聚氨酯改性环氧树脂的制备及性能的研究
摘要
环氧树脂(EP)是工业中重要的热固性树脂之一。由于其优秀的附着性、高强度以及抗化学腐蚀性,被广泛的应用于黏结剂、涂料、封装材料等领域。然而,由于环氧树脂的固化密度高所引起的脆性大和抗冲击性差的缺点阻碍了其进一步的应用。本文研究的主要目的是将聚氨酯预聚体加入到环氧树脂体系中,形成环氧树脂/聚氨酯互穿网络聚合体(EP/PU IPNs),得到EP/PU复合材料。通过力学测试,DSC,TGA,SEM等方法研究改性材料的机械性能、热性能以及微观结构,并通过非等温DSC法研究了改性材料的固化动力学。
实验考察了反应时间和反应温度对聚氨酯预聚物的影响,得到了制备聚氨酯预聚物的适宜温度为70℃,反应时间为70～90min。对聚氨酯预聚物的红外分析表明,各官能团基本反应完全,得到了预期的产物,并讨论了水对预聚物的影响因素。
力学测试表明,用聚氨酯改性后的环氧树脂的韧性得到了很大程度的提高,同时其力学性能也有较大的提高。对端异氰酸酯基聚氨酯改性环氧树脂而言,15%的聚氨酯与环氧树脂能够很好的形成互穿网络结构,使得互穿材料的拉伸性能比纯环氧树脂的提高了48.1%,冲击强度提高了14.9%;对端羟基聚氨酯改性环氧树脂而言,12%的聚氨酯与环氧树脂能够很好的形成互穿网络结构,使得互穿材料的拉伸性能比纯环氧树脂的提高了23.7%,冲击强度提高了78.9%。
TG-DSC研究表明,聚氨酯改性环氧树脂的热稳定性较纯环氧树脂有较大的提高。这是因为聚氨酯和环氧树脂形成了两相互穿网络结构,使其热稳定性大幅增强。
采用非等温DSC法对改性环氧树脂的固化动力学研究表明,填加了PU的改性EP的表观活化能降低,固化反应的活性提高。
Epoxy resins(EP)are the most important class of thermosetting matrices used in engineering because of their outstanding adhesion to most surfaces,high mechanical strength,and chemical resistance.They have been used as adhesives,coatings and resin matrices for advanced composites. However,their brittle behavior with low elongation and impact strength restrict the utility for high performance applications.The major concern of this paper is to study the preparation of the EP/PU IPNs on improving mechanical and thermal properties of pure EP were investigated by mechanical test,SEM,TEM,DSC,TGA.And EP/PU IPNs' curing dynamics is researched by using Non-uniform temperature DSC methard.
Reaction time and reaction temperature of the PU prepolymer are researched,and obtained the preparation matters concerned temperature for 70℃,the reaction time is 70～90min.Indicated to the polyurethane prepolymer's infrared analysis that the various functional groups are complete reacted,obtained the anticipated product,and discussed the water's influence to the prepolymer.
Mechanics test indicated that the mechanical properties of the epoxy resin with polyurethane modificated was strengthened while its toughness improved highly.For the epoxy resin with wt15%-NCO terminated polyurethane modificated,the tensile strength of EP/PU IPNs could increase by 48.1%,the impact strength could increase by 14.9%,which compared with pure epoxy resin.For the epoxy resin with 12%-OH terminated polyurethane modificated,the tensile strength of EP/PU IPNs could increase by23.7%,the impact strength could increase by 78.9%.
TG-DSC showed the thermostability of hybrid materials were greatly improved,because the IPNs were formed mutually by polyurethane and epoxy resin,which improved its thermostabilit'y in a wide range.
Non-uniform temperature DSC test indicated that,compared with pure epoxy resin,the apparent activation e.nergy of the modified epoxy resin with polyurethane decreased and its activity of curing reaction increased.
实验考察了反应时间和反应温度对聚氨酯预聚物的影响,得到了制备聚氨酯预聚物的适宜温度为70℃,反应时间为70～90min。对聚氨酯预聚物的红外分析表明,各官能团基本反应完全,得到了预期的产物,并讨论了水对预聚物的影响因素。
力学测试表明,用聚氨酯改性后的环氧树脂的韧性得到了很大程度的提高,同时其力学性能也有较大的提高。对端异氰酸酯基聚氨酯改性环氧树脂而言,15%的聚氨酯与环氧树脂能够很好的形成互穿网络结构,使得互穿材料的拉伸性能比纯环氧树脂的提高了48.1%,冲击强度提高了14.9%;对端羟基聚氨酯改性环氧树脂而言,12%的聚氨酯与环氧树脂能够很好的形成互穿网络结构,使得互穿材料的拉伸性能比纯环氧树脂的提高了23.7%,冲击强度提高了78.9%。
TG-DSC研究表明,聚氨酯改性环氧树脂的热稳定性较纯环氧树脂有较大的提高。这是因为聚氨酯和环氧树脂形成了两相互穿网络结构,使其热稳定性大幅增强。
采用非等温DSC法对改性环氧树脂的固化动力学研究表明,填加了PU的改性EP的表观活化能降低,固化反应的活性提高。
Epoxy resins(EP)are the most important class of thermosetting matrices used in engineering because of their outstanding adhesion to most surfaces,high mechanical strength,and chemical resistance.They have been used as adhesives,coatings and resin matrices for advanced composites. However,their brittle behavior with low elongation and impact strength restrict the utility for high performance applications.The major concern of this paper is to study the preparation of the EP/PU IPNs on improving mechanical and thermal properties of pure EP were investigated by mechanical test,SEM,TEM,DSC,TGA.And EP/PU IPNs' curing dynamics is researched by using Non-uniform temperature DSC methard.
Reaction time and reaction temperature of the PU prepolymer are researched,and obtained the preparation matters concerned temperature for 70℃,the reaction time is 70～90min.Indicated to the polyurethane prepolymer's infrared analysis that the various functional groups are complete reacted,obtained the anticipated product,and discussed the water's influence to the prepolymer.
Mechanics test indicated that the mechanical properties of the epoxy resin with polyurethane modificated was strengthened while its toughness improved highly.For the epoxy resin with wt15%-NCO terminated polyurethane modificated,the tensile strength of EP/PU IPNs could increase by 48.1%,the impact strength could increase by 14.9%,which compared with pure epoxy resin.For the epoxy resin with 12%-OH terminated polyurethane modificated,the tensile strength of EP/PU IPNs could increase by23.7%,the impact strength could increase by 78.9%.
TG-DSC showed the thermostability of hybrid materials were greatly improved,because the IPNs were formed mutually by polyurethane and epoxy resin,which improved its thermostabilit'y in a wide range.
Non-uniform temperature DSC test indicated that,compared with pure epoxy resin,the apparent activation e.nergy of the modified epoxy resin with polyurethane decreased and its activity of curing reaction increased.
引文
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[2]李国米.合成树脂及玻璃钢.北京:化学工业出版社,1999.53
[3]赵玉庭,姚希曾.复合材料基体与界面.上海:华东化工学院出版社,1991.55-57
[4]宣兆龙,易建政,张倩.环氧树脂的弹性体增韧改性研究.现在塑料加工应用,2003,15(6):58-60
[5]Gouri C,Ramaswamy R,Ninan K N.Studies on the adhesive properties of solid elaslomer-modified novolac epoxy resin.International Journal of Adhesion and Adhesives,2000,20(4):305-314
[6]秦传香,赵石林.双马来酞亚胺/环氧树脂胶粘剂增韧改性的研究.化学与粘合,2000,29(2):61-63
[7]Wise C W,Cook W D,Goodwin A A.CTBN rubber phase precipitation in model epoxy resins.Polymer,2000,41:4625-4633
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[12]Mimura K,Ito H,Fujioka H.Improvement morphologies of thermal and mechanical properties by control of morphologies in PES-modified epoxy resins.Polymer,1998,41(12):4451-4459
[13]葛青山,常安宇.聚砜改性环氧树脂胶粘剂的研究.粘接,1997,18(5):8-12.
[14]Hourston D J,Lane J M,The toughening of epoxy resins with thermoplastics:1.Trifunctional epoxy resin-polyetherimide blends.Polymer,1992,33(7):1379-1383
[15]R.A.Pearson,A.EYee.Toughening Mechanisms in Thermoplastic Modified Epoxies:Modification using Poly(phenyleneoxide).polymer,1993,34(17):3658-3670
[16]Takao Lijima,Tsutomu Nishina,Wakichi Fukuda.Effect of Matrix Compositions on Modification of Bismaleimide Resin by N-Phenyimaleimide-styrene Copolymers.Appl Polym Sci.,1996,60(1):37-45
[17]Soo Jin Park,Dong Ⅱ Seo,Nah Changwoon.Effect of acidic surface treatment of red mud on mechanical interfacial proper ties of epoxy/red mud nanocomposites.Journal of Colloid and Inter face Science,2002,1:225-229
[18]董元彩,孟卫,魏欣等.环氧树脂/二氧化钛纳米复合材料的制备及性能.塑料工业,1999,27(6):37-38
[19]李小兵.纳米SiO_2/环氧树脂复合材料的制备和性能.[硕士学位论文].湖南:湘潭大学,1999
[20]Tonghui Chen,Hansheng Li,Yue Gao.J.Appl.Polym.Sci.,1998,69:887-893
[21]施利毅,张剑平,华彬.聚氨酯/环氧树脂接枝互穿网络聚合物制备和材料拉伸伸性能.上海大学学报,1998,4(6):675-680
[22]管云林,郭锦棠,邵蕾等.聚氨酯/环氧树脂互穿网络聚合物相行为与断裂拉伸强度.材料研究学报,1996,10(3):313-318
[23]刘竞超,刘朋生,曾大桥.聚氨酯/双酚 A 环氧树脂互穿网络体系力学性能研究.湘潭大学自然科学学报,1997,19(3):63-66
[24]Lange F F.Model for the toughness of epoxy-robber particulate filled epoxide resins.PhilMag,1970,27(22):983-985
[25]钟文彬.利用液晶固化剂改性环氧树脂固化物的研究.[硕士学位论文].湖南:湘潭大学,2000
[26]梁伟荣,王惠民.热致液晶聚合物增韧环氧树脂的研究.玻璃钢/复合材料,1997,4:3-5
[27]Jun Yeob Lee,Tvong Sik Jang.IR study of by drogen bonding in novel liquid crystalline epoxy/GEBA blends.Polymer Bull,1997,38(4):439
[28]熊佳,黄英,王琦洁等.环氧树脂增韧研究进展.塑料,2004,33(3):58-61
[29]Day R J,Lovell P A,Wazzan A A.Toughened carbon/epoxy composites made by using core/shell particles.Composites Science and Technology,2001,61(1):41-56
[30]张龙彬,朱光明.环氧树脂增韧的研究进展.塑料科技,2004,164(6):57-61
[31]Yan Cheng.Numerical and experimental studies on the behavior of rubber-toughened epoxy inbulkspecirrenand laminatedccrrposites.Mater Sci,2002,37(5):921-927
[32]张凯,黄渝鸿,周德惠等.聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳型粒子增韧环氧树脂的研究.绝缘材料,2003,19,(4):7-9
[33]赵德仁.高聚物合成工艺学.北京:化学工业出版社,1995
[34]马天信,姜波.聚氨酯材料在航空工业方舱中的应用.聚氨酯工业,2003,18(1):32-34
[35]赵彩荣,刘朝晖,杨洁等.PTMG型聚氨酯预聚体的研制.合成橡胶工业,2003,26(2):85-87
[36]尹力力,宁霞,朱聪慧.聚氨酯树脂预聚物的控制--二正丁胺法的探讨.皮革化工,1998,15(2):36-37
[37]吴存雷.聚氨酯预聚体技术及其应用.聚氨酯工业,2000,15(3):1-4
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