苯并噁嗪单体的分子设计及其合成研究进展
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摘要
聚苯并噁嗪是近二三十年发展起来的一类新型热固性树脂.其重复单元是含氮、氧杂环结构的化合物,高温下可在无催化剂的情况下发生开环反应形成聚合物.聚苯并噁嗪具备熔体黏度低、易加工、成型收缩率接近零以及固化过程无挥发性物质产生等独特的优点,同时还保持了传统酚醛树脂优良的热稳定性、电绝缘性和机械性能.苯并噁嗪单体最大的优点在于其分子设计的灵活性,通过设计反应底物或者控制固化工艺可合成各种具有特定结构和性质的苯并噁嗪单体和树脂.主要从单官能度、双官能度、多官能度三方面概述了几种苯并噁嗪单体的类型及其合成方法.
Benzoxazine resin is a novel type of thermosetting resin that has attracted increasing attention in the past decades. The benzoxazine monomer is a compound containing nitrogen and oxygen heterocyclic structure,which can form a polymer with catalyst-free thermal ring-opening polymerization. Benzoxazines have the advantages of low melt viscosity,easy processing,zero shrinkage or a slight expansion upon curing and without the release of any byproducts,while also retaining excellent thermal stability,electrical insulation and mechanical properties of conventional phenolic resins. The greatest advantage of benzoxazine monomers is their flexibility in molecular design. A variety of benzoxazine monomers and resins with specific structures and properties can be synthesized by designing the reaction substrates or controlling the curing process. The types of benzoxazine monomer and their synthetic methods are summarized from the aspects of monofunctional,bifunctional and multifunctional aspects.
Benzoxazine resin is a novel type of thermosetting resin that has attracted increasing attention in the past decades. The benzoxazine monomer is a compound containing nitrogen and oxygen heterocyclic structure,which can form a polymer with catalyst-free thermal ring-opening polymerization. Benzoxazines have the advantages of low melt viscosity,easy processing,zero shrinkage or a slight expansion upon curing and without the release of any byproducts,while also retaining excellent thermal stability,electrical insulation and mechanical properties of conventional phenolic resins. The greatest advantage of benzoxazine monomers is their flexibility in molecular design. A variety of benzoxazine monomers and resins with specific structures and properties can be synthesized by designing the reaction substrates or controlling the curing process. The types of benzoxazine monomer and their synthetic methods are summarized from the aspects of monofunctional,bifunctional and multifunctional aspects.
引文
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[16]XU Y,DAI J,RAN Q C,et al.Greatly improved thermal properties of polybenzoxazine viamodication by acetylene/aldehyde groups[J].Polymer,2017,123:232-239.
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[20]MA H X,ZHAO C,QIU J J,et al.Synthesis of branched benzoxazine monomers with high molecular mass,wide processing window,and properties of corresponding polybenzoxazines[J].Journal of Applied Polymer Science,2017,134(6):44453.
[21]孙闯.本质阻燃生物基苯并噁嗪单体的合成,固化机理和阻燃性能的研究[D].杭州:浙江大学,2016.SUN C.Study on the synthesis,curing mechanisms and flame retardant properties of benzoxazine monomer with flame retardant bio-based bio-based[D].Zhejiang University,2016.
[22]DUMAS L,BONNAUD L,OLIVIER M,et al.Chavicol benzoxazine:Ultrahigh Tg biobased thermoset with tunable extended network[J].European Polymer Journal,2016,81:337-346.
[23]杨坡,顾宜.两种含苯并杂环二胺型苯并噁嗪的设计与性能[C].全国苯并噁嗪树脂应用研讨会论文集,2011.YANG P,GU Y.Design and properties of two benzxazines containing benzo heterocyclic diamine type[C].National Benzoxazine Resin Application Seminar,2011.
[24]SPONTN M,ESTENOZ D,LLIGADAS G,et al.Synthesis and characterization of a hybrid material based on a trimethoxysilane functionalized benzoxazine[J].Journal of Applied Polymer Science,2012,126(4):1369-1376.
[25]WU X,LIU S Z,TIAN D T,et al.Well-defined organicinorganic hybrid benzoxazine monomers based on cyclotriphosphazene:Synthesis,properties of the monomers and polybenzoxazines[J].Polymer,2011,52(19):4235-4245.
[2]RIMDUSIT S,TIPTIPAKORN S,JUBSILP C,et al.Polybenzoxazine alloys and blends:some unique properties and applications[J].Reactive&Functional Polymers,2013,73(2):369-380.
[3]TIPTIPAKORN S.Physical characterizations and hardness of polymers obtained from irradiated benzoxazine monomer[J].International Journal of Chemical Engineering and Applications,2012,3(1):76-81.
[4]曾鸣,王洛礼,刘景民.苯并噁嗪树脂的研究进展[J].石化技术与应用,2000,18:103-107.ZENG M,WANG L L,LIU J M.Research progress of benzoxazine resin[J].Petrochemical Technology and Application,2000,18:103-107.
[5]HAMERTON I,MCNAMARA L,HOWLIN B,et al.Examining the initiation of the polymerization mechanism and network development in aromatic polybenzoxazines[J].Macromolecules,2013,46(13):5117-5132.
[6]LI W,CHU J,LIANG H,et al.A novel thermal-resistant copolymer from polysiloxane-based polybenzoxazine precursor and ferrocene-based benzoxazine monomer[J].Polymer,2013,54(18):4909-4922.
[7]HOLLY F,COPE A.Condensation products of aldehydes and ketones with o-aminobenzyl alcohol and o-hydroxybenzylamine[J].Journal of the American Chemical Society,1944,66(11):1875-1879.
[8]BURKE W,STEPHENS C.Monomeric products from the condensation of phenol with formaldehyde and primary amines[J].Journal of the American Chemical Society,1952,74(6):1518-1520.
[9]BURKE W,KOLBEZEN M,STEPHENS C.Condensation of halophenols with formaldehyde and primary amines1[J].Journal of the American Chemical Society,1952,74(14):3601-3605.
[10]BURKE W,MURDOCK K,EC G.Condensation of hydroxyaromatic compounds with formaldehyde and primary aromatic amines[J].Journal of the American Chemical Society,1954,76(6):1677-1679.
[11]AGAG T,TAKEICHI T.Synthesis and characterization of novel benzoxazine monomers containing allyl groups and their high performance thermosets[J].Macromolecules,2003,36(16):6010-6017.
[12]龚蕊,李胜方.2种溴化苯并噁嗪单体的合成与表征[N].湖北理工学院学报,2009,25:18-21.GONG R,LI S F.Synthesis and characterization of two types of brominated benzoxazine monomers[N].Journal of Hubei Institute of Technology,2009,25:18-21.
[13]SPONTN M,LLIGADAS G,RONDA J C,et al.Development of a DOPO-containing benzoxazine and its highperformance flame retardant copolybenzoxazines[J].Polymer Degradation&Stability,2009,94(10):1693-1699.
[14]QU L,XIN Z.Preparation and surface properties of novel low surface free energy fluorinated silane-functional polybenzoxazine films[J].Langmuir,2011,27(13):8365-8370.
[15]LI W,WEI T,GAO Y,et al.Preparation of novel benzoxazine monomers containing ferrocene moiety and properties of polybenzoxazines[J].Polymer,2012,53(6):1236-1244.
[16]XU Y,DAI J,RAN Q C,et al.Greatly improved thermal properties of polybenzoxazine viamodication by acetylene/aldehyde groups[J].Polymer,2017,123:232-239.
[17]HSIEH C Y,SU W C,WU C S,et al.Benzoxazine-containing branched polysiloxanes:Highly efficient reactivetype flame retardants and property enhancement agents for polymers[J].Polymer,2013,54(12):2945-2951.
[18]CHOI S W,OHBA S,BRUNOVSKA Z,et al.Synthesis,characterization and thermal degradation of functional benzoxazine monomers and polymers containing phenylphosphine oxide[J].Polymer Degradation&Stability,2006,91(5):1166-1178.
[19]余丽丽.新型含磷硅苯并噁嗪的合成与性能[D].开封:河南大学,2015.YU L L.Synthesis and characterization of benzoxazine resins containing phosphorus and silicon[D].Henan University,2015.
[20]MA H X,ZHAO C,QIU J J,et al.Synthesis of branched benzoxazine monomers with high molecular mass,wide processing window,and properties of corresponding polybenzoxazines[J].Journal of Applied Polymer Science,2017,134(6):44453.
[21]孙闯.本质阻燃生物基苯并噁嗪单体的合成,固化机理和阻燃性能的研究[D].杭州:浙江大学,2016.SUN C.Study on the synthesis,curing mechanisms and flame retardant properties of benzoxazine monomer with flame retardant bio-based bio-based[D].Zhejiang University,2016.
[22]DUMAS L,BONNAUD L,OLIVIER M,et al.Chavicol benzoxazine:Ultrahigh Tg biobased thermoset with tunable extended network[J].European Polymer Journal,2016,81:337-346.
[23]杨坡,顾宜.两种含苯并杂环二胺型苯并噁嗪的设计与性能[C].全国苯并噁嗪树脂应用研讨会论文集,2011.YANG P,GU Y.Design and properties of two benzxazines containing benzo heterocyclic diamine type[C].National Benzoxazine Resin Application Seminar,2011.
[24]SPONTN M,ESTENOZ D,LLIGADAS G,et al.Synthesis and characterization of a hybrid material based on a trimethoxysilane functionalized benzoxazine[J].Journal of Applied Polymer Science,2012,126(4):1369-1376.
[25]WU X,LIU S Z,TIAN D T,et al.Well-defined organicinorganic hybrid benzoxazine monomers based on cyclotriphosphazene:Synthesis,properties of the monomers and polybenzoxazines[J].Polymer,2011,52(19):4235-4245.