Molecular weight distribution analysis

A Waters Model 150C ALC/GPC was interfaced to a minicomputer system by means of a microcomputer for automated data collection and analysis. Programs were developed for conventional molecular weight distribution analysis of the data and for liquid chromatographic quantitative composition analysis of oligomeric materials. Capability has been provided to utilize non-standard detectors such as a continuous viscometer detector and spectroscopic detectors for compositional analysis. The automation of the instrument has resulted in greater manpower efficiency and improved record keeping. 

Arturson G, Granath K. Dextrans as test molecules in studies of functional ultrastracture of biological membranes— molecular weight distribution analysis by gel chromatography. Clin Chim Acta 1972 37 309-322. 

Four commercial agarose type gels have been used at enhanced flow rates for the molecular weight distribution analysis of dextran. The performances of the gels were discussed in terms of resolution, molecular weight correction factors, and variations in plate height as a function of flow rates. 

Howardt describes a model system used to test the molecular weight distribution of a condensation polymer The polymer sample was an acetic acid-stabilized equilibrium nylon-6,6. Analysis showed it to have the following end group composition (in equivalents per 10 g) acetyl = 28.9,... 

Among the techniques employed to estimate the average molecular weight distribution of polymers are end-group analysis, dilute solution viscosity, reduction in vapor pressure, ebuUiometry, cryoscopy, vapor pressure osmometry, fractionation, hplc, phase distribution chromatography, field flow fractionation, and gel-permeation chromatography (gpc). For routine analysis of SBR polymers, gpc is widely accepted. Table 1 lists a number of physical properties of SBR (random) compared to natural mbber, solution polybutadiene, and SB block copolymer. 

The molecular weight and molecular weight distribution may be determined by conventional techniques. As the resins are of comparatively low molecular weight it is possible to measure this by ebullioscopic and by end-group analysis techniques. 

Nonionic polysaccharides are one of the most simple substances to analyze by size exclusion chromatography because they seldom exhibit nonsize exclusion effects. Due to their wide molecular weight distribution, TSK-GEL PW columns are recommended for their analysis. 

SEC measurements were made using a Waters Alliance 2690 separation module with a 410 differential refractometer. Typical chromatographic conditions were 30°C, a 0.5-ml/min flow rate, and a detector sensitivity at 4 with a sample injection volume of 80 fil, respectively, for a sample concentration of 0.075%. All or a combination of PEO standards at 0.05% concentration each were used to generate a linear first-order polynomial fit for each run throughout this work. Polymer Laboratories Caliber GPC/SEC software version 6.0 was used for all SEC collection, analysis, and molecular weight distribution overlays. 

The comparison among these techniques is tabulated in Table 22.1. In summary, HdC is a separation technique with low selectivity however, the efficiency can be very high. Especially in PCHdC, high analysis speed can be achieved over a wide MW range. ThFFF performs best for the separation of high MW samples. SEC has an intermediate selectivity between FldC and ThFFF. Practicality makes SEC the most suitable method for the common MW range of synthetic polymers. SEC is by far the most commonly used technique for molecular weight distribution determinations. However, HdC is better for the fast analysis purpose. 

In PLP the sample is subjected to a series of short (<30 ns) laser pulses at intervals t. Analysis of the molecular weight distribution gives the length of chain formed between successive pulses (v) and this yields a value for kp (eq. 13). 

The most used method is based on application of the Mayo equation (eq. 5). For low (zero) conversion polymerizations carried out in the presence of added transfer agent T, it follows from eq. 5 that a plot of 1/ Xn vs [T]0/[M]0 should yield a straight line with slope Clr.12 Thus, a typical experimental procedure involves evaluation of the degree of polymerization for low conversion polymerizations earned out in the presence of several concentrations of added transfer agent. The usual way of obtaining Xn values is by GPC analysis of the entire molecular weight distribution. 

The influence of selectivity in the initiation, termination or chain transfer steps on the distribution of monomer units within the copolymer chain is usually neglected. Galbraith et a .u provided the first detailed analysis of these factors. They applied Monte Carlo simulation to examine the influence of the initiation and termination steps on the compositional heterogeneity and molecular weight distribution of binary and ternary copolymers. Spurting et a/.250 extended this... 

Using IR spectroscopy and NMR, one can analyze the chemical structure of PA. The molecular weight and molecular weight distribution can be analyzed by endgroup analysis, viscometry, and high-pressure liquid chromatography (HPLC). The crystalline order can be analyzed by WAXS, small-angle X-ray spectroscopy... 

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