过氧甲酸法低相对分子质量聚丁二烯环氧化的动力学研究

Kinetic Studies of the Epoxidation of Low Relative Molecular Mass Poly(1,2-butadiene) by Peroxyformic Acid

红外光谱表明过氧甲酸法可以实现对低相对分子质量聚(1,2-丁二烯)(LPB)的改性,得到环氧化低相对分子质量聚丁二烯(LOPB)。反应温度大于50℃会造成开环化反应或过度交联。在反应温度45℃,通过间隔取样法,由实验测定的环氧值-时间关系曲线与理论推导速率方程的拟合结果表明,LPB的环氧化反应为一级反应,反应速率方程简化为r=kC(C为环氧值),反应速率常数k=0.074 5 kg.L-1.h-1;得到环氧值随时间呈指数变化C=0.4 e0.42t。

Low relative molecular mass poly （1, 2-butadiene ）epoxy resin （LOPB） could been successfully obtained through chemical modification of low relative molecular mass poly （1, 2- butadiene） （LPB） by peroxyformic acid as shown by FTIR spectra. Temperature played the most important role in controlling the epoxy value of LOPB, and the ring opening and crosslinking reaction would be occurred when the reaction temperature was above 50 ℃. At 45℃, by using interval sampling method, based on the experimental results of epoxy values variation with time and the theoretical derivation rate equation, the epoxidation reaction was defined as first -order reaction, and the reaction rate equation could be simplified as r =kC（ C：epoxy values,kg/100 kg） with constant k =0. 074 5 kg · L^ -1· h^-1. Furthermore, in reaction time t, the epoxy values C could be directly calculated from equation C = 0. 4e^0.42t which is very valuable for controlling this reaction in the industry.