Polystyrene chromatography standards

Figure 26-15 Larger CdSe quantum dots are eluted before smaller quantum dots by 0.1 M trioctylphosphine in toluene at 1.0 mL/min in size exclusion chromatography on a 7.5 x 300 mm cross-linked polystyrene column of 100-nm pore size Polymer Labs PLgel 5 (im. Triangles are CdSe and squares are polystyrene calibration standards. The size of the CdSe core was measured with a transmission electron microscope and the length of 1-dodecanethiol endcaps (0.123 nm) was added to the radius. [Data from K. M. Krueger. A. M. Al-Somall, J. C. Falkner, and V. L. Colvin, "Characterization of Nanocrystalline CdSe by Size Exclusion Chromatography," Anal. Chem. 2005, 77,3511.]...

The polystyrene seed latex was monodispersed. Even after several grow-ups (polymerizations) the final 1650 A latex was monodispersed. Hydrodynamic chromatography on the 1650 A latex gave a mean diameter of 1660 a with a size variance as small as for normal polystyrene latex standards (typical standard of 1760 8 with a standard deviation of 23 a). The final latex particle size could be accurately predicted from the initial particle size and the total amounts of monomer and polymer used. 

MFI = melt flow index IV = intrinsic viscosity in CH2CI2 at 25°C From gel-permeation chromatography using polystyrene standards. 

A novel cross-linked polystyrene-divinylbenzene copolymer has been produced from suspension polymerization with toluene as a diluent, having an average particle size of 2 to 50 /rm, with an exclusive molecular weight for the polystyrene standard from about 500 to 20,000 in gel-permeation chromatography. A process for preparing the PS-DVB copolymer by suspension polymerization in the presence of at least one free-radical polymerization initiator, such as 2,2 -azo-bis (2,4-dimethylvaleronitrile) with a half-life of about 2 to 60 min at 70°C, has been disclosed (78). 

The packing material for liquid chromatography is produced from styrene and divinylbenzene dissolved in 50 to 300% by weight of organic solvent to both monomers. The constitution of divinylbenzene in the monomer mixture is not less than 60% by weight. In gel-permeation chromatography, the exclusive molecular weight is not less than 1 X 10 in terms of standard polystyrene (79). 

ASTM D 5296 - 92 (1994). Standard Test Method for Molecular Weight Averages and Moleeular Weight Distribution of Polystyrene by High Performance Size-Exclusion Chromatography. Annual Book of ASTM Standards, Vol.08.03, pp. 419-431. 

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). 

Traditionally, column efficiency or plate counts in column chromatography were used to quantify how well a column was performing. This does not tell the entire story for GPC, however, because the ability of a column set to separate peaks is dependent on the molecular weight of the molecules one is trying to separate. We, therefore, chose both column efficiency and a parameter that we simply refer to as D a, where Di is the slope of the relationship between the log of the molecular weight of the narrow molecular weight polystyrene standards and the elution volume, and tris simply the band-broadening parameter (4), i.e., the square root of the peak variance. 

Gel permeation chromatography (GPC) or size exclusion chromatography (SEC) has been routinely used to estimate die molecular weight of die polymers. The molecular weight measured by GPC is relative to a polymer standard, typically polystyrene GPC is dius a relative method rather than an absolute one. For those polymers whose structure is very different from polystyrene, GPC molecular weight values could significantly differ from the real ones. In those cases, GPC values should only be regarded as a reference. 

The Separation of Some Polystyrene Standards by Exclusion Chromatography on Silica Gel... 

As for conventional linear polymers, gel permeation chromatography (GPC) can be used to find information on the composition of dendrimers, including their polydispersities. Obtaining standards of known relative molar mass and polydispersity is a problem with dendrimers, so the approach that has been taken most often is to use polystyrene standards, as described in Chapter 6. 

Molecular weights were measured by gel permeation chromatography on a Perkin-Elmer Series 10 Liquid Chromatograph using tetrahydro-furan as solvent and refractive index as the detection mode. Standards were polystyrene, and reported molecular weights for the poly-siloxanes do not include a correction. 

Gel permeation chromatography was performed in tetrahydrofuran using a Waters pump system and a Model 410 differential refractive index detector for the eluant. Five Ultrastyragel columns with nominal porosities ranging from 500 to 105 angstroms were used for all the samples and the polystyrene standards. 

Molecular weights of the copolymers were determined by gel permeation chromatography (GPC) with four p-styragel (Haters) columns calibrated using polystyrene standards. Chloroform was used as the eluate at a flow rate 1.5 ml/min. An LKB-2140 Ultraviolet Photodiode Array detector was used to detect the polymer with a scan range from 190 to 370 nm. 

Figure 1. Size exclusion chromatography of Ru3(C0)i2 catalyzed polymerization of MeNH-[H2SiNMe]x-H as a function of time. Polystyrene standards used for calibration.

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