Molecular weight distribution chromatography

Fig. 3. Molecular weight distribution curves as determined by gel-permeation chromatography. A represents i9f2v (9-phthahc resins B, highest molecular...

Size-exclusion chromatography (sec) easily and rapidly gives the complete molecular weight distribution and any desired average (6). Thus, it has become the technique of choice for determining molecular weights despite its relatively high initial cost. 

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. 

Molecular weights of PVDC can be determined directly by dilute solution measurements in good solvents (62). Viscosity studies indicate that polymers having degrees of polymerization from 100 to more than 10,000 are easily obtained. Dimers and polymers having DP < 100 can be prepared by special procedures (40). Copolymers can be more easily studied because of thek solubiUty in common solvents. Gel-permeation chromatography studies indicate that molecular weight distributions are typical of vinyl copolymers. 

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. 

Showa Denko K.K. started the Shodex HPLC business in 1973 by developing columns to determine the molecular weight distributions of polymers produced at its petrochemical plant. Since then, more than 600 items of columns have been developed to achieve various kinds of analyses. Among them are several series of columns that can be used for size exclusion chromatography. The abundant variety of columns is one of the important characteristics of Shodex. Any kind of analytical requirements can be satisfied by choosing the appropriate column supplied by Showa Denko. 

Determinarion of MW and MWD by SEC using commercial narrow molecular weight distribution polystyrene as calibration standards is an ASTM-D5296 standard method for polystyrene (11). However, no data on precision are included in the 1997 edition of the ASTM method. In the ASTM-D3536 method for gel-permeation chromatography from seven replicates, the M of a polystyrene is 263,000 30,000 (11.4%) for a single determination within the 95% confidence level (12). A relative standard deviation of 3.9% was reported for a cooperative determination of of polystyrene by SEC (7). In another cooperative study, a 11.3% relative standard deviation in M, of polystyrene by GPC was reported (13). 

ASTM D-5296-92, Standard Test Method for Molecular Weight Averages and Molecular Weight Distribution of Polystyrene by High Performance Size-Exclusion Chromatography. ASTM Annual Book of ASTM Standards, Vol.08.03, pp. 425-438. 

In industry and academia the need often arises to isolate portions of a polymer sample, whether it be to separate low molecular weight material from a sample or to actually fractionate the polymer across its molecular weight distribution. If gram quantities of isolated polymer are needed, true preparative chromatography equipment and techniques are usually necessary. 

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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