Synthesis of Poly(methyl methacrylate)-<italic style="font-style: italic">b</italic>-Poly(ethylene oxide) Bottlebrush Block Copolymers and Their Interfacial Self-assembly Toward Structural Colored Pigments

Ling-feng Huang; Dong-po Song; Yue-sheng Li

doi:10.11777/j.issn1000-3304.2024.24101

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

Research Article | 更新时间：2024-12-24

- Synthesis of Poly(methyl methacrylate)-b-Poly(ethylene oxide) Bottlebrush Block Copolymers and Their Interfacial Self-assembly Toward Structural Colored Pigments
- Acta Polymerica Sinica Vol. 55, Issue 11, Pages: 1504-1517(2024)
- 作者机构：
  
  天津大学材料科学与工程学院天津 300350
- 作者简介：
  
  Dong-po Song, E-mail: dongpo.song@tju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24101
  CLC：
- CSTR：32057.14.GFZXB.2024.7258
- Received：04 April 2024，
  
  Accepted：2024-04-30，
  
  Published Online：22 July 2024，
  
  Published：20 November 2024
- 稿件说明：
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黄凌峰, 宋东坡, 李悦生. 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. 高分子学报, 2024, 55(11), 1504-1517

Huang, L. F.; Song, D. P.; Li, Y. S. Synthesis of poly(methyl methacrylate)‍-b-poly(ethylene oxide) bottlebrush block copolymers and their interfacial self-assembly toward structural colored pigments. Acta Polymerica Sinica, 2024, 55(11), 1504-1517
黄凌峰, 宋东坡, 李悦生. 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. 高分子学报, 2024, 55(11), 1504-1517 DOI： 10.11777/j.issn1000-3304.2024.24101. CSTR： 32057.14.GFZXB.2024.7258.

Huang, L. F.; Song, D. P.; Li, Y. S. Synthesis of poly(methyl methacrylate)‍-b-poly(ethylene oxide) bottlebrush block copolymers and their interfacial self-assembly toward structural colored pigments. Acta Polymerica Sinica, 2024, 55(11), 1504-1517 DOI： 10.11777/j.issn1000-3304.2024.24101. CSTR： 32057.14.GFZXB.2024.7258.

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-

-聚甲基丙烯酸甲酯)-

-(聚降冰片烯-

-聚环氧乙烷) (PMMA-

-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.

Abstract

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-

-PMMA)-

-(poly(norbornene-

-PEO)) (PMMA-

-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 eco-friendliness 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.

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

DOI：10.11777/j.issn1000-3304.2024.24101

摘要

Abstract

关键词

Keywords

references