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.
引文
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