基于淀粉液化APF树脂的固化动力学研究
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摘要
采用非等温差热分析法(DSC)对液化淀粉改性酚醛树脂(APF)的固化行为及固化动力学进行了研究。由Kissinger和Ozawa等方法计算得到固化反应的表观活化能(E_a)、反应级数(n)及频率因子(A),进而建立了APF树脂的固化反应动力学模型。结果表明,相比PF树脂,APF树脂的固化反应起始温度(T_i)由99.4℃增至100.3℃,峰值温度(T_p)由127.8℃降至122.1℃,终止温度(T_f)由150.2℃降至146.3℃,表观活化能(E_a)由96.94 kJ/mol降至87.94 kJ/mol。APF树脂的贮存稳定性更好,并可在较低的固化温度下固化,固化反应更容易进行。APF树脂的固化反应动力学模型为da/dt=9.56#10~(10 e-87940/RTP)^1-ah~(0.9385)。
The curing behavior and curing kinetics of modified phenolic resin based on liquified amylum(APF) were studied by differential scanning calorimetry(DSC). The curing kinetic parameters such as apparent activation energy(E_a), reaction order(n) and frequency factor(A) were calculated using Kissinger and Ozawa methods. Furthermore, the curing kinetic model of APF resin was established. Compared with PF resin, the curing initial temperature(T_i) was increased from 99.4 ℃ to 100.3 ℃, the peak temperature(T_p) was reduced from 127.8 ℃ to 122.1 ℃, the curing final temperature(T_f) was reduced from 150.2 ℃ to 146.3 ℃, and the apparent activation energy(E_a) was reduced from 96.94 kJ/mol to 87.94 kJ/mol. The results showed that APF resin with better storage stability could be cured easily under a lower temperature than PF resin. The curing reaction kinetic model of APF resin was da/dt=9.56#10~(10 e-87940/RTP)^1-ah~(0.9385)。
The curing behavior and curing kinetics of modified phenolic resin based on liquified amylum(APF) were studied by differential scanning calorimetry(DSC). The curing kinetic parameters such as apparent activation energy(E_a), reaction order(n) and frequency factor(A) were calculated using Kissinger and Ozawa methods. Furthermore, the curing kinetic model of APF resin was established. Compared with PF resin, the curing initial temperature(T_i) was increased from 99.4 ℃ to 100.3 ℃, the peak temperature(T_p) was reduced from 127.8 ℃ to 122.1 ℃, the curing final temperature(T_f) was reduced from 150.2 ℃ to 146.3 ℃, and the apparent activation energy(E_a) was reduced from 96.94 kJ/mol to 87.94 kJ/mol. The results showed that APF resin with better storage stability could be cured easily under a lower temperature than PF resin. The curing reaction kinetic model of APF resin was da/dt=9.56#10~(10 e-87940/RTP)^1-ah~(0.9385)。
引文
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[25]魏立婷,杨松,韩淑伟,等.黄顶菊秸秆pH值、缓冲容量及脲醛树脂固化特性的研究[J].林业机械与木工设备,2017,45(8):28-31.
[2]宁培森,郭振宇,丁著明.生物质酚醛树脂的研究进展[J].塑料助剂,2017(3):1-9.
[3]占均志,甘卫星,马庆,等.基于马占相思栲胶单宁酚醛树脂胶黏剂的合成与热压工艺研究[J].林产工业,2013,40(4):32-35.
[4]Yan L,Cui Y,Gou G,et al.Liquefaction of lignin in hot-compressed water to phenolic feedstock for the synthesis of phenol-formaldehyde resins[J].Composites Part B:Engineering,2017,112:8-14.
[5]甘卫星,罗建举.我国木材胶黏剂的发展现状[J].国际木业,2006(12):34-36.
[6]李强,王建军.合成树脂胶黏剂在木材工业中的应用[J].林产工业,2017,44(1):35-37.
[7]吴志刚,雷洪,杜官本,等.新型酚醛树脂改性大豆蛋白胶的研究(Ⅱ)[J].西北林学院学报,2016,31(3):252-256.
[8]Qiao W,Li S,Guo G,et al.Synthesis and characterization of phenolformaldehyde resin using enzymatic hydrolysis lignin[J].Journal of Industrial and Engineering Chemistry,2015,21:1417-1422.
[9]雷洪,杜官本,A Pizzi.单宁基木材胶黏剂的研究进展[J].林产工业,2008,35(6):15-19.
[10]徐文凤,熊姗姗,施豫庆,等.Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition:a Theoretical Investigation[J].结构化学,2012,31(6):821-828.
[11]晁威.木质素基酚醛树脂的制备及应用研究[D].吉林:吉林大学,2017.
[12]巫国富,许忠允,潘晖.液化木基酚醛树脂制备胶合板的热压工艺研究[J].湖北农业科学,2013,52(7):1644-1646.
[13]傅深渊,栾复友,程书娜,等.竹材液化物酚醛树脂胶固化及固化动力学研究[J].生物质化学工程,2009,43(4):33-37.
[14]Kissinger H E.Reaction kinetics in differential thermal analysis[J].Analytical chemistry,1957,29(11):1702-1706.
[15]Ozawa T.Kinetic analysis of derivative curves in thermal analysis[J].Journal of Thermal Analysis and Calorimetry,1970,2(3):301-324.
[16]Crane L W,Dynes P J,Kaelble D H.Analysis of curing kinetics in polymer composites[J].Journal of Polymer Science Part C:Polymer Letters,1973,11(8):533-540.
[17]刘晓欢,傅深渊,宗恩敏,等.液化竹基酚醛树脂/竹粉复合体系固化动力学研究[J].热固性树脂,2011,26(2):7-11.
[18]于红卫,刘志坤,方群,等.淀粉-碱木素改性酚醛树脂的粘接性能及固化动力学研究[J].浙江农林大学学报,2014,31(1):129-135.
[19]张一甫,杨海兵,甘卫星,等.蔗糖-三聚氰胺-甲醛树脂的反应动力学分析[J].桂林理工大学学报,2016,36(2):314-319.
[20]杨海兵,潘礼成,张一甫,等.麦芽糖-三聚氰胺-甲醛共缩聚树脂的热性能分析[J].桂林理工大学学报,2015,35(3):595-601.
[21]徐卫兵,鲍素萍,沈时骏,等.酚醛树脂/蒙脱土纳米复合材料的制备及固化反应动力学研究[J].高分子学报,2002,1(4):457-461.
[22]宋世谟,王正烈,李文斌.物理化学[M].第3版.北京:高等教育出版社,1993:229-231.
[23]ASTM E 698-2005 Standard Test Method for Arrhenius Kinetic Constants for Thermally Unstable Materials[S].USA:ASTM,2005.
[24]刘晶如,罗运军.非等温DSC研究Al/HTPB/TDI体系的固化反应动力学[J].含能材料,2009,17(1):83-86.
[25]魏立婷,杨松,韩淑伟,等.黄顶菊秸秆pH值、缓冲容量及脲醛树脂固化特性的研究[J].林业机械与木工设备,2017,45(8):28-31.