钼酚醛树脂改性BMI树脂和海因环氧树脂的研究
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摘要
双马来酰亚胺(BMI)与环氧树脂(EP),常作为复合材料基体、涂料、胶黏剂,被广泛应用于航空航天、交通、化工、建筑等领域。但随着电气工业及航空航天等领域的发展,由于使用条件越来越苛刻,对材料的耐热性提出更为严格的要求,所以开发高耐热BMI和EP显得尤为重要。为进一步提高BMI和海因环氧树脂(HY)的耐热性,将高耐热性钼酚醛树脂(Mo-PF)作为改性剂对BMI和HY进行改性。
在一定条件下,以苯酚、甲醛、钼酸及催化剂氢氧化钠为原料合成热固性Mo-PF。运用FTIR考察了树脂的化学结构；GPC分析得出,所合成的Mo-PF的重均分子量在918左右,树脂主要由二聚体或三聚体构成；通过凝胶时间曲线求得Mo-PF固化反应活化能为28.219kJ/mol。TG分析得,900℃时,Mo-PF的残炭率为20%左右。
以Mo-PF为改性剂(质量分数分别为10%、30%)对BMI进行共混改性,通过DTA对树脂体系的固化反应动力学进行研究,推导Mo-PF(10%)/BMI体系的固化反应动力学方程为推导Mo-PF(30%)/BMI体系的固化反应动力学方程为通过TG对树脂固化物的热分解动力学进行研究,推导钼酚醛树脂(10%)/BMI体系的分解反应动力学方程为推导钼酚醛树脂(30%)/BMI体系的热分解反应动力学方程为
以Mo-PF为改性剂(质量分数为50%)对HY进行共混改性,通过DTA对Mo-PF/HY体系的固化反应动力学进行研究,因树脂体系的固化反应比较复杂,故研究分两个阶段进行,推导Mo-PF/HY体系固化反应第一阶段动力学方程为第二阶段的动力学方程为通过TG对树脂体系固化物的热分解动力学进行研究,推导Mo-PF/HY体系的热分解反应动力学方程为da/dt=2.47×108exp(-26564.8/T)(1-a)1.02。
BMI and EP are widely used in aerospace, transportation, construction and so on. Butwith the development of electric industry, aerospace, strict conditions of use are increasinglydemanding, requirements of heat resistance of materials are put forward more strict, so thedevelopment of BMI and EP with high heat resistant is very important.
In this paper, molebdenum-phenolic resol resin were sythetised at first, and then BMIand hydantoin epoxy resin were modified by it. Many modern analysis techniques were usedto characterizated the microstructure, solidification performance, thermal decompositionproperties of molybdenum phenolic resin, Mo-PF / BMI, Mo-PF / hydantoin epoxy resin.
Molebdenum-phenolic resol resin was synthesized by phenol, formaldehyde, molybdateand sodium hydroxide. Optimal synthesis technology was obtained by orthogonal test withchar yields as index. Curing reaction of the resin was investigated by FTIR. Molecular weightdistribution of the resin was characterizated by GPC. The curing reaction activation energywas analyzed by gel time at different temperatures. Thermal stability was characterizated byTG.
BMI was modified by Mo-PF, curing reaction kinetics of the system was characterizatedby DTA.Thermal decomposition kinetics was characterizated by TG.The kinetic equation wasdeduced by various kinetic parameters of the system.
Hydantoin epoxy resin was modified by Mo-PF, curing reaction kinetics of the systemwas characterizated by DTA.Thermal decomposition kinetics was characterizated by TG.Thekinetic equation was deduced by various kinetic parameters of the system.
在一定条件下,以苯酚、甲醛、钼酸及催化剂氢氧化钠为原料合成热固性Mo-PF。运用FTIR考察了树脂的化学结构；GPC分析得出,所合成的Mo-PF的重均分子量在918左右,树脂主要由二聚体或三聚体构成；通过凝胶时间曲线求得Mo-PF固化反应活化能为28.219kJ/mol。TG分析得,900℃时,Mo-PF的残炭率为20%左右。
以Mo-PF为改性剂(质量分数分别为10%、30%)对BMI进行共混改性,通过DTA对树脂体系的固化反应动力学进行研究,推导Mo-PF(10%)/BMI体系的固化反应动力学方程为推导Mo-PF(30%)/BMI体系的固化反应动力学方程为通过TG对树脂固化物的热分解动力学进行研究,推导钼酚醛树脂(10%)/BMI体系的分解反应动力学方程为推导钼酚醛树脂(30%)/BMI体系的热分解反应动力学方程为
以Mo-PF为改性剂(质量分数为50%)对HY进行共混改性,通过DTA对Mo-PF/HY体系的固化反应动力学进行研究,因树脂体系的固化反应比较复杂,故研究分两个阶段进行,推导Mo-PF/HY体系固化反应第一阶段动力学方程为第二阶段的动力学方程为通过TG对树脂体系固化物的热分解动力学进行研究,推导Mo-PF/HY体系的热分解反应动力学方程为da/dt=2.47×108exp(-26564.8/T)(1-a)1.02。
BMI and EP are widely used in aerospace, transportation, construction and so on. Butwith the development of electric industry, aerospace, strict conditions of use are increasinglydemanding, requirements of heat resistance of materials are put forward more strict, so thedevelopment of BMI and EP with high heat resistant is very important.
In this paper, molebdenum-phenolic resol resin were sythetised at first, and then BMIand hydantoin epoxy resin were modified by it. Many modern analysis techniques were usedto characterizated the microstructure, solidification performance, thermal decompositionproperties of molybdenum phenolic resin, Mo-PF / BMI, Mo-PF / hydantoin epoxy resin.
Molebdenum-phenolic resol resin was synthesized by phenol, formaldehyde, molybdateand sodium hydroxide. Optimal synthesis technology was obtained by orthogonal test withchar yields as index. Curing reaction of the resin was investigated by FTIR. Molecular weightdistribution of the resin was characterizated by GPC. The curing reaction activation energywas analyzed by gel time at different temperatures. Thermal stability was characterizated byTG.
BMI was modified by Mo-PF, curing reaction kinetics of the system was characterizatedby DTA.Thermal decomposition kinetics was characterizated by TG.The kinetic equation wasdeduced by various kinetic parameters of the system.
Hydantoin epoxy resin was modified by Mo-PF, curing reaction kinetics of the systemwas characterizated by DTA.Thermal decomposition kinetics was characterizated by TG.Thekinetic equation was deduced by various kinetic parameters of the system.
引文
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[3] Li Chen, Su Chen, Latex interpenetrating networks based on polyurethane, polyacrylateand epoxy resin[J]. Progress in Organic Coatings. 2004, 49: 252-258.
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[5]李芝华，卢健体，丑纪能等.高性能TDE-85/E-51环氧树脂的聚氨酯增韧改性[J].中南大学学报(自然科学版). 2008, 39(6): 1239-1243
[6] F.J.Hua, etc. Interpenetrating polymer networks of epoxy resin and urethane acrylate resin2. Morphology and mechanical property[J]. European Polymer Journal. 2000, 36: 27-33
[7]黄发荣.酚醛树脂及其应用[M].北京:化学工业出版社, 2003.
[8] Ahmad Reza Bahramian, Mehrdad Kokabi, et al. High temperature ablation of kaolinitelayered silicate/phenolic resin/asbestos cloth nanocomposite[J]. Journal of HazardousMaterials, 2008(150): 136-145.
[9]周励民,刘润山.液态和混合烯丙基酚改性BMI树脂研究.高分子材料科学与工程,2000(5): 138-141.
[10]李玲,梁国正.烯丙基酚氧树脂改性BMI的研究.高分子材料科学与工程, 1996
[11]许亚洪,益小苏.硼酚醛改性BMI树脂的研究.工程塑料应用, 2001, 29(4): 1-3.
[12] K.S. Santhosh Kunmar, C.P. Reghunadhan Nair, R. Sadhana, K.N. Ninan.Benzoxazine-bismaleimide blends: Curing and thermal properties[J]. European PolymerJournal, 2007(43): 5084-5096.
[13] Ali Nazakat,吴寅,张秋禹,陈营. PES／PEK改性BMI树脂的性能研究.西北工业大学学报, 2012(1): 149-153.
[14] Reghunadhan Nair C P. Advances in addition-cure phenolic resins[J]. Progress inPolymer Science, 2004(29): 401-498.
[15]刘云峰,刘伟区,于丹.聚苯醚再分配产物改性环氧树脂的研究.化学建材,2009(5): 16-18.
[16]曹诺，罗方敏，肖圣洁等.纳米丁苯吡弹性体增韧环氧树脂的研究[J].塑料工业. 2006,34(5): 9-11.
[17] Shiqiang Deng, Jianing Zhang, Lin Ye, etc. Toughening epoxies with halloysitenanotubes[J]. Polymer. 2008, 49: 5119-5127.
[18] Jia Liu (Daniel), Hung-Jue Sue, Zachary J. Thompson, etc. Strain rate effect ontoughening of nano-sized PEP-PEO block copolymer modified epoxy[J]. Acta Materialia.2009, 57: 2691-2701.
[19]蒋玉梅等.联苯型液晶聚氨酯增韧噶性环氧树脂的制备与性能[J].高分子材料科学与工程. 2009, 25(9): 150-153.
[20]贾荣勋.酚醛改性环氧树脂的应用.四川化工与腐蚀控制, 1999(6): 44~46.
[21] Wei Jiang, Shinn-Horng Chen, et al. Nanocomposites from phenolic resin and variousorgano-modified montmorillonites: Preparation and Thermal Stability[J]. Journal of AppliedPolymer Science, 2006, 102(6): 5336-5343.
[22]戴羚羚，吴键儒,陈大俊.酚醛树脂/凹凸棒土纳米复合材料的制备与表征[J].塑料工业, 2010, 38(2): 15-18,45.
[23]刘运传,魏莉萍.硼酚醛改性环氧树脂的成炭性能及热解动力学.四川兵工学报,2009（8）: 7~10.
[24]徐伟箭，余霞，刘汉平等.二氧化双环戊二烯环氧树脂/聚氨酯互穿聚合物网络制备与性能研究[J].涂料工业. 2008, 38(1): 8-11.
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