."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Li, S., and Zou, T. (2012). Synthesis, Characterization of New Carboxylic Acid-Containing Benzoxazine and Its Cocuring Behaviors with Bisoxazoline. J. Appl. Polym. Sci., 123.","DOI":"10.1002\/app.34535"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"7257","DOI":"10.1021\/ma0107915","article-title":"Novel Benzoxazine Monomers Containing p-Phenyl Propargyl Ether:\u2009 Polymerization of Monomers and Properties of Polybenzoxazines","volume":"34","author":"Agag","year":"2001","journal-title":"Macromolecules"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8412","DOI":"10.1021\/acs.macromol.5b02285","article-title":"Synthesis and Characterization of Cyanate Ester Functional Benzoxazine and Its Polymer","volume":"48","author":"Ohashi","year":"2015","journal-title":"Macromolecules"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Zhang, H., and Lu, Z. (2010). Synthesis and characterization of novel benzoxazines containing nitrile and allyl groups and their polymers. e-Polymers, 10.","DOI":"10.1515\/epoly.2010.10.1.1578"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"971","DOI":"10.1177\/0954008315612139","article-title":"Preparation and characterization of novel polybenzoxazine hybrid materials","volume":"28","author":"Chiu","year":"2016","journal-title":"High Perform. Polym."},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Mohamed, M.G., and Kuo, S.-W. (2016). Polybenzoxazine\/Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites. Polymers, 8.","DOI":"10.3390\/polym8060225"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1007\/BF00486222","article-title":"New materials based on the reaction of cyclo- and poly-(organo phosphazenes) with SiO2, TiO2 and ZrO2 precursors","volume":"2","author":"Guglielmi","year":"1994","journal-title":"J. Sol Gel Sci. Technol."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"6555","DOI":"10.1039\/C5NJ00364D","article-title":"Development of halogen-free flame retardant phosphazene and rice husk ash incorporated benzoxazine blended epoxy composites for microelectronic applications","volume":"39","author":"Krishnadevi","year":"2015","journal-title":"N. J. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4047","DOI":"10.1021\/am300843c","article-title":"Novel Spirocyclic Phosphazene-Based Epoxy Resin for Halogen-Free Fire Resistance: Synthesis, Curing Behaviors, and Flammability Characteristics","volume":"4","author":"Sun","year":"2012","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4710","DOI":"10.3390\/ma3104710","article-title":"Phosphorus-based Flame Retardancy Mechanisms\u2014Old Hat or a Starting Point for Future Development?","volume":"3","author":"Schartel","year":"2010","journal-title":"Materials"},{"key":"ref_17","first-page":"216","article-title":"Phosphazenes","volume":"Volume 42","author":"Allen","year":"2013","journal-title":"Organophosphorus Chemistry"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"286","DOI":"10.1134\/S1560090419030084","article-title":"Physicochemical Properties of Epoxy Composites Modified with Epoxyphosphazene","volume":"61","author":"Onuchin","year":"2019","journal-title":"Polym. Sci. Ser. B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"45467","DOI":"10.1002\/app.45467","article-title":"Fluorine containing self-crosslinking acrylic latexes with reduced flammability and their application as polymer binders for heterogeneous cation-exchange membranes","volume":"134","author":"Machotova","year":"2017","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1004","DOI":"10.1016\/j.polymer.2011.01.003","article-title":"Highly branched benzoxazine monomer based on cyclotriphosphazene: Synthesis and properties of the monomer and polybenzoxazines","volume":"52","author":"Wu","year":"2011","journal-title":"Polymer"},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Ma, H.-X., Zhao, C., Qiu, J.-J., Liu, Y., and Liu, C.-M. (2017). Synthesis of branched benzoxazine monomers with high molecular mass, wide processing window, and properties of corresponding polybenzoxazines. J. Appl. Polym. Sci., 134.","DOI":"10.1002\/app.44453"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"389","DOI":"10.1021\/acssuschemeng.7b02657","article-title":"Eco-Friendly Halogen-Free Flame Retardant Cardanol Polyphosphazene Polybenzoxazine Networks","volume":"6","author":"Amarnath","year":"2018","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"906","DOI":"10.1177\/0954008314533980","article-title":"Synthesis and properties of main-chain oligomeric benzoxazine precursor containing cyclotriphosphazene units","volume":"26","author":"Tan","year":"2014","journal-title":"High Perform. Polym."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"4235","DOI":"10.1016\/j.polymer.2011.07.037","article-title":"Well-defined organic\u2013inorganic hybrid benzoxazine monomers based on cyclotriphosphazene: Synthesis, properties of the monomers and polybenzoxazines","volume":"52","author":"Wu","year":"2011","journal-title":"Polymer"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1134\/S1560090413020048","article-title":"Synthesis of oligomeric chlorophosphazenes in the presence of ZnCl2","volume":"55","author":"Sirotin","year":"2013","journal-title":"Polym. Sci. Ser. B"},{"key":"ref_26","unstructured":"Riddick, J.A., Bunger, W.B., and Sakano, T.K. (1986). Organic Solvents: Physical Properties and Methods of Purification, Wiley."},{"key":"ref_27","unstructured":"Gelman, N.E. (1987). Methods of Quantitative Organic Elemental Microanalysis, Khimiya."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2409","DOI":"10.1021\/ma970156s","article-title":"Synthesis and Characterization of Structurally Uniform Model Oligomers of Polybenzoxazine","volume":"31","author":"Ishida","year":"1998","journal-title":"Macromolecules"},{"key":"ref_29","unstructured":"Ishida, H. (1994). Process for preparation of benzoxazine compounds in solventless systems. (5,543,516), U.S. Patent."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1121","DOI":"10.1002\/pola.1994.080320614","article-title":"Phenolic materials via ring-opening polymerization: Synthesis and characterization of bisphenol-A based benzoxazines and their polymers","volume":"32","author":"Ning","year":"1994","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_31","unstructured":"Wang, D., and Kincaid, D.S. (2012). Method for Producing Benzoxazine Compounds. (20140148597), U.S. Patent Application."},{"key":"ref_32","unstructured":"Aizawa, T., Hirai, Y., and Numata, S. (2002). Method for producing benzoxazine resin. (20040138345), U.S. Patent Application."},{"key":"ref_33","unstructured":"Liu, J. (1995). Synthesis, Characterization, Reaction Mechanism and Kinetics of 3,4-dihydro-2H-1,3-benzoxazine and Its Polymer. [Ph.D. Thesis, Case Western Reserve University]."},{"key":"ref_34","first-page":"62","article-title":"Structural Study of Bisphenol-A Benzoxazine by Tandem Mass Analysis","volume":"560\u2013561","author":"Yoo","year":"2012","journal-title":"Adv. Mater. Res."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3346","DOI":"10.1039\/C5GC03102H","article-title":"Breaking the symmetry of dibenzoxazines: A paradigm to tailor the design of bio-based thermosets","volume":"18","author":"Puchot","year":"2016","journal-title":"Green Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1903","DOI":"10.1134\/S1070427213120161","article-title":"Oligomeric hydroxy-aryloxy phosphazene based on cyclic chlorophosphazenes","volume":"86","author":"Sirotin","year":"2013","journal-title":"Russ. J. Appl. Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1061","DOI":"10.1016\/0584-8539(94)00114-Q","article-title":"Vibrational assignments of 3-alkyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazines in the fingerprint region","volume":"51","author":"Dunkers","year":"1995","journal-title":"Spectrochim. Acta Part A Mol. Biomol. Spectrosc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"182","DOI":"10.1134\/S1560090418020069","article-title":"Features of Curing of a Diane Epoxy Oligomer Modified with Epoxyphosphazene","volume":"60","author":"Onuchin","year":"2018","journal-title":"Polym. Sci. Ser. B"},{"key":"ref_39","unstructured":"Van Krevelen, D.W., Krevelen, D.W., and Nijenhuis, K. (2009). Properties of Polymers: Their Correlation with Chemical Structure, Elsevier. Their Numerical Estimation and Prediction from Additive Group Contributions."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1417","DOI":"10.1007\/s00289-015-1345-0","article-title":"Performances improvement of traditional polybenzoxazines by copolymerizing with cyclotriphosphazene-based benzoxazine monomers","volume":"72","author":"Tan","year":"2015","journal-title":"Polym. Bull."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/12\/6\/1225\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:33:18Z","timestamp":1760175198000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/12\/6\/1225"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,5,28]]},"references-count":40,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2020,6]]}},"alternative-id":["polym12061225"],"URL":"https:\/\/doi.org\/10.3390\/polym12061225","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,5,28]]}}}