交联/多相体系化学流变研究与群子理论的应用

【作者】 姜志国；

【导师】 金日光； 周亨近；

【作者基本信息】 北京化工大学 ， 高分子材料， 1999， 博士

【摘要】 本文从聚氨酯材料出发，研究了多相／交联体系的化学流变性能。针对快速反应的特点，首先开发研制了化学流变测试方法。设计制造了三种粘度计：等温粘度计、绝热粘度计和凝胶计。三种粘度计各有特点，其中等温粘度计用于测量等温状态下的化学反应过程中粘度变化；绝热粘度计的测试条件更加接近实际生产过程，可以测量绝热状态下反应过程中粘度的变化和反应过程中的绝热温升—反应程度—的变化情况；凝胶计主要用于精确测定凝胶时间和凝胶点附近的粘度变化。利用以上实验装置，作者测定了实验配方对原料反应过程中的粘度变化，主要测定了包括催化剂的品种和含量变化对反应粘度的影响，催化剂包括三乙烯二胺、二月桂酸二丁基锡和胺锡复合催化剂。在实验中观察到了凝胶点附近的粘度下降现象，证明粘度下降现象是温度与反应过程的相分离的共同作用结果。应用JRG模糊群子理论对粘度下降现象进行了数学处理和解释，明确了交联／多相体系反应过程中微观结构的变化和相分离过程，用数学模型表明了各个不同反应阶段的流动结构对反应粘度的不同影响程度。首次依据反应特点、微观结构特征和流变性质对交联／多相体系的聚氨酯反应过程进行了划分：反应初期，均一的液相体系，扩散为反应速度的控制因素，0级反应；加速反应期，由均一的液相向固／液悬浮体系过渡，化学反应为反应速度的控制因素，2级反应；凝胶阶段，由固／液两相体系向单一的固相体系过渡，扩散因素对反应速度的影响作用逐渐加大，为2与0级之间变化的反应；固化阶段，单一的固相体系，反应速度较慢，扩散因素是主导作用，0级反应。对各个反应阶段的流变同时测量，可以明确了解化学反应对流变性能的影响。更多还原

【Abstract】 The chemorheology of multiphase/cure system were studied in this paper based on polyurethane materials. In the first place, the test methods of chemorheology for fast reaction system have been developed. There are three viscometers used for measuring chemorheology. They are isotherm viscometer, absolute viscometer and gel meter. The rheology can be measured by isotherm viscometer in favor of investigating infection of chemical reaction, because of without temperature factor. The testing condition of insulation viscometer is close to practice manufacture process. The viscosity and reaction conversion can be gain from it. The gel meter can be used for measuring gel time and reactive viscosity nearly. The viscosity rise effected by breed and content of catalyst were being tested. The catalyst was amine and tin. The viscosity drop phenomena near gel point was become conscious. This phenomenon was result in temperature and phase separation. The viscosity drop was took order with JRG " Vague Sub-Cluster Theory".The microstructure and phase separate were studied at same time. The mathematics model was set up based on flow machinery. The reaction process was parted for the first time according to reaction characteristics and microstructure. The reaction process was divided into 4 part.(1)Reaction initial stage: homogeneous liquid phase system; reaction order is 0; The control factor is diffusion.(2)Reaction accelerates stage: The homogeneous liquid phase system become to solid/liquid system, The reaction order is 2. The reaction is control factor. (3)Gel stage: The solid/liquid 2-phase system become solid phase. The effect of diffusion varied more important as reaction. The order is 6.(4)Cure stage: solid phase system. Diffusion is dominant factor. The reaction order is 0.Because the conversion is tested as soon as viscosity, we can clearly see the relationship between rheology and reaction. Finally, using test parameters, author works on experiment of on-line filling mold for RIM, and put up a new filling mathematics molded for filling mold.Polyurethane foam was developed by basic theories of reactiono更多还原