Effective Studies of bio-derived free radical polymerizable hydroxyl functional macromonomer for replacement of Hydroxylethyl Methacrylate (HEMA) in acrylic polyols and their polyurethane-urea coatings
{"title":"Effective Studies of bio-derived free radical polymerizable hydroxyl functional macromonomer for replacement of Hydroxylethyl Methacrylate (HEMA) in acrylic polyols and their polyurethane-urea coatings","authors":"Allauddin Shaik, Kiran Kumar Nehete, Subarna Shyamroy","doi":"10.1007/s10965-025-04295-2","DOIUrl":null,"url":null,"abstract":"<div><p>The present work aims to study the impact of replacing HEMA monomer with a bio-based free radical hydroxyl functional macromonomer derived from castor oil (CO) in the synthesis of acrylic polyols. It also evaluates the coating properties of the resulting polyurethanes (PUs) in comparison to conventional acrylic polyols (AP-HEMA) derived from HEMA. To achieve this, castor oil was first reacted with maleic anhydride (MA) to produce the castor oil-derived free radical polymerizable hydroxyl functional macromonomer (COMA). Subsequently, castor oil-based acrylic hybrid polyols were synthesized using acrylate monomers, specifically methyl methacrylate (MMA) and butyl acrylate (BA), along with varying weight percentages of COMA through a conventional radical copolymerization process. The successful replacement of HEMA with COMA in the acrylic polymerization was verified through Fourier transform infrared (FTIR) spectroscopy, hydroxyl value analysis, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The acrylic hybrid polyols derived from castor oil exhibited reduced viscosity, lower glass transition temperature (Tg), and decreased molecular weight compared to AP-HEMA. Both castor oil based, and AP-HEMA based acrylic polyols were further reacted with Isophorone diisocyanate (IPDI) at an OH: NCO ratio of 1:1.6 to form isocyanate-terminated polyurethane prepolymers. The Tg of the castor oil-based acrylic hybrid polyurethane coating films was found to be lower than that of petroleum-derived HEMA based acrylic polyols, demonstrating enhanced performance in terms of contact angle, water resistance, flexibility, adhesion, and abrasion resistance. The overall findings highlight the feasibility of using castor oil-derived COMA as a sustainable alternative in acrylic polyol formulations. The bio-derived free radical polymerizable hydroxyl functionality exhibits polymerization tendency within the conventional acrylic polymerization framework, indicating its potential as a substitute for the HEMA monomer in the synthesis of acrylic polyols, thereby yielding high solid content resins suitable for high-performance polyurethane coating applications.</p></div>","PeriodicalId":658,"journal":{"name":"Journal of Polymer Research","volume":"32 2","pages":""},"PeriodicalIF":2.8000,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Polymer Research","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10965-025-04295-2","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
The present work aims to study the impact of replacing HEMA monomer with a bio-based free radical hydroxyl functional macromonomer derived from castor oil (CO) in the synthesis of acrylic polyols. It also evaluates the coating properties of the resulting polyurethanes (PUs) in comparison to conventional acrylic polyols (AP-HEMA) derived from HEMA. To achieve this, castor oil was first reacted with maleic anhydride (MA) to produce the castor oil-derived free radical polymerizable hydroxyl functional macromonomer (COMA). Subsequently, castor oil-based acrylic hybrid polyols were synthesized using acrylate monomers, specifically methyl methacrylate (MMA) and butyl acrylate (BA), along with varying weight percentages of COMA through a conventional radical copolymerization process. The successful replacement of HEMA with COMA in the acrylic polymerization was verified through Fourier transform infrared (FTIR) spectroscopy, hydroxyl value analysis, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The acrylic hybrid polyols derived from castor oil exhibited reduced viscosity, lower glass transition temperature (Tg), and decreased molecular weight compared to AP-HEMA. Both castor oil based, and AP-HEMA based acrylic polyols were further reacted with Isophorone diisocyanate (IPDI) at an OH: NCO ratio of 1:1.6 to form isocyanate-terminated polyurethane prepolymers. The Tg of the castor oil-based acrylic hybrid polyurethane coating films was found to be lower than that of petroleum-derived HEMA based acrylic polyols, demonstrating enhanced performance in terms of contact angle, water resistance, flexibility, adhesion, and abrasion resistance. The overall findings highlight the feasibility of using castor oil-derived COMA as a sustainable alternative in acrylic polyol formulations. The bio-derived free radical polymerizable hydroxyl functionality exhibits polymerization tendency within the conventional acrylic polymerization framework, indicating its potential as a substitute for the HEMA monomer in the synthesis of acrylic polyols, thereby yielding high solid content resins suitable for high-performance polyurethane coating applications.
期刊介绍：
Journal of Polymer Research provides a forum for the prompt publication of articles concerning the fundamental and applied research of polymers. Its great feature lies in the diversity of content which it encompasses, drawing together results from all aspects of polymer science and technology.
As polymer research is rapidly growing around the globe, the aim of this journal is to establish itself as a significant information tool not only for the international polymer researchers in academia but also for those working in industry. The scope of the journal covers a wide range of the highly interdisciplinary field of polymer science and technology, including:
polymer synthesis;
polymer reactions;
polymerization kinetics;
polymer physics;
morphology;
structure-property relationships;
polymer analysis and characterization;
physical and mechanical properties;
electrical and optical properties;
polymer processing and rheology;
application of polymers;
supramolecular science of polymers;
polymer composites.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
