瓶刷嵌段共聚物聚甲基丙烯酸甲酯-b-聚环氧乙烷的合成与乳液界面自组装制备结构色颜料  

Synthesis of Poly(methyl methacrylate)-b-Poly(ethylene oxide)Bottlebrush Block Copolymers and Their Interfacial Self-assembly Toward Structural Colored Pigments

作　　者：黄凌峰 宋东坡 李悦生[1] Ling-feng Huang;Dong-po Song;Yue-sheng Li(School of Materials Science and Engineering,Tianjin University,Tianjin 300350)

机构地区：[1]天津大学材料科学与工程学院,天津300350

出　　处：《高分子学报》2024年第11期1504-1517,共14页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52273214)资助项目.

摘　　要：针对车漆涂料等应用场景对结构色材料较高的耐候性能要求,本工作利用有序自发乳化机制成功制备了聚甲基丙烯酸甲酯(PMMA)为骨架的有序多孔光子微球,展现了靓丽可调的结构色.通过原子转移自由基聚合(ATRP)合成了窄分子量分布的PMMA,并利用巯烯反应高效除去了因歧化终止而产生的端末双键,进一步利用酯化反应合成了末端带有降冰片烯单元的PMMA大单体.通过顺序开环易位聚合(ROMP)的合成方法,成功合成了(聚降冰片烯-g-聚甲基丙烯酸甲酯)-b-(聚降冰片烯-g-聚环氧乙烷)(PMMA-b-PEO)嵌段共聚物刷(BBCPs),数均分子量在174 kDa~359 kDa范围内可调,PDI维持在1.2以下.在有序自发乳化制备结构色颜料的过程中,采用生物来源、安全环保的苯甲醚作为油相溶剂替代甲苯,使得材料制备过程更加安全环保,消除了产物中可能的有害残留,有利于规模制备与应用.PMMA材质的结构色颜料预期具有良好的耐候性能,有望用于车漆涂料等应用场景.High environmental tolerance is a critical requirement for coating applications,particularly in automotive paint.This study successfully fabricated ordered porous photonic microspheres with poly(methyl methacrylate)(PMMA)as the framework using an organized spontaneous emulsification(OSE)mechanism,showing vibrant and adjustable structural colors.PMMA with narrow molecular weight distributions was synthesized via atom transfer radical polymerization(ATRP),and the efficient removal of terminal double bonds resulting from disproportionation termination was achieved through thiol-ene click reactions.Additionally,PMMA macromonomers with norbornene units were prepared through esterification reactions.By employing sequential ring-opening metathesis polymerization(ROMP),(poly(norbornene-g-PMMA)-b-poly(norbornene-g-PEO))(PMMA-b-PEO)bottlebrush block copolymers(BBCPs)were successfully synthesized with tunable number-average molecular weights ranging from 174 kDa to 359 kDa and low PDIs below 1.2.Pore diameter is tunable in a large range from 178 nm to 287 nm,resulting in photonic bandgaps changing from 437 nm to 618 nm.Photonic pigments with various colors across the whole visible range are therefore obtained.In addition,bio-based and environmentally safe anisole was utilized as the oil phase instead of toluene during the OSE process,enhancing the safety and ecofriendliness of the material preparation process,eliminating potential harmful residues,and facilitating large-scale production and application.PMMA-based structural color pigments are anticipated to demonstrate outstanding weather resistance and offer significant potential for applications like automotive paint coatings.

关 键 词：嵌段共聚物 自组装 环保材料 结构色 

分 类 号：TQ620.4[化学工程—精细化工]