Molecular Weight Distributions of Elastomers—Comparison of Gel Permeation Chromatography with Other Techniques

1965 ◽  
Vol 38 (4) ◽  
pp. 823-831 ◽  
Author(s):  
Leon W. Gamble ◽  
Lowell Westerman ◽  
Ebnest A. Knipp
Keyword(s):  
Molecular Weight ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Gel Permeation Chromatography ◽  
Molecular Weights ◽  
The Past ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
Gel Permeation ◽  
Polymer Fractionation

Abstract During the past decade interest in polymer fractionation for evaluating molecular weight distribution has increased. New polymers, such as polypropylene, high density polyethylene and many others have been subjected to extensive characterization, but some older polymers, including natural rubber have not. In recent years column fractionation has received a great deal of attention; a review has been made by Schneider. Most of the techniques of polymer fractionation, such as precipitation from solution and column fractionation, are quite lengthy and require days or even weeks to complete. A more rapid method for molecular weight distribution has been the goal of polymer chemists for years. The most promising of the rapid methods are turbidimetric and gel permeation chromatography by which analysis is accomplished in a few hours. This paper discusses application of gel permeation chromatography to fractionation of elastomers. In addition this technique is compared with data from column fractionation, light scattering and osmometry. Some of the assumed factors used in converting gel permeation data into molecular weights are in error. But by calibration of the gel permeation chromatograph with classical methods reliable data can be obtained.

Structural studies of oligosilanes produced by catalytic dehydrogenative coupling of primary organosilanes

1987 ◽  
Vol 65 (8) ◽  
pp. 1804-1809 ◽  
Author(s):  
C. Aitken ◽  
J. F. Harrod ◽  
U. S. Gill
Keyword(s):  
Molecular Weight ◽  
Nuclear Magnetic Resonance ◽  
Gel Permeation Chromatography ◽  
Structural Studies ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Dehydrogenative Coupling ◽  
Weight Distributions ◽  
Gel Permeation ◽  
End Groups

The structures of some poly(organosilylenes), [Formula: see text] (R = Ph, p-tolyl, n-hexyl, and benzyl), produced by catalytic dehydrogenative coupling of primary silanes have been studied by infrared, nuclear magnetic resonance, and mass spectroscopies. These results, combined with data on molecular weights and molecular weight distributions from vapour pressure osmometry and gel permeation chromatography, lead to the conclusion that the polymers are linear and have SiH2R end groups. The polymers all have degrees of polymerization of ca. 10 and very narrow molecular weight dipersions. Some possible features of the mechanism that gives rise to this behaviour are discussed.

The Investigation of Molecular-Weight Distribution in Rubberlike Polymers

1957 ◽  
Vol 30 (2) ◽  
pp. 507-527 ◽  
Author(s):  
S. E. Bresler ◽  
I. Y. Poddubnyĭ ◽  
S. Y. Frenkel
Keyword(s):  
Molecular Weight ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Polymerization Reaction ◽  
Continuous Series ◽  
Gaussian Shape ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
Asymmetric Shape

Abstract In an investigation of three different synthetic rubbers, methods of fractionation were examined and measurements were made of the molecular-weight distribution by analysis of fractions. The following conclusions may be drawn. (1) The method of equivalent Gaussian distributions correctly reproduces the distribution within each fraction and makes it possible to distinguish the broadening of the sedimentation curve attributable to diffusion and that attributable to polydispersion. (2) The method of accounting for the final concentration of the solution under investigation introduced by us result in correct values of molecular weights of fractions and correct values of standard deviations. (3) Comparison of a series (about 10) of fractions of a given polymer makes it possible to transpose the sedimentation constant distributions into the distribution of molecular weights in a simple and natural way. An investigation of the three rubbers demonstrates two facts. (1) Fractionation of rubbers by precipitation from solutions gives true fractions, i.e., mode values of molecular weights and sedimentation constants do not overlap but form continuous series. By this means fractionation of K-1 and K-3 resulted in very homogeneous fractions of Gaussian shape having dispersion coefficients smaller than 0.33. Fractionation of K-2 resulted in less homogeneous fractions of somewhat asymmetric shape; however, in this case, the broadness and asymmetry of fractions, as it is easy to show, does not exceed the limits predicted by the theory of fractionation. (2) The method of determination of molecular-weight distributions by tracing the steplike curve of precipitation, with subsequent smoothing by graphic differentiation, gives a correct picture of the distribution function of polymers for molecular weights; however, the finer details of distribution can be distorted and lost in tracing the steplike curve. The molecular-weight distributions of synthetic rubbers by the ultracentrifuge method must be closely related to the process of genesis of a polymer, i.e., with the mechanism of the polymerization reaction. Thus, with proper experimental technique our method can be applied to the investigation of various mechanisms of polymerization and polycondensation.

Effect of Molecular-Weight Distribution on Physical Properties of Natural and Synthetic Polymers

1948 ◽  
Vol 21 (3) ◽  
pp. 654-666 ◽  
Author(s):  
B. L. Johnson
Keyword(s):  
Molecular Weight ◽  
Physical Properties ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Synthetic Polymers ◽  
Natural Polymers ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Styrene Copolymers ◽  
Weight Distributions

Abstract The molecular weights of rubberlike polymers are average values for mixtures of macromolecules which differ greatly in size. The heterogeneity of natural rubber was recognized as early as 1929 by Whitby. The fact that solutions of higher quality crude rubbers are more viscous than lower quality rubbers was observed by Axelrod in 1905. Other workers have separated rubber solutions into fractions of differing molecular weight and have studied the properties of the fractions. In the case of synthetic polymers, these heterogeneous mixtures of molecules have been characterized by fractional precipitation and construction of molecular-weight distribution curves. The particular type of distribution determined in this investigation is that obtained from weight average properties based on viscosity measurements of fractions of the polymers. Application of these methods to the characterization of natural polymers confirmed observations that a variety of molecular-weight distributions existed in the case of the natural polymers. The physical properties of the natural polymers having these diverse molecular-weight distributions were well known. Therefore a correlation of their physical properties and weight distributions seemed pertinent to an evaluation of the fractionation technique. Such a correlation had not been possible on early butadiene-styrene copolymers because of the similarity of the distributions then obtained, even under different polymerization conditions.

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