氧化木薯淀粉改性MUF树脂的性能与固化特征
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摘要
通过在三聚氰胺-尿素-甲醛树脂(MUF)合成反应的不同阶段添加氧化木薯淀粉,制备得到了不同系列树脂,分别为MUF0、MUF1和MUF2,并对其基本性能及粘接强度进行了测试和分析。为了进一步了解氧化木薯淀粉对MUF树脂固化反应的影响,借助差示扫描量热分析仪(DSC)对树脂在不同升温速率条件下的固化特征参数及固化行为进行了表征。结果表明,在合成反应不同阶段加入氧化木薯淀粉,可有效提升树脂的粘接性能并降低树脂中的游离甲醛含量,特别是在树脂合成反应的第3阶段进行添加,效果更为显著。利用Kissinger方程对不同树脂的固化动力学参数进行分析,得到了树脂固化反应的表观活化能E a,表观频率因子A和反应级数n,并建立了固化反应动力学模型。在本试验条件下,树脂经过氧化木薯淀粉改性后,虽然固化所需活化能有不同程度的提高,但可形成更高的粘接强度。
Various MUF resins, namely MUF0, MUF1 and MUF2, were prepared by adding the oxidized cassava starch at the different stages of resin synthesis, and the basic properties and bonding strength of the resins were tested and analyzed. In order to learn the effects of oxidized cassava starch on resins curing performance, differential scanning calorimeter(DSC) was employed to obtain the character parameters of resins in the condition of different heating rates and explore the curing behavior. The results showed that the resins performance was improved by adding the oxidized cassava starch, the bonding properties was increased and the freee formaldehyde content in the resins decreased, especially the results were more excellent when the oxidized cassava starch was added at the third stage of resin synthesis. By using Kissinger equation, the curing kinetic parameters were analyzed, and the apparent activation energy E a, apparent frequency factor A and reaction order n were obtained. The curing reaction kinetics model was established. In this work, the resin modified with oxidized cassava starch had higher bonding strength although its reaction activation energy was higher than that of the pure MUF resin.
Various MUF resins, namely MUF0, MUF1 and MUF2, were prepared by adding the oxidized cassava starch at the different stages of resin synthesis, and the basic properties and bonding strength of the resins were tested and analyzed. In order to learn the effects of oxidized cassava starch on resins curing performance, differential scanning calorimeter(DSC) was employed to obtain the character parameters of resins in the condition of different heating rates and explore the curing behavior. The results showed that the resins performance was improved by adding the oxidized cassava starch, the bonding properties was increased and the freee formaldehyde content in the resins decreased, especially the results were more excellent when the oxidized cassava starch was added at the third stage of resin synthesis. By using Kissinger equation, the curing kinetic parameters were analyzed, and the apparent activation energy E a, apparent frequency factor A and reaction order n were obtained. The curing reaction kinetics model was established. In this work, the resin modified with oxidized cassava starch had higher bonding strength although its reaction activation energy was higher than that of the pure MUF resin.
引文
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[12]李永锋,赵光龙,张志强,等.国内木薯淀粉化学改性的研究进展[J].热带农业科学,2007,27(5):64-67,72.
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[14]王辉,李吏详,刘斯宁,等.反应原料用量对MUF共缩聚树脂分子量分布的影响[J]森林与环境学报,2017,37(1):124-128.
[15]GB/T14074-2006,木材胶粘剂及其树脂检验方法[S].北京:中国标准出版社,2006.
[16]李文环,刘晓欢,徐斌斌,等.三聚氰胺树脂-竹粉复合体系固化动力学研究[J].热固性树脂,2016,31(4):21-24.
[17]盛江峰,陈雁芳,琚小双,等.非等温DSC法研究环氧树脂固化反应动力学过程[J].中国胶粘剂,2013,22(6):9-12.
[2]俞丽珍,刘东东,刘璇,等.氧化淀粉改性脲醛树脂胶粘剂的合成工艺研究[J].中国胶粘剂,2013,22(8):27-31.
[3]甘卫星,唐贤明,伍能文,等.蔗糖-三聚氰胺-甲醛共缩聚树脂胶粘剂的合成工艺及结构表征[J].桂林理工大学学报,2011,31(3):423-429.
[4]孙丽丽,邱凤仙,杨冬亚,等.氧化淀粉改性脲醛树脂的研究[J].化工时刊,2007,21(9):14-16.
[5]席雪冬,雷洪,杜官本,等.单宁改性室温固化型MUF树脂性能研究[J].西南林业大学学报,2016,36(6):143-147.
[6]彭园花,曾祥钦,卢红梅.木质素的提纯及其在脲醛树脂胶粘剂中的应用[J].贵州化工,2006,35(4):16-17.
[7]张本刚,朱来来,席雪冬,等.单宁改性集成材用MUF树脂胶粘剂[J].粘接,2017,38(10):31-34.
[8]付茂辰,许升,吴康,等.玉米淀粉改性低毒脲醛树脂的性能研究[J].化学与黏合,2015,37(4):244-246.
[9]Wu L,Guo J F,Zhang Z Y,et al.Influence of Oxidized Starch and Modified Nano-SiO on 2Performance of Urea-Formaldehyde(UF)Resin[J].,2017,41(1):83-89.
[10]Zhu X F,Xu E G,Lin R H,et al.Decreasing the formaldehyde emission in urea-formaldehyde using modified starch by strongly acid process[J].Journal of Applied Polymer Science,2014,131(9):40202-1-40202-6.
[11]席雪冬,雷洪,杜官本,等.大豆蛋白改性集成材用三聚氰胺-尿素-甲醛树脂[J].森林与环境学报,2017,58(1):119-123.
[12]李永锋,赵光龙,张志强,等.国内木薯淀粉化学改性的研究进展[J].热带农业科学,2007,27(5):64-67,72.
[13]吴俊华,孙玮鸿,赵思思,等.氧化木薯淀粉改性胶黏剂的制备[J].林产工业,2017,24(1):29-31,34.
[14]王辉,李吏详,刘斯宁,等.反应原料用量对MUF共缩聚树脂分子量分布的影响[J]森林与环境学报,2017,37(1):124-128.
[15]GB/T14074-2006,木材胶粘剂及其树脂检验方法[S].北京:中国标准出版社,2006.
[16]李文环,刘晓欢,徐斌斌,等.三聚氰胺树脂-竹粉复合体系固化动力学研究[J].热固性树脂,2016,31(4):21-24.
[17]盛江峰,陈雁芳,琚小双,等.非等温DSC法研究环氧树脂固化反应动力学过程[J].中国胶粘剂,2013,22(6):9-12.