[工学]ch2-2聚合速率.pdfVIP

Kinetics of Free- Radical Polymerization 2.3 The Rate of Radical polymerization 2.3.1 Polymerization rate and measuring method 2.3.2 Steady-state polymerization rate equation 2.3.3 Effect of temperature on polymerization rate 2.3.4 Rate constants of elementary reaction and main parameter 2.3.5 Autoacceleration 2.3.6 Types of rate changing during the polymerization process 2.3.7 Inhibition and retardation 2.3.1 Polymerization Rate and Measuring Method Polymerization rate The decrease of The increase of monomer concentration polymer concentration with the reaction time with the reaction time Experimentally, the change of conversion （转 化率）is measured. Polymerization rate also can be expressed as the conversion change in unit time Or C % t Fig 1 Plot of conversion versus time Measurement of the Conversion Change with Time  Contains direct, and indirect method. precipitation method （沉淀法）is used most in direct method 一定温度下聚合，定时取样，求得不同t时的 聚合物量. 也可通过分析单体的浓度而求得某时刻的转化 率 Indirect method— 即测定聚合体系的比容、 粘度、折光率、吸收光谱等物理化学性质的 变化，推算出反应体系中单体浓度的减少， 或聚合物量的增加 Principles of Dilatometer(膨胀计) Method According to the linear relationship between the volume contraction(体积收缩)and the conversion of the reaction system  The conversion （C ％）has a linear relationship with the volume contraction. Measuring the volume contraction value at different time, we can get the conversion change with time, and get the polymerization rate. 2.3.2 Steady-state Polymerization