{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T02:45:21Z","timestamp":1760237121491,"version":"build-2065373602"},"reference-count":20,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2020,3,5]],"date-time":"2020-03-05T00:00:00Z","timestamp":1583366400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>In the present article, we report on the chemical modifications of some carbohydrate-based substrates, such as potato starch, dextran, \u03b2-cyclodextrin, agar agar and tamarind, by reacting with diethylchlorophosphate (DECP), in dispersions in dichloromethane (DCM), in the presence of triethylamine (TEA) as the base. The modified substrates, after recovery and purification, were analyzed for their chemical constitutions, thermal stabilities and calorimetric properties using a variety of analytical techniques. These included: solid-state 31P NMR, inductively coupled plasma-optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The unmodified counterparts were also subjected to the same set of analyses with a view to serving as controls. Phosphorus analyses, primarily through ICP-OES on the recovered samples, showed different degrees of incorporation. Such observations were optionally verified through solid-state 31P NMR spectroscopy. The thermograms of the modified substrates were noticeably different from the unmodified counterparts, both in terms of the general profiles and the amounts of char residues produced. Such observations correlated well with the relevant parameters obtained through PCFC runs. Overall, the modified systems containing phosphorus were found to be less combustible than the parent substrates, and thus can be considered as promising matrices for environmentally benign fire-resistant coatings.<\/jats:p>","DOI":"10.3390\/polym12030588","type":"journal-article","created":{"date-parts":[[2020,3,6]],"date-time":"2020-03-06T07:33:46Z","timestamp":1583480026000},"page":"588","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Thermal and Calorimetric Evaluations of Some Chemically Modified Carbohydrate-Based Substrates with Phosphorus-Containing Groups"],"prefix":"10.3390","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6644-5895","authenticated-orcid":false,"given":"Ananya","family":"Thomas","sequence":"first","affiliation":[{"name":"Institute for Sustainable Industries and Liveable Cities, Victoria University, P.O. Box 14428, Melbourne, VIC 8001, Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5503-9979","authenticated-orcid":false,"given":"Paul","family":"Joseph","sequence":"additional","affiliation":[{"name":"Institute for Sustainable Industries and Liveable Cities, Victoria University, P.O. Box 14428, Melbourne, VIC 8001, Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1831-6754","authenticated-orcid":false,"given":"Khalid","family":"Moinuddin","sequence":"additional","affiliation":[{"name":"Institute for Sustainable Industries and Liveable Cities, Victoria University, P.O. Box 14428, Melbourne, VIC 8001, Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6352-7633","authenticated-orcid":false,"given":"Haijin","family":"Zhu","sequence":"additional","affiliation":[{"name":"Institute for Frontier Materials, Deakin University, Melbourne, VIC 3125, Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1012-0597","authenticated-orcid":false,"given":"Svetlana","family":"Tretsiakova-McNally","sequence":"additional","affiliation":[{"name":"Belfast School of Architecture and the Built Environment, Ulster University, Newtownabbey BT37 0QB, Northern Ireland, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,3,5]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.mser.2017.04.001","article-title":"Bio-based flame retardants: When nature meets fire protection","volume":"117","author":"Costes","year":"2017","journal-title":"Mater. Sci. Eng. R Rep."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"713","DOI":"10.1021\/ie1017157","article-title":"Flame retardancy and thermal degradation of intumescent flame retardant poly (lactic acid)\/starch biocomposites","volume":"50","author":"Wang","year":"2010","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1016\/S0141-3910(00)00102-6","article-title":"Chemical modification of starch based biodegradable polymeric blends: Effects on water uptake, degradation behaviour and mechanical properties","volume":"70","author":"Elvira","year":"2000","journal-title":"Polym. Degrad. Stab."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1002\/fam.810060203","article-title":"Action of phosphorus compounds on fire-retardancy of cellulosic materials: A review","volume":"6","author":"Kishore","year":"1982","journal-title":"Fire Mater."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1619","DOI":"10.1002\/(SICI)1097-4628(19960307)59:10<1619::AID-APP14>3.0.CO;2-R","article-title":"Synthesis and flame-retardant properties of phosphorus-containing polymers based on poly (4-hydroxystyrene)","volume":"59","author":"Liu","year":"1996","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"138","DOI":"10.1016\/j.polymdegradstab.2004.02.023","article-title":"Flame retardancy of biodegradable polymers and biocomposites","volume":"88","author":"Matko","year":"2005","journal-title":"Polym. Degrad. Stab."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"46","DOI":"10.1002\/masy.201400152","article-title":"The Synthesis of Bio-Based Flame-Retarded Epoxy-Precursors","volume":"352","author":"Keglevich","year":"2015","journal-title":"Macromol. Symp."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"445","DOI":"10.1016\/S1360-1385(02)02332-4","article-title":"Starch phosphorylation: A new front line in starch research","volume":"7","author":"Blennow","year":"2002","journal-title":"Trends Plant Sci."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"621","DOI":"10.1002\/star.200900168","article-title":"Starch phosphate hydrogels. Part I: Synthesis by mono-phosphorylation and cross-linking of starch","volume":"61","author":"Passauer","year":"2009","journal-title":"Starch St\u00e4rke"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"85","DOI":"10.1016\/S0144-8617(99)00120-4","article-title":"Effect of pH on phosphorylation of sago starch","volume":"42","author":"Muhammad","year":"2000","journal-title":"Carbohydr. Polym."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1016\/S0144-8617(99)00082-X","article-title":"Starch molecular structure and phosphorylation investigated by a combined chromatographic and chemometric approach","volume":"41","author":"Blennow","year":"2000","journal-title":"Carbohydr. Polym."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1177\/0734904106068426","article-title":"A review of recent progress in phosphorus-based flame retardants","volume":"24","author":"Levchik","year":"2006","journal-title":"J. Fire Sci."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"426","DOI":"10.1177\/073490419601400602","article-title":"Mechanisms for flame retardancy and smoke suppression-a review","volume":"14","author":"Green","year":"1996","journal-title":"J. Fire Sci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/j.polymdegradstab.2003.10.024","article-title":"Developments in flame retardant textiles\u2014A review","volume":"88","author":"Horrocks","year":"2005","journal-title":"Polym. Degrad. Stab."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1016\/S0141-3910(96)00038-9","article-title":"Developments in flame retardants for heat and fire resistant textiles\u2014The role of char formation and intumescence","volume":"54","author":"Horrocks","year":"1996","journal-title":"Polym. Degrad. Stab."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/S0165-2370(03)00096-2","article-title":"Pyrolysis combustion flow calorimetry","volume":"71","author":"Lyon","year":"2004","journal-title":"J. Anal. Appl. Pyrolysis"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"395","DOI":"10.1002\/pat.1900","article-title":"Reactive modifications of some chain-and step-growth polymers with phosphorus-containing compounds: Effects on flame retardance\u2014A review","volume":"22","author":"Joseph","year":"2011","journal-title":"Polym. Adv. Technol."},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Tretsiakova-McNally, S., and Joseph, P. (2018). Thermal and calorimetric evaluations of polyacrylonitrile containing covalently-bound phosphonate groups. Polymers, 10.","DOI":"10.3390\/polym10020131"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"453","DOI":"10.3390\/polym7030453","article-title":"Pyrolysis combustion flow calorimetry studies on some reactively modified polymers","volume":"7","author":"Joseph","year":"2015","journal-title":"Polymers"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2531","DOI":"10.1016\/j.polymdegradstab.2012.07.014","article-title":"Combustion behaviours of chemically modified polyacrylonitrile polymers containing phosphorylamino groups","volume":"97","author":"Joseph","year":"2012","journal-title":"Polym. Degrad. Stab."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/12\/3\/588\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:04:26Z","timestamp":1760173466000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/12\/3\/588"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,3,5]]},"references-count":20,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2020,3]]}},"alternative-id":["polym12030588"],"URL":"https:\/\/doi.org\/10.3390\/polym12030588","relation":{},"ISSN":["2073-4360"],"issn-type":[{"type":"electronic","value":"2073-4360"}],"subject":[],"published":{"date-parts":[[2020,3,5]]}}}