{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,10]],"date-time":"2026-08-10T23:06:57Z","timestamp":1786403217496,"version":"build-2736575974"},"reference-count":44,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2021,11,22]],"date-time":"2021-11-22T00:00:00Z","timestamp":1637539200000},"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>Global enhancement of crop yield is achieved using chemical fertilizers; however, agro-economy is affected due to poor nutrient uptake efficacy (NUE), which also causes environmental pollution. Encapsulating urea granules with hydrophobic material can be one solution. Additionally, the inverse vulcanized copolymer obtained from vegetable oils are a new class of green sulfur-enriched polymer with good biodegradation and better sulfur oxidation potential, but they possess unreacted sulfur, which leads to void generations. In this study, inverse vulcanization reaction conditions to minimize the amount of unreacted sulfur through response surface methodology (RSM) is optimized. The copolymer obtained was then characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). FTIR confirmed the formation of the copolymer, TGA demonstrated that copolymer is thermally stable up to 200 \u00b0C temperature, and DSC revealed the sulfur conversion of 82.2% (predicted conversion of 82.37%), which shows the goodness of the model developed to predict the sulfur conversion. To further maximize the sulfur conversion, 5 wt% diisopropenyl benzene (DIB) as a crosslinker is added during synthesis to produce terpolymer. The urea granule is then coated using terpolymer, and the nutrient release longevity of the coated urea is tested in distilled water, which revealed that only 65% of its total nutrient is released after 40 days of incubation. The soil burial of the terpolymer demonstrated its biodegradability, as 26% weight loss happens in 52 days of incubation. Thus, inverse vulcanized terpolymer as a coating material for urea demonstrated far better nutrient release longevity compared with other biopolymers with improved biodegradation; moreover, these copolymers also have potential to improve sulfur oxidation.<\/jats:p>","DOI":"10.3390\/polym13224040","type":"journal-article","created":{"date-parts":[[2021,12,1]],"date-time":"2021-12-01T02:34:05Z","timestamp":1638326045000},"page":"4040","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["A Degradable Inverse Vulcanized Copolymer as a Coating Material for Urea Produced under Optimized Conditions"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3239-9250","authenticated-orcid":false,"given":"Ali Shaan Manzoor","family":"Ghumman","sequence":"first","affiliation":[{"name":"Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 32610, Perak Darul Ridzuan, Malaysia"},{"name":"HICoE, Centre for Biofuel and Biochemical Research (CBBR), Institute of Sustainable Building, Universiti Teknologi PETRONAS, Seri Iskandar 32610, Perak, Malaysia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8683-596X","authenticated-orcid":false,"given":"Rashid","family":"Shamsuddin","sequence":"additional","affiliation":[{"name":"Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 32610, Perak Darul Ridzuan, Malaysia"},{"name":"HICoE, Centre for Biofuel and Biochemical Research (CBBR), Institute of Sustainable Building, Universiti Teknologi PETRONAS, Seri Iskandar 32610, Perak, Malaysia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0192-5107","authenticated-orcid":false,"given":"Mohamed Mahmoud","family":"Nasef","sequence":"additional","affiliation":[{"name":"Department of Chemical and Environmental Engineering, Malaysia Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, Kuala Lumpur 54100, Malaysia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Efrem G.","family":"Krivoborodov","sequence":"additional","affiliation":[{"name":"Institute of Chemistry and Sustainable Development, Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sohaira","family":"Ahmad","sequence":"additional","affiliation":[{"name":"Department of Electrical Engineering, Wah Engineering College, University of Wah, Wah Cantt 47040, Punjab, Pakistan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6195-3399","authenticated-orcid":false,"given":"Alexey A.","family":"Zanin","sequence":"additional","affiliation":[{"name":"Institute of Chemistry and Sustainable Development, Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yaroslav O.","family":"Mezhuev","sequence":"additional","affiliation":[{"name":"Institute of Chemistry and Sustainable Development, Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4212-1663","authenticated-orcid":false,"given":"Amin","family":"Abbasi","sequence":"additional","affiliation":[{"name":"Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 32610, Perak Darul Ridzuan, Malaysia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2021,11,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"8016","DOI":"10.1021\/es901162d","article-title":"Markets, Climate Change, and Food Security in West Africa","volume":"43","author":"Brown","year":"2009","journal-title":"Environ. Sci. Technol."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Chien, S., Prochnow, L., and Cantarella, H. (2009). Recent Developments of Fertilizer Production and Use to Improve Nutrient Efficiency and Minimize Environmental Impacts, Advances in Agronomy Academic Press. Chapter 8.","DOI":"10.1016\/S0065-2113(09)01008-6"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1016\/j.jconrel.2016.01.037","article-title":"Slow release coating remedy for nitrogen loss from conventional urea: A review","volume":"225","author":"Naz","year":"2016","journal-title":"J. Control. Release"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/j.jconrel.2017.12.017","article-title":"A review of mathematical modeling and simulation of controlled-release fertilizers","volume":"271","author":"Irfan","year":"2018","journal-title":"J. Control Release"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1016\/j.jconrel.2014.02.020","article-title":"Review on materials & methods to produce controlled release coated urea fertilizer","volume":"181","author":"Azeem","year":"2014","journal-title":"J. Control Release"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1039\/b903311d","article-title":"Interplay of metal ions and urease","volume":"1","author":"Carter","year":"2009","journal-title":"Metallomics"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"894","DOI":"10.1007\/s00284-010-9801-4","article-title":"Characterization of Urease and Carbonic Anhydrase Producing Bacteria and Their Role in Calcite Precipitation","volume":"62","author":"Achal","year":"2011","journal-title":"Curr. Microbiol."},{"key":"ref_8","first-page":"77","article-title":"Producing slow release urea by coating with Starch\/Acrylic Acid in fluid bed spraying","volume":"11","author":"Anggoro","year":"2011","journal-title":"Int. J. Eng. Technol."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"387","DOI":"10.1080\/03602559.2012.752831","article-title":"Preparation and Characterization of Biodegradable Cellulose Acetate-Starch Membrane","volume":"52","author":"Zarei","year":"2013","journal-title":"Polym. Technol. Eng."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"375206","DOI":"10.1155\/2014\/375206","article-title":"Characterization of Modified Tapioca Starch Solutions and Their Sprays for High Temperature Coating Applications","volume":"2014","author":"Naz","year":"2014","journal-title":"Sci. World J."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/S0065-2113(01)71011-5","article-title":"Advances in controlled-release fertilizers","volume":"71","author":"Shaviv","year":"2001","journal-title":"Adv. Agron."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"685","DOI":"10.1081\/DRT-120002824","article-title":"Coating of urea with an aqueous polymeric suspension in a two-dimensional spouted bed","volume":"20","author":"Donida","year":"2002","journal-title":"Dry. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"510","DOI":"10.1016\/j.partic.2011.01.004","article-title":"Experimental modeling of polymer latex spray coating for producing controlled-release urea","volume":"9","author":"Lan","year":"2011","journal-title":"Particuology"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"126","DOI":"10.1007\/s11595-012-0421-7","article-title":"Synthesis and performance of polyurethane coated urea as slow\/controlled release fertilizer","volume":"27","author":"Li","year":"2012","journal-title":"J. Wuhan Univ. Technol. Sci. Ed."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"11229","DOI":"10.1021\/jf302813g","article-title":"Improving the Quality of Polymer-Coated Urea with Recycled Plastic, Proper Additives, and Large Tablets","volume":"60","author":"Yang","year":"2012","journal-title":"J. Agric. Food Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"5415","DOI":"10.1016\/j.ces.2005.04.023","article-title":"Design of multi-layer coated particles with sigmoidal release pattern","volume":"60","author":"Ito","year":"2005","journal-title":"Chem. Eng. Sci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"915","DOI":"10.1016\/j.indcrop.2011.02.011","article-title":"Lignin based controlled release coatings","volume":"34","author":"Mulder","year":"2011","journal-title":"Ind. Crop. Prod."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3796","DOI":"10.1002\/app.27987","article-title":"Lignin and ethylcellulose as polymers in controlled release formulations of urea","volume":"108","year":"2008","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"518","DOI":"10.1038\/nchem.1624","article-title":"The use of elemental sulfur as an alternative feedstock for polymeric materials","volume":"5","author":"Chung","year":"2013","journal-title":"Nat. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"10467","DOI":"10.1039\/C5CC03419A","article-title":"Nanoparticle\u2013sulphur \u201cinverse vulcanisation\u201d polymer composites","volume":"51","author":"Bear","year":"2015","journal-title":"Chem. Commun."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"100158","DOI":"10.1016\/j.scp.2019.100158","article-title":"Copolymerization of vegetable oils and bio-based monomers with elemental sulfur: A new promising route for bio-based polymers","volume":"13","author":"Abbasi","year":"2019","journal-title":"Sustain. Chem. Pharm."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"15486","DOI":"10.1002\/anie.201604615","article-title":"Sulfur and Its Role in Modern Materials Science","volume":"55","author":"Boyd","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"172","DOI":"10.1680\/jgrma.19.00053","article-title":"Sulfur Based Polymers by Inverse Vulcanization: A Novel Path to Foster Green Chemistry","volume":"8","author":"Abbasi","year":"2020","journal-title":"Green Mater."},{"key":"ref_24","first-page":"1333","article-title":"Evaluation of properties of sulfur-based polymers obtained by inverse vulcanization: Techniques and challenges","volume":"29","author":"Ghumman","year":"2021","journal-title":"Polym. Polym. Compos."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"16219","DOI":"10.1002\/chem.201702871","article-title":"Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils","volume":"23","author":"Worthington","year":"2017","journal-title":"Chem. Eur. J."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1800024","DOI":"10.1002\/adsu.201800024","article-title":"Sustainable Polysulfides for Oil Spill Remediation: Repurposing Industrial Waste for Environmental Benefit","volume":"2","author":"Worthington","year":"2018","journal-title":"Adv. Sustain. Syst."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1929","DOI":"10.1039\/C8OB02130A","article-title":"Sulfur polymer composites as controlled-release fertilisers","volume":"17","author":"Mann","year":"2019","journal-title":"Org. Biomol. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1232","DOI":"10.1039\/C7RA11999B","article-title":"Polysulfides made from re-purposed waste are sustainable materials for removing iron from water","volume":"8","author":"Lundquist","year":"2018","journal-title":"RSC Adv."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/adsu.201900111","article-title":"Mercury Sorbents Made By Inverse Vulcanization of Sustainable Triglycerides: The Plant Oil Structure Influences the Rate of Mercury Removal from Water","volume":"4","author":"Tikoalu","year":"2020","journal-title":"Adv. Sustain. Syst."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1180","DOI":"10.1002\/slct.202004554","article-title":"Synthesis and Characterization of Sustainable Inverse Vulcanized Copolymers from Non-Edible Oil","volume":"6","author":"Ghumman","year":"2021","journal-title":"ChemistrySelect"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"123553","DOI":"10.1016\/j.polymer.2021.123553","article-title":"Optimization of synthesis of inverse vulcanized copolymers from rubber seed oil using response surface methodology","volume":"219","author":"Ghumman","year":"2021","journal-title":"Polymer (Guildf)"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"02014","DOI":"10.1051\/e3sconf\/202128702014","article-title":"Conversion of palm oil to new sulfur-based polymer by inverse vulcanization","volume":"287","author":"Abbasi","year":"2021","journal-title":"E3S Web Conf."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1600303","DOI":"10.1002\/macp.201600303","article-title":"Sulfur-Based Polymer Composites from Vegetable Oils and Elemental Sulfur: A Sustainable Active Material for Li-S Batteries","volume":"218","author":"Hoefling","year":"2017","journal-title":"Macromol. Chem. Phys."},{"key":"ref_34","first-page":"1179","article-title":"Preparation and characterization of green polymer by copolymerization of corn oil and sulphur at molten state","volume":"29","author":"Abbasi","year":"2021","journal-title":"Polym. Polym. Compos."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"102","DOI":"10.1016\/j.polymdegradstab.2019.02.011","article-title":"Sulfur fertilizer based on inverse vulcanization process with soybean oil","volume":"162","author":"Valle","year":"2019","journal-title":"Polym. Degrad. Stab."},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Liu, Y., Chen, Y., Zhang, Y., Chen, Y., Wang, L., Zan, X., and Zhang, L. (2020). Density-Adjustable Bio-Based Polysulfide Composite Prepared by Inverse Vulcanization and Bio-Based Fillers. Polymers, 12.","DOI":"10.3390\/polym12092127"},{"key":"ref_37","unstructured":"Sadzawka, M.M.A., Carrasco, M., and Grez, R. (2021, November 01). M\u00e9todos de An\u00e1lisis de Tejidos Vegetales. Available online: http:\/\/www.schcs.cl\/doc\/libros\/An%C3%A1lisi%20de%20tejidos%20vegetales.pdf."},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Azeem, B., KuShaari, K., Naqvi, M., Keong, L.K., AlMesfer, M.K., Al-Qodah, Z., Naqvi, S.R., and Elboughdiri, N. (2020). Naqvi Production and Characterization of Controlled Release Urea Using Biopolymer and Geopolymer as Coating Materials. Polymers, 12.","DOI":"10.3390\/polym12020400"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1021\/jf103839j","article-title":"Optimization of Conditions for Anthocyanin Hydrolysis from Red Wine Using Response Surface Methodology (RSM)","volume":"59","author":"Pinho","year":"2011","journal-title":"J. Agric. Food Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"8432","DOI":"10.1021\/acsomega.9b03363","article-title":"Experimental Modeling and Optimization of CO2 Absorption into Piperazine Solutions Using RSM-CCD Methodology","volume":"5","author":"Pashaei","year":"2020","journal-title":"ACS Omega"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"4603","DOI":"10.1021\/acs.energyfuels.9b03692","article-title":"Parametric Studies on Hydrodeoxygenation of Rubber Seed Oil for Diesel Range Hydrocarbon Production","volume":"34","author":"Ameen","year":"2020","journal-title":"Energy Fuels"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"105","DOI":"10.1002\/jsl.55","article-title":"Evaluation of the oxidative properties of vegetable oils as base stocks for industrial lubricants using spectroscopic and thermogravimetric analyses","volume":"25","author":"Jayadas","year":"2008","journal-title":"J. Synth. Lubr."},{"key":"ref_43","first-page":"79","article-title":"Investigation on oxidation and thermal stability of Jatropha oil","volume":"77","author":"Lubis","year":"2015","journal-title":"J. Teknol."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1704","DOI":"10.1002\/pola.29436","article-title":"Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid","volume":"57","author":"Smith","year":"2019","journal-title":"J. Polym. Sci. Part A Polym. Chem."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/22\/4040\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T07:33:48Z","timestamp":1760168028000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/22\/4040"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,11,22]]},"references-count":44,"journal-issue":{"issue":"22","published-online":{"date-parts":[[2021,11]]}},"alternative-id":["polym13224040"],"URL":"https:\/\/doi.org\/10.3390\/polym13224040","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,11,22]]}}}