The chemical reactivity and network and properties after curing of diglycidyl ether of bisphenol A(DGEBA)/amine systems were studied using viscosity analysis,different scanning calorimetry analysis(DSC),thermogravimetric analysis and universal testing machine.using three different diluents,including 1,4-butanediol diglycidyl ether,phenyl glycidyl ether and decylglycide ether.The result showed that the addition of aromatic diluents PGE into DGEBA curing system accelerated the curing reaction to a certain extent,resulted in enhancement of tensile and flexural strength and modulus,but led to a reduction of both elongation and the impact strength.However,the addition of the other two diluents had the contrary effects on these properties and the DGE which had the longest fatty chain segment had the most obvious effects.All tested modified epoxy compositions had lower thermal stability than unmodified epoxy resin.- DOI:10.3969/j.issn.1000-1565.2016.06.007活性稀释剂对环氧树脂结构和性能的影响李山剑1,邓双辉2,冯云龙2,刘超凡1,刘坐镇1,2(1.华东理工大学 材料科学与工程学院,特种功能高分子材料及相关技术教育部重点实验室,上海 200237;2.华东理工大学 华昌聚合物有限公司,上海防腐蚀新材料工程技术研究中心,上海 200237)摘 要:选用3种具有不同分子结构和官能度的缩水甘油醚——1,4-丁二醇二缩水甘油醚(BDDGE)、苯基缩水甘油醚(PGE)和癸基缩水甘油醚(DGE)作为活性稀释剂,通过黏度、DSC、热重分析和万能实验机等方法考察了其对双酚A环氧-胺固化体系的反应活性、交联网络结构和性能的影响.结果表明:芳香类稀释剂的加入,对环氧-胺固化体系的反应活性影响不大甚至有所提升,且固化物的强度和模量提高,韧性降低;而脂肪族稀释剂则明显降低了固化体系的反应活性,随着脂肪链长度的增加,固化物的强度和模量下降,韧性提高;3种稀释剂的加入均降低了环氧体系的耐热性能.关键词:环氧树脂;活性稀释剂;反应活性;交联结构;性能中图分类号:O631 文献标志码:A 文章编号:1000-1565(2016)06-0604-10Effects of reactive diluents type on chemical structure and property of epoxy resin systemLI Shanjian1,DENG Shuanghui2,FENG Yunlong2,LIU Chaofan1,LIU Zuozhen1,2(1.Key Laboratory for Special Functional Polymers and Related Technology of Ministry of Education,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237; 2.Shanghai Engineering Research Center of New Anti-corrosion Materials,Sino Polymer Co Ltd,East ChinaUniversity of Science and Technology,Shanghai 200237,China)Abstract: The chemical reactivity and network and properties after curing of diglycidyl ether of bisphenol A(DGEBA)/amine systems were studied using viscosity analysis,different scanning calorimetry analysis(DSC),thermogravimetric analysis and universal testing machine.using three different diluents,including 1,4-butanediol diglycidyl ether,phenyl glycidyl ether and decylglycide ether.The result showed that the addition of aromatic diluents PGE into DGEBA curing system accelerated the curing reaction to a certain extent,resulted in enhancement of tensile and flexural strength and modulus,but led to a reduction of both elongation and the impact strength.However,the addition of the other two diluents had the contrary effects on these properties and the DGE which had the longest fatty chain segment had the most obvious effects.All tested modified epoxy compositions had lower thermal stability than unmodified epoxy resin.- 收稿日期:2016-07-01 基金项目:上海市重大科技攻关项目(12dz1100401);上海工程技术研究中心能力提升项目(13DZ2280900) 第一作者:李山剑(1992—),男,江苏如皋人,华东理工大学在读硕士研究生.E-mail:lsj262728@126.com 通信作者:刘坐镇(1965—),男,河南新密人,华东理工大学教授,主要从事热固性树脂及其复合材料的研究.E-mail:lzz@hchp.com.cn第6期李山剑等:活性稀释剂对环氧树脂结构和性能的影响
LI Shanjian
,
DENG Shuanghui
,
FENG Yunlong
,
LIU Chaofan
,
LIU Zuozhen
. Effects of reactive diluents type on chemical structure and property of epoxy resin system[J]. Journal of Hebei University(Natural Science Edition), 2016
, 36(6)
: 604
-613
.
DOI: 10.3969/j.issn.1000-1565.2016.06.007
[1] K DUSEK.Epoxy resins and composites IV[M].Berlin:Springer-Verlag,1986:173-202.
[2] CHEN Zhenkun,YANG Guo,YANG Jiaoping,et al.Simultaneously increasing cryogenic strength,ductility and impact resistance of epoxy resins modified by n-butyl glycidyl ether[J].Polymer,2009,50(5):1316-1323.DOI:10.1016/j.polymer.2008.12.048.
[3] BESSONOV I V,POLEZHAEV A V,KUZNETSOVA M N,et al.Rheological and thermal analysis of low-viscosity epoxy-furan composites[J].Polymer Science Series D,2013,6(4):308-311.DOI:10.1134/S1995421213040023.
[4] ZHENG Yun,JIN Xiaolin,WEI Ping,et al.Study on the curing reaction,dielectric and thermal performances of epoxy impregnating resin with reactive silicon compounds as new diluents[J].Journal of Applied Polymer Science,2008,107(5):3127-3136.DOI:10.1002/app.27502.
[5] BAKAR M,SZYMANSKA J,RUDECKA J,et al.effect of reactive diluents and kaolin on the mechanical properties of epoxy resin[J].Polymers for Polymer Composites,2010,18(9):503-510.
[6] 李广琦,王联合,王美林,等.稀释剂用量对环氧固化物玻璃化温度的影响[J].热固性树脂,2010,25(5):32-33.DOI:10.13650/j.cnki.rgxsz.2010.05.008. LI G Q,WANG L H,WANG M L,et al.Effect of diluent amount on the glass transition temperature of epoxy curing products[J].Thermosetting Resin,2010,25(5):32-33.DOI:10.13650/j.cnki.rgxsz.2010.05.008.
[7] 林益军,邓青华,金日光.稀释剂对BPA型环氧树脂188EL及其固化物性能的影响[J].热固性树脂,2014,29(4):19-22.DOI:10.13650/j.cnki.rgxsz.2014.04.005. LIN Y J,DENG Q H,JIN R G.Effect of diluent on the properties of BPA epoxy resin 188EL and its cured product[J].Thermosetting Resin,2014,29(4):19-22.DOI:10.13650/j.cnki.rgxsz.2014.04.005.
[8] 杨涛,程珏,张重锋,等.稀释剂对双酚F环氧树脂/酸酐体系流变性及力学性能的影响[J].北京化工大学学报(自然科学版),2014,41(3):76-81.DOI:10.13543/j.cnki.bhxbzr.2014.03.012. YANG T,CHENG J,ZHANG C F,et al.The influence of diluents on the rheological and mechanical properties of epoxy/anhydride systems[J].Journal of Beijing University of Chemical Technology(Nature Science),2014,41(3):76-81.DOI:10.13543/j.cnki.bhxbzr.2014.03.012.
[9] 孙曼灵.环氧树脂应用原理与技术[M].北京:机械工业出版社,2002:18-20.
[10] 肖卫东,何培新,李剑.环氧树脂胺加成物的合成及其固化性能研究[J].粘接,2001,22(3):13-15. XIAO W D,HE P X,LI J.The synthesis of amine-epoxy adduct and its cure reaction[J].Zhanjie,2001,22(3):13-15.
[11] FEDTKE M.Acceleration mechanisms in curing reactions involving model systems[J].MakromolekulareChemie.Macromolecular Symposia,1987,7(1):153-168.DOI:10.1002/masy.19870070114.
[12] TEH P L,MARIATTI M,AKIL H M,et al.Effect of ethanol as diluent on the properties of mineral silica filled epoxy composites [J].Journal of Composite Materials,2008,42(2):129-142.DOI:10.1177/0021998307078721.
[13] LIU Y,DOU Z J,ZHANG C,et al.Curing behavior and thermal properties of multifunctional epoxy resin with methylhexahydrophthalic anhydride[J].Journal of Applied Polymer Science,2007,103(3):2041-2048.DOI:10.1002/app.25291.
[14] 蔡佩芝,张昊,赵东林,等.稀释剂对DDM/E-51环氧树脂体系力学性能的影响[J].高分子材料科学与工程,2010,26(11):75-77+82. CAI P Z,ZHANG H,ZHAO D L,et al.Effect of diluents on mechanical properties of DDM/E-51 epoxy resin system[J].Polymer Materials Science and Engineering,2010,26(11):75-77+82.
