{"title":"Epoxy composite microspheres as a versatile platform for enhancement of chlorophyll dispersion and photostability in coatings","authors":"Zilin Yi , Zihan Shan , Xinlong Tang , Xuetai Yu , Xiang Cheng , Liang Fang , Chunhua Lu , Zhongzi Xu","doi":"10.1016/j.porgcoat.2024.108745","DOIUrl":null,"url":null,"abstract":"<div><p>Chlorophyll (Chl), as a rich natural pigment, is limited in applications due to poor photostability. The hydrophobic properties of Chl attributed to the tetrapyrrole ring and terminal long-chain hydrocarbons further constrains its dispersion in aqueous coatings. In this work, chlorophyll/epoxy composite microspheres (Chl/EMs) were prepared as candidate pigments via emulsion polymerization to provide a versatile platform for enhanced dispersion and photostability. The optimal reaction temperature of 75 °C for achieving the appropriate particle size distribution of epoxy microspheres (EMs) was first determined. Chl/EMs were then prepared by (1) the combination of Chl and DGEBA in the emulsification process, or by (2) mixing Chl with <em>m</em>-xylylenediamine (MXDA) during curing. The effects of Chl introduction at different steps on the emulsification, curing agent diffusion, and curing process were studied using off-site microscopy observation and aggregation-induced emission technique, to clarify the structure and morphology evolution during emulsion polymerization. The particle size of the microspheres was mainly determined by the emulsification process of the epoxy precursor. Chl participates in emulsification of Chl/EMs in case (1), resulting in a large average particle size and poor particle size distribution. In case (2), the diffusion of MXDA into epoxy emulsion particles is completed within 30 min and does not impede the quicker diffusion process of Chl which was mixed with MXDA. The prepared Chl/EMs with size ranging from 1 to 10 μm create a conducive oxygen blocking environment. Compared to the complete degradation period of untreated Chl coatings, the photostability of Chl/EMs coatings increased nearly 7-fold. Remarkably, Chl/EMs exhibit superior dispersion capability in waterborne polyurethane coatings compared to pure Chl coatings. The EMs with controllable morphology and size can be used as a versatile platform for enhancing dispersion and photostability of other organic or natural dyes and pigments in waterborne coatings.</p></div>","PeriodicalId":20834,"journal":{"name":"Progress in Organic Coatings","volume":"196 ","pages":"Article 108745"},"PeriodicalIF":6.5000,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Progress in Organic Coatings","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S030094402400537X","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
Chlorophyll (Chl), as a rich natural pigment, is limited in applications due to poor photostability. The hydrophobic properties of Chl attributed to the tetrapyrrole ring and terminal long-chain hydrocarbons further constrains its dispersion in aqueous coatings. In this work, chlorophyll/epoxy composite microspheres (Chl/EMs) were prepared as candidate pigments via emulsion polymerization to provide a versatile platform for enhanced dispersion and photostability. The optimal reaction temperature of 75 °C for achieving the appropriate particle size distribution of epoxy microspheres (EMs) was first determined. Chl/EMs were then prepared by (1) the combination of Chl and DGEBA in the emulsification process, or by (2) mixing Chl with m-xylylenediamine (MXDA) during curing. The effects of Chl introduction at different steps on the emulsification, curing agent diffusion, and curing process were studied using off-site microscopy observation and aggregation-induced emission technique, to clarify the structure and morphology evolution during emulsion polymerization. The particle size of the microspheres was mainly determined by the emulsification process of the epoxy precursor. Chl participates in emulsification of Chl/EMs in case (1), resulting in a large average particle size and poor particle size distribution. In case (2), the diffusion of MXDA into epoxy emulsion particles is completed within 30 min and does not impede the quicker diffusion process of Chl which was mixed with MXDA. The prepared Chl/EMs with size ranging from 1 to 10 μm create a conducive oxygen blocking environment. Compared to the complete degradation period of untreated Chl coatings, the photostability of Chl/EMs coatings increased nearly 7-fold. Remarkably, Chl/EMs exhibit superior dispersion capability in waterborne polyurethane coatings compared to pure Chl coatings. The EMs with controllable morphology and size can be used as a versatile platform for enhancing dispersion and photostability of other organic or natural dyes and pigments in waterborne coatings.
期刊介绍：
The aim of this international journal is to analyse and publicise the progress and current state of knowledge in the field of organic coatings and related materials. The Editors and the Editorial Board members will solicit both review and research papers from academic and industrial scientists who are actively engaged in research and development or, in the case of review papers, have extensive experience in the subject to be reviewed. Unsolicited manuscripts will be accepted if they meet the journal''s requirements. The journal publishes papers dealing with such subjects as:
• Chemical, physical and technological properties of organic coatings and related materials
• Problems and methods of preparation, manufacture and application of these materials
• Performance, testing and analysis.
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