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纸质出版日期:1963-10-20,
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应琦琮, 钱人元. 分子量分森的简易测定与分级数据的处理[J]. 高分子学报, 1963,5(2):77-83.
Ying Chi-tsung, CHIEN JEN-YUAN. SIMPLIFIED PROCEDURES FOR THE DETERMINATION OFMOLECULAR WEIGHT DISTRIBUTION AND THETREATMENT OF FRACTIONATION DATA[J]. Acta Polymerica Sinica, 1963,5(2):77-83.
本文对作者等以前提出的应用溶度函数的简易分级法
和应用董履和函数处理沉淀分级数据作了进一步的简化和考验。用在良溶剂和θ溶剂中测定两个特性粘数值来决定 级分的分布参数
在一般的实验条件下不可能达到所要求的精确度
因此改用分相参数Q=R的近似来决定简易分级法中两个级分的分布参数
实际的计算说明Q的取值可以有相当大的变化范围而对结果的影响不大
这样对简易分级法提供了一个简便的权宜办法。对应用董履和函数计算普通分级法的分级数据时
除第一级分和最后级分外
其他各级分的累积分布均可采用直綫近似
此直綫通过M(I=1/2)=(?)_η
M(I=0)=1/2(?)_η两点
可以简省计算
而对结果的影响极小。本文中对一个聚甲基丙烯酸甲酯试样的两种分级数据进行计算的结果
说明上面两种方法都比习惯应用的Schulz-Dinlinger法计算结果更接近于用沉降速度法测定的分子量分布。
In this paper,further simplifications are suggested for the two-fraction method based on the solubility function and the treatment of fractionation data by using Tung functiorr which were proposed by the present authors in previous publications.The evaluation of the distribution parameters for a fraction from two intrinsic vis-cosity measurements in a good solvent and in a θ-solvent is shown to be not practical
because the required precision is not attainable in ordinary measurements. A new ap-proximation is suggested by taking the phase separation parameter Q to be equal to the volume ratio R of the concentrated and dilute phases.Then,the distribution para- meters for the two-fraction method can be readily evaluated. Actual calculations show that the distribution parameters thus calculated is not very sensitive to the value of Q taken,and therefore this approximation is iustified as a tentative simplification of the two.fraction method for the determination of molecular weight distributions.In the treatment of ordinary fractionation data by means of Tung function,all fractions except the first and the last ones can be approximated by a straight line for the integral distribution curve.The line passes through the points M (1=1-2)=Mn,M(1=0)=1-2Mn which corresponds roughly to a straight line with equal slope as the Tung function at M1-2 with b=2.7—3.0.This leads to a considerable saving in corn-putation but very slight difference to the result.The suggested simplifications have been applied to a sample of PMMA.The in-tegral distribution curve obtained by the suggested method are closer to the actual one obtained by sedmentation rate method than the usual Schulz-Dinlinger treatment.
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