CAJ | 학술논문

为研究三炔基化合物与聚叠氮缩水甘油醚（GAP）在无催化剂时的交联反应活性和反应动力学，以三炔丙基间苯三酚醚（TPPG）、均苯三甲酸三炔丙酯（TPTM）、均苯三甲酸三炔丁酯（TBTM）为对象，通过傅里叶红外（FT-IR）跟踪反应进程并观察反应过程中特征官能团的变化，采用差示扫描量热法（DSC）研究了交联反应动力学，建立了反应动力学方程并模拟实际等温反应历程。结果表明，在60℃下，3种三炔基化合物可与GAP 发生1，3-偶极环加成反应生成三唑交联体系，TPPG、TPTM、TBTM交联反应活性依次降低，TPPG 的低温反应活性最好；根据DSC 曲线计算出3种体系的活化能分别为78．8、80．3、87．6 kJ／mol，交联反应级数约为0．92；n级动力学模型可以很好地预测等温反应进程，预测结果与验证结果基本符合。
위연구삼결기화합물여취첩담축수감유미（GAP）재무최화제시적교련반응활성화반응동역학，이삼결병기간분삼분미（TPPG）、균분삼갑산삼결병지（TPTM）、균분삼갑산삼결정지（TBTM）위대상，통과부리협홍외（FT-IR）근종반응진정병관찰반응과정중특정관능단적변화，채용차시소묘량열법（DSC）연구료교련반응동역학，건립료반응동역학방정병모의실제등온반응역정。결과표명，재60℃하，3충삼결기화합물가여GAP 발생1，3-우겁배가성반응생성삼서교련체계，TPPG、TPTM、TBTM교련반응활성의차강저，TPPG 적저온반응활성최호；근거DSC 곡선계산출3충체계적활화능분별위78．8、80．3、87．6 kJ／mol，교련반응급수약위0．92；n급동역학모형가이흔호지예측등온반응진정，예측결과여험증결과기본부합。
In order to study the reactivity and reaction kinetics of the crosslinking reaction between three acetylene-terminated compounds and glycidyl azide polymer(GAP),selecting 1 ,3 ,5-tris(prop-2-yn-1-yloxy)benzene(TPPG), tri(but-3-yn-1-yl)benzene-1,3,5-tricarboxylate (TBTM)and tripropargyl trimesate (TPTM)as objects,the changes of characteristic functional groups during the reaction were observed by FT-IR,and the reaction kinetics of the three systems were explored by differential scanning calorimetry(DSC).The kinetic equation was established to simulate the actual isothermal reaction course.The results indicate that the three acetylene-terminated compounds can react with GAP by 1 ,3-dipolar cycloaddition reaction at 60 ℃,and cross-linking reactivity of TPPG,TPTM and TBTM decreases in turn during the reaction.TPPG shows best activity at low temperature.According to the DSC curves,the activation energies of the three systems are 78.8,80.3 and 87.6 kJ/mol,respectively,and the reaction order is about 0.92.n-order kinetic model can predict the isothermal reaction process,and the isothermal reaction prediction results are in consistent with the verification results.