Measurement average molecular weight

Chapter 3 reviews the essentials of practical techniques for measuring average molecular weights and characterizing molecular weight distributions. 

Suppose the measured average molecular weight at f = 53 min is accurate. For living polymerization, the number average molecular weight, M , is a linear function of conversion. (Column 3 of Table 10.3 also shows the recalcu-... 

The measured average molecular weights, eg, obtained from molecular weight distributions, of macromolecules generated by free radical polymerization processes are often lower than those predicted by accounting for initiation, propagation, and termination processes. This experimental observation can be attributed to chain stopping events via chain transfer reactions (163,164). The transfer reaction can be described via equations 22 and 23. 

Various types of detector have been employed for the detection of polymers separated by liquid adsorption chromatography, including conductimetric detectors for polyoxyethylenes [115] and UV detectors for ethyl methacrylate-butyl methacrylate copolymers [116]. Hancock and Synovec [117] carried out a rapid characterisation of linear and star branched polymers, particularly PS by a gradient detection method. This method measures average molecular weight in methylene dichloride solutions of the polymers and gives more specific... 

As with the diene homopolymers many of the characterization procedures used, such as those to measure average molecular weight, molecular weight distribution and branching, are those in use for characterizing polymers generally and this brief discussion will be confined to ... 

In this section we consider common techniques for measuring average molecular weights with the object of gaining a qualitative understanding of their operation and an appreciation for their advantages and limitations. Additional theoretical and experimental details are available elsewhere."... 

Using this concept, Burdett developed a method in 1955 to obtain the concentrations in mono-, di- and polynuclear aromatics in gas oils from the absorbances measured at 197, 220 and 260 nm, with the condition that sulfur content be less than 1%. Knowledge of the average molecular weight enables the calculation of weight per cent from mole per cent. As with all methods based on statistical sampling from a population, this method is applicable only in the region used in the study extrapolation is not advised and usually leads to erroneous results. 

An important application of Eq. (3.39) is the evaluation of M, . Flory et al.t measured the tensile force required for 100% elongation of synthetic rubber with variable crosslinking at 25°C. The molecular weight of the un-cross-linked polymer was 225,000, its density was 0.92 g cm , and the average molecular weight of a repeat unit was 68. Use Eq. (3.39) to estimate M. for each of the following samples and compare the calculated value with that obtained from the known fraction of repeat units cross-linked ... 

MI is an approximate measure of the weight—average molecular weight logjo (MI) = X logj (M )... 

The width of molecular weight distribution (MWD) is usually represented by the ratio of the weight—average and the number—average molecular weights, MJM. In iadustry, MWD is often represented by the value of the melt flow ratio (MER), which is calculated as a ratio of two melt indexes measured at two melt pressures that differ by a factor of 10. Most commodity-grade LLDPE resias have a narrow MWD, with the MJM ratios of 2.5—4.5 and MER values in the 20—35 range. However, LLDPE resias produced with chromium oxide-based catalysts have a broad MWD, with M.Jof 10—35 and MER of 80-200. 

Mass Spectrometry. Field desorption mass spectrometry has been used to analy2e PPO (179). Average molecular weight parameters (M and could be determined using either protonated (MH + ) or cation attachment (MNa + ) ions. Good agreement was found between fdms and data supphed by the manufacturer, usually less than 5% difference in all cases up to about 3000 amu. Laser desorption Fourier transform mass spectrometry was used to measure PPG ion and it was claimed that ions up to m/2 9700 (PEG) can be analy2ed by this method (180). 

One further point might be made here. Although the example illustrates the difference between the two types of molecular weight average, the weight average molecular weight in this example cannot be said to be truly representative, an essential requirement of any measure of central tendency. In such circumstances where there is a bimodal, i.e. two-peaked, distribution additional data should be provided such as the modal values (100 and 100000 in this case) of the two peaks. 

---