高压二氧化碳强化的聚氨酯等温固化反应  

Polyurethane Isothermal Curing Reaction Reinforced by High Pressure Carbon Dioxide

作　　者：周晨 杨泽 许志美[1] 刘涛[1] 赵玲[1] Zhou Chen;Yang Ze;Xu Zhimei;Liu Tao;Zhao Ling(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237

出　　处：《化学反应工程与工艺》2018年第4期334-341,共8页Chemical Reaction Engineering and Technology

基　　金：国家重点研发计划项目(2016YFB0302200);国家自然科学基金面上项目(21676092)

摘　　要：采用高压差示扫描量热法研究了40～100℃,0.1～9.0 MPa的二氧化碳(CO_2)氛围中的聚醚三醇和多亚甲基多苯基多异氰酸酯合成聚氨酯的等温固化反应,并采用扩散修正后的Kamal自催化模型及等转化率法进行了动力学研究。结果表明,与相同压力的氦气中的聚氨酯固化反应相比,高压CO_2氛围中反应速率快,最终固化度高;并且随着CO_2压力的上升,反应速率和最终固化度均提高,这是因为高压CO_2的溶剂化作用降低了聚氨酯齐聚物的玻璃化转变温度和体系黏度,强化了传质;扩散修正的Kamal自催化模型所得的活化能和等转化率法计算出的不同固化度的表观活化能都随CO_2压力的升高而减小,证明了高压CO_2对聚氨酯固化反应的促进作用。The polyurethane (PU) isothermal curing reaction between the polyether triol and the polyaryl polymethylene polyisocyanate was investigated by high-pressure differential scanning calorimeter method at 40-100 ℃ with the carbon dioxide (CO2) atmosphere at the pressures of 0.1-9.0 MPa. The modified Kamal autocatalytic model and the isoconversional method were used to study the kinetics. The results showed that PU curing reaction in high-pressure CO2 atmosphere was accelerated and had higher final curing degrees compared with those in high-pressure helium atmosphere. With the rising of CO2 pressure,both PU curing rate and final curing degree increased. This was because the solvation effect of high-pressure CO2,which decreased the glass-transition temperature and viscosity of the polyurethane oligomers in the PU curing systems,thus intensified the mass transfer in curing process. Both the activation energies obtained by the diffusion-amended autocatalytic kinetic model and the apparent activation energies of different curing degrees calculated by isoconversional method decreased with the increase of CO2 pressure,which proved the promotion effect of high pressure CO2 on the PU curing reaction.

关 键 词：聚氨酯 高压二氧化碳 等温固化反应 溶剂化效应 自催化动力学模型 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业] TQ013.2