《厦门大学学报（自然科学版）》

阻燃剂多尺度结构设计与绿色火安全材料研发

许一婷¹,王华进²,王子超³,曾碧榕¹,袁丛辉¹,卢伟²,Jean-Francois Gerard⁴,戴李宗¹*

(1.厦门大学材料学院,福建省防火阻燃材料重点实验室,福建厦门 361005; 2.海洋涂料国家重点实验室,海洋化工研究院有限公司,山东青岛 266071; 3.厦门大平工贸有限公司,福建厦门 361004; 4.Ingénierie des Matériaux Polymères-UMR CNRS #5223,INSA de Lyon,69621 Villeurbanne Cedex(France))

关键词：防火阻燃材料; 多尺度结构设计; 多元素杂化; 有机/无机纳米复合材料

Research and development of green fire safety materials based on multi-scale structural design of fire retardant

XU Yiting¹,WANG Huajin²,WANG Zichao³,ZENG Birong¹,YUAN Conghui¹,LU Wei²,GERARD Jean-Francois⁴,DAI Lizong¹*

(1.Fujian Provincial Key Laboratory of Fire and Flame Retardant Materials,College of Materials,Xiamen University,Xiamen 361005,China; 2.State Key Laboratory of Marine Coatings,Marine Chemical Research Institute,Qingdao 266071,China; 3.Xiamen Daping Indust

DOI: 10.6043/j.issn.0438-0479.202010034

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通用聚合物具有易燃性,遇火迅速燃烧并释放大量有毒烟气,严重威胁着人类的生命财产安全.因此,绿色火安全材料的研发是符合国家战略发展需求的重要课题之一.运用多元素杂化改性、超分子自组装等前沿新方法、新技术,从不同尺度对无卤阻燃剂的结构进行设计,可以实现对高性能聚合物材料的阻燃改性,构筑绿色火安全材料.本文主要介绍厦门大学及其合作单位在防火阻燃材料领域的研究工作,包括分子水平上的P/N阻燃体系与多面体低聚倍半硅氧烷(POSS)基多元素阻燃体系设计、纳米尺度的无机材料表面有机功能化阻燃剂体系设计等方面的研究,以及在环氧树脂、聚氨酯发泡材料、防火涂料的应用研究,并提出防火阻燃材料的发展趋势.

Most general-purpose polymer materials are flammable,and they burn quickly in case of fire.The release of large amounts of toxic gases and smoke seriously threatens the safety of human life and property.Therefore,the construction of green fire safety materials is one of the important topics in line with the national strategic development.By using multi-element hybrid modification technology,supramolecular self-assembly,and other frontier new methods and new technologies,the structure of halogen-free flame retardant is designed from different scales,which can realize high flame retardant and high performance of the polymer materials,to build green fire safety materials.This paper mainly introduces the researches by Xiamen University and her collaborators in design of the P/N flame retardant unit at molecular level,the polyhedral oligomeric silsequioxane(POSS)-based organic/inorganic hybrid multi-element flame retardant system,and the surface organic functionalized inorganic nanoparticles flame retardant smoke suppression system on nano scale.Their applications in epoxy resin,polyurethane foam material and fire retardant coating are also presented and the development trend of fireproof and flame retardant materials is put forward.Obviously,the work provides reference and guidance for the development of green fire safety materials.

引言
1 分子尺度上的阻燃剂设计
2 纳米尺度的无机材料表面有机功能化阻燃剂体系的设计
3 防火阻燃材料的应用
4 总结和展望

图1 P/N协同阻燃剂PNOH、PNNO和DPN(A)[7],以及TAT-triDOPO、TAT-hexaDOPO和TAT-enneaDOPO的合成路线(B)[8]<br/>Fig.1 Synthetic routes of P/N synergistic flame retardants PNOH,PNNO,DPN(A)[7],and TAT-triDOPO,TAT-hexaDOPO,TAT-enneaDOPO(B)[8]

图1 P/N协同阻燃剂PNOH、PNNO和DPN(A)[7],以及TAT-triDOPO、TAT-hexaDOPO和TAT-enneaDOPO的合成路线(B)[8]
Fig.1 Synthetic routes of P/N synergistic flame retardants PNOH,PNNO,DPN(A)[7],and TAT-triDOPO,TAT-hexaDOPO,TAT-enneaDOPO(B)[8]

图2 P-N-polyol的合成路线[9]<br/>Fig.2 Synthetic route of P-N-polyol[9]

图2 P-N-polyol的合成路线[9]
Fig.2 Synthetic route of P-N-polyol[9]

图3 分子水平上的POSS基多元素杂化阻燃剂设计<br/>Fig.3 Design of POSS-based multi-element hybrid flame retardants at the molecular level

图3 分子水平上的POSS基多元素杂化阻燃剂设计
Fig.3 Design of POSS-based multi-element hybrid flame retardants at the molecular level

图4 有机功能化硅酸盐纳米粒子阻燃剂SiO2-PHDG(A)[41]和SiO2-RGO-ZHS(B)[42]的合成路线<br/>Fig.4 Synthetic routes of organic functionalized silicate nanoparticles flame retardants SiO2-PHDG(A)[41] and SiO2-RGO-ZHS(B)[42]

图4 有机功能化硅酸盐纳米粒子阻燃剂SiO2-PHDG(A)[41]和SiO2-RGO-ZHS(B)[42]的合成路线
Fig.4 Synthetic routes of organic functionalized silicate nanoparticles flame retardants SiO2-PHDG(A)[41] and SiO2-RGO-ZHS(B)[42]

图5 有机改性GO阻燃剂FGO(A)[47]、GOMT(B)[48]、GO-MD-MP(C)[49]、GO-D-P(D)[50]和HM-GO(E)[51]的制备路线<br/>Fig.5 The preparation routes of organically modified GO flame retardants FGO(A)[47],GOMT(B)[48], GO-MD-MP(C)[49],GO-DP(D)[50] and HM-GO(E)[51]

图5 有机改性GO阻燃剂FGO(A)[47]、GOMT(B)[48]、GO-MD-MP(C)[49]、GO-D-P(D)[50]和HM-GO(E)[51]的制备路线
Fig.5 The preparation routes of organically modified GO flame retardants FGO(A)[47],GOMT(B)[48], GO-MD-MP(C)[49],GO-DP(D)[50] and HM-GO(E)[51]

图6 h-BN-OH@CPBP的合成示意图(A)与扫描电镜(SEM)图(B～D)[54]<br/>Fig.6 Synthesis schematic diagram(A)and SEM images(B-D)of h-BN-OH@CPBP[54]

图6 h-BN-OH@CPBP的合成示意图(A)与扫描电镜(SEM)图(B～D)[54]
Fig.6 Synthesis schematic diagram(A)and SEM images(B-D)of h-BN-OH@CPBP[54]

图7 有机功能化金属化合物纳米粒子P-MnMo6(A)[59]和FeOOH@HP(B)[62],空心金属-硼酸酯纳米颗粒(C)[66]和硼酸酯聚合物包覆无机纳米粒子(D)[67]的制备路线<br/>Fig.7 Preparation routes of organic functionalized metal compound nanoparticles P-MnMo6(A)[59], FeOOH@HP(B)[62],hollow metal-borate nanoparticles(C)[66] and borate polymer coated inorganic nanoparticles(D)[67]

图7 有机功能化金属化合物纳米粒子P-MnMo6(A)[59]和FeOOH@HP(B)[62],空心金属-硼酸酯纳米颗粒(C)[66]和硼酸酯聚合物包覆无机纳米粒子(D)[67]的制备路线
Fig.7 Preparation routes of organic functionalized metal compound nanoparticles P-MnMo6(A)[59], FeOOH@HP(B)[62],hollow metal-borate nanoparticles(C)[66] and borate polymer coated inorganic nanoparticles(D)[67]

图8 多尺度结构设计的阻燃剂在环氧树脂中的应用<br/>Fig.8 The application of flame retardants designed with multi-scale structure in epoxy resin

图8 多尺度结构设计的阻燃剂在环氧树脂中的应用
Fig.8 The application of flame retardants designed with multi-scale structure in epoxy resin

图9 环氧树脂/POSS-bisDOPO的自组装和刻蚀前后的SEM图(A)[17]和环氧树脂/Ti-POSS-bisDOPO的阻燃机理和SEM图(B)[19]<br/>Fig.9 SEM images of EP/POSS-bisDOPO before and after resin self-assembly and etching(A)[17] and flame-retardant mechanism and SEM images of EP/Ti-POSS-bisDOPO(B)[19]

图9 环氧树脂/POSS-bisDOPO的自组装和刻蚀前后的SEM图(A)[17]和环氧树脂/Ti-POSS-bisDOPO的阻燃机理和SEM图(B)[19]
Fig.9 SEM images of EP/POSS-bisDOPO before and after resin self-assembly and etching(A)[17] and flame-retardant mechanism and SEM images of EP/Ti-POSS-bisDOPO(B)[19]

图10 阻燃聚氨酯的燃烧情况<br/>Fig.10 The combustion of flame-retardant polyurethane

图10 阻燃聚氨酯的燃烧情况
Fig.10 The combustion of flame-retardant polyurethane

图11 双组分环氧树脂超薄膨胀型钢结构防火涂层膨胀前后示意图<br/>Fig.11 Schematic diagram of two-component epoxy resin ultra-thin intumescent fire-retardant coating for steel structure before and after expansion

图11 双组分环氧树脂超薄膨胀型钢结构防火涂层膨胀前后示意图
Fig.11 Schematic diagram of two-component epoxy resin ultra-thin intumescent fire-retardant coating for steel structure before and after expansion

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学报简介

《厦门大学学报（自然科学版）》于1931年创刊，是由教育部主管，厦门大学主办，国内外公开发行的综合性学术期刊（双月刊），是我国自然科学核心期刊。本刊以印刷版、网络版的方式同时出版。主要刊载自然科学各学科的最新研究成果，包括自然科学基础理论研究、应用基础研究、高新技术方面的学术论文。所刊载的论文分三大类型：（1）“快讯”：报道某前沿领域具有突破性的最新研究成果。（2）“研究论文”：刊载理工科基础理论研究与实验研究学术论文。（3）“研究简报”：刊载内容新颖、实用（或阶段性）的成果。更多>>

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引言

1 分子尺度上的阻燃剂设计

2 纳米尺度的无机材料表面有机功能化阻燃剂体系的设计

3 防火阻燃材料的应用

4 总结和展望

学报简介