在线红外法研究季戊四醇丙烯醛树脂的预聚反应动力学
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摘要
采用在线红外法研究了季戊四醇丙烯醛树脂的预聚反应动力学,在反应温度为338.15,348.15 K和358.15 K及催化剂硫酸二乙酯酸(DES)的用量为2%和4%时,监测反应体系中官能团=CH_2浓度的变化,计算得出了该聚合反应的动力学方程,并对固化产物的力学性能进行了研究。结果表明:该反应为二级反应,但该反应初期和后期的表观反应速率、反应活化能相差很大,当DES用量为2%时,反应初期和后期的活化能分别为36.5 kJ·mol~(-1)和49.6.kJ·mol~(-1);当DES用量为4%时,反应初期和后期的活化能分别为61.0 k J·mol~(-1)和69.1 kJ·mol~(-1);DES用量为2%和4%时,DES的用量对固化产物的力学性能影响不明显;反应温度对固化产物的力学性能有显著影响,当DES的用量为2%和4%时,出现在338.15 K时的最大抗拉强度分别为41.99 MPa和41.17 MPa,出现在358.15 K时的最大断裂延伸率分别为8.47%和7.27%。
The reaction kinetic parameters have an important guiding significance for the prepolymerization of acrolein-pentaerythritol resin.Online IR method was used to study the prepolymerization reaction kinetics of acrolein-pentaerythritol resin. When the reaction temperature was 338. 15,348. 15 K and 358. 15 K,and the dosage of diethyl sulfate( DES) as catalyst was 2% and 4% respectively,by monitoring the change in concentration of functional group= CH_2 in the reaction system,the kinetic equation of the polymerization reaction was obtained by calculation and the mechanical property of cured product was studied. The results show that the reaction is a second-order reaction,but the apprent reaction rate and reaction activation energy in the early stage and late stage for the reaction have a large difference. When the dosage of DES is 2%,the apparent activation energy in the early stage and late stage of the reaction is 36. 5 kJ·mol~(- 1)and 49. 6 kJ·mol~(- 1)respectively. When the dosage of DES is 4%,the apparent activation energy in the early stage and late stage of the reaction is 61. 0 kJ·mol~(- 1)and69. 1 kJ·mol~(- 1)respectively. When the dosage of DES is 2% and 4%,the effect of dosage of DES on the mechanical property of cured product is not obvious. The reaction temperature on the mechanical property of cured product has a remarkable influence,when the dosage of DES is 2% and 4%,the maximum tensile strength appeared at 338. 15 K is 41. 99 MPa and 41. 17 MPa,respectively,the maximum elongation at break appeared at 358. 15 K is 8. 47% and 7. 27%,respectively.
The reaction kinetic parameters have an important guiding significance for the prepolymerization of acrolein-pentaerythritol resin.Online IR method was used to study the prepolymerization reaction kinetics of acrolein-pentaerythritol resin. When the reaction temperature was 338. 15,348. 15 K and 358. 15 K,and the dosage of diethyl sulfate( DES) as catalyst was 2% and 4% respectively,by monitoring the change in concentration of functional group= CH_2 in the reaction system,the kinetic equation of the polymerization reaction was obtained by calculation and the mechanical property of cured product was studied. The results show that the reaction is a second-order reaction,but the apprent reaction rate and reaction activation energy in the early stage and late stage for the reaction have a large difference. When the dosage of DES is 2%,the apparent activation energy in the early stage and late stage of the reaction is 36. 5 kJ·mol~(- 1)and 49. 6 kJ·mol~(- 1)respectively. When the dosage of DES is 4%,the apparent activation energy in the early stage and late stage of the reaction is 61. 0 kJ·mol~(- 1)and69. 1 kJ·mol~(- 1)respectively. When the dosage of DES is 2% and 4%,the effect of dosage of DES on the mechanical property of cured product is not obvious. The reaction temperature on the mechanical property of cured product has a remarkable influence,when the dosage of DES is 2% and 4%,the maximum tensile strength appeared at 338. 15 K is 41. 99 MPa and 41. 17 MPa,respectively,the maximum elongation at break appeared at 358. 15 K is 8. 47% and 7. 27%,respectively.
引文
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[4]罗雪梅,左玉芬,黄黎明,等.硫酸二乙酯酸值对123树脂固化的影响研究[J].含能材料,2001,9(1):34-36.LUO Xue-mei,ZUO Yu-fen,HUANG Li-ming,et al.Influence of acid value in diethyl sulfate on the curing progess of 123 resin[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2001,9(1):34-36.
[5]蔡贾林,高登攀,郑申声,等.季戊四醇丙烯醛树脂体系固化动力学及流变特性[J].含能材料,2015,23(6):558-562.CAI Jia-lin,GAO Deng-pan,ZHEN Shen-sheng,et al.Curing kinetics and rheology property of acrolein-pentaerythritol resin system[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(6):558-562.
[6]杨鹏飞,李天铎.甲苯-2,4-二异氰酸酯-聚环氧丙烷二元醇聚合反应在线红外研究[J].化学反应工程与工艺,2008,24(5):472-475.YANG Peng-fei,LI Tian-duo.Kinetic study on tolylene-2,4-diisocyanate-poly(propylene oxide)bulk polymerization by react IR[J].Chemical Reaction Engineering and Technology,2008,24(5):472-475.
[7]韩涛,王晓云,于萍,等.甲基丙烯酸十八酯基油溶性聚合物反应过程的在线红外研究[J].山东大学学报,2011,41(2):144-148.HANG Tao,WANG Xiao-yun,YU Ping,et al.React IR study of the synthesis of octadecyl methacry late-based oil soluble polymer[J].Journal of Shang Dong University,2011,41(2):144-148.
[8]彭云云,武书彬.TG-FTIR联用研究半纤维素的热裂解特性[J].化工进展,2009,28(8):1478-1484.PENG Yun-yun,WU Shu-bin.Characteristics and kinetics of sugarcane bagasse hemicellulose pyrolysis by TG-FTIR[J].Chemical Industry and Engineering Progress,2009,28(8):1478-1484.
[9]闫泽群,王洪武,黄岐善,等.MDI与PPG预聚反应动力学[J].高分子材料科学与工程,2009,25(12):5-8.YAN Ze-qun,WANG Hong-wu,HUANG Qi-shan,et al.Prepolymer reaction kinetics of MDI and PPG[J].Polymer Materials Science and Engineering,2009,25(12):5-8.
[10]陈建福,张卫英,李晓,等.PHA与TDI本体聚合反应动力学[J].高分子材料科学与工程,2012,28(5):77-80.CHEN Jian-fu,ZHANG Wei-ying,LI Xiao,et al.Reaction kinetics of the PHA/TDI bulk polymerization[J].Polymer Materials Science and Engineering,2012,28(5):77-80.
[11]王洪武,张红,郑辰,等.在线红外研究H12MDI与PCDL预聚反应动力学[J].聚氨酯工业,2009,24(3):17-20.WANG Hong-wu,ZHANG Hong,ZHENG Chen,et al.Study on prepolymer reation kinetics of H12MDI and PCDL by online IR technology[J].Polyurethane Industry,2009,24(3):17-20.
[12]邓芹英,刘岚,邓慧敏.波谱分析教程[M].北京:科学出版社,2003:2-3.
[13]武卓,李洪旭,庞爱民,等.FT-IR法研究键合剂与N-100的反应动力学[J].火炸药学报,2012,35(5):41-44.WU Zhuo,LI Hong-xu,PANG Ai-min,et al.Study on the reaction kinetics of bonding agents and N-100 by FT-IR[J].Chinese Journal of Explosives&Propellants,2012,35(5):41-44.
[14]Griffith AA.Theory of rupture.In:Proceeding of the 1st international conference on applied mechanics[C]∥Delft,Holland,1924:55-63.