Gel-permeation chromatography. IX. Instrumental design and computer interfacing of a GPC molecular weight detector system

The detailed design and computer interfacing of a GPC molecular weight detector based on a real time viscometer are described. The working drawings presented will permit one to fabricate and duplicate the viscometer and the complete GPC molecular weight detector system. The uses and advantages of a laboratory automation system in analyzing GPC results are also described.     

Gel-permeation chromatographic studies of cellulose degradation. I. Treatment with hydrochloric acid

The molecular weight distribution in various celluloses degraded with hydrochloric acid has been studied by gel-permeation chromatography. Measurements were made on the residue after hydrolysis, on the degradation products solubilized by the acid, and on whole degraded samples comprising the product soluble in the acid plus the residue. It is shown that the total number of crystallites decreases during hydrolysis while the chain length distribution remains constant. The crystallites are gradually broken down into molecular fragments which show a size distribution centered on species with a degree of polymerization of about 8. Possible interpretations of these results are discussed.     

Radiation effects on polymers—XII. Molecular weight and molecular weight distribution of cellulose acetate-grafted polyacrylamide side-chains and homopolyacrylamide using gel permeation chromatography

Calibration of gel permeation chromatography was carried out to determine molecular weight and molecular weight distribution of the side-chains and homopolymer formed during grafting of cellulose acetate with acrylamide monomer using accelerated electrons. Polyacrylamide in side-chains and in homopolymer was found to be of very high molecular weight; the grafting event was found to be as low as 1–10 polyacrylamide chains per 10³ cellulose acetate chains.     

Gel permeation chromatography. I. A new method for molecular weight distribution of high polymers

Polystyrene gels crosslinked in the presence of dilucnts have been made in fine-mesh bead form suitable for packing into chromatographic columns. A series of narrow molecular weight range polymer fractions was eluted through such columns with aromatic and chlorinated solvents. Effluent concentrations were detected and recorded by a continuous differential refractometer. The fractions were shown to be efficiently separated. Columns capable of separating adjacent polymeric samples of high molecular weight were prepared from gels crosslinked in the presence of large amounts of diluents having little or no solvent action on polystyrene. Smaller proportions of diluents and those with more solvent action yielded columns with lower molecular weight permeability limits. Such studies provided a unique quantitative view of the topology of the gels. They also demonstrated that rapid repetitive molecular weight distribution data can be obtained in this way on polymers for which solvents compatible with the gels are available.     

Gel-permeation chromatographic studies of cellulose degradation. III. Methanolysis of cellulose

The molecular weight distribution in various celluloses degraded by methanolysis has been studied by gel-permeation chromatography. It is shown that the accessible portion of the sample apparently degrades preferentially into molecular fragments with a size distribution centered on species with a degree of approximately 8. This result is interpreted as indicating the presence of weak links in the cellulose chains.     

Gel-permeation chromatography of cellulose esters. Effect of average DP,DS, substituent size,and primary hydroxyl content

Hydrolyzed cellulose acetates and cellulose tripropionates prepared over wide ranges of intrinsic viscosity (DP) were fractionated by gel-permeation chromatography (GPC). An increase was observed in the polystyrene equivalent length (PSEL) at 50% cumulative height with increasing DP of the ester. Cellulose acetates and propionates over wide range of acyl content (DS), and a homologous series of triesters (propionate through heptanoate) of the same DP were fractionated by GPC. Increased amount and size of acyl gave relatively small increases in PSEL. The molecular size of cellulose acetates was not affected by the amount of primary hydroxyl present in the esters. The breadth of molecular weight distribution of the cellulose esters, as measured by the weight-average to number-average molecular size ratio, M?_w/M?_n, was not affected by any variation in the composition of the esters. A blend of cellulose tripropionates of widely differing DP gave a broadened GPC curve in agreement with that calculated from the components of the blend.     

Gel-permeation chromatography: X. Molecular weight detection by low-angle laser light scattering

Effluent from a gel-permeation chromatographic column has been simultaneously and continuously monitored with a differential refractometer and a low-angle laser light-scattering (LALLS) photometer. This provides a true and direct determination of molecular weight distribution rather than through a calibration method as obtained by conventional GPC techniques. Computer assisted data reduction provides a rapid determination of M?_w, M?_n, M?_z, M?_w/M?_n, as well as a plot of molecular weight distribution. Samples of very narrow molecular weight distribution (MWD) polystyrene from Pressure Chemicals Co. and relatively wide MWD samples of poly(methyl methacrylate) in chloroform have been characterized.     

Polymerization mechanisms and molecular weight distribution. I. Mathematical treatment

A novel method for determining the polymerization mechanism and the kinetic rate constants from the molecular weight distribution is proposed. The particular criterion function used as basis for parameter adjustment is where θ is the vector of dependent variables, y(r, θ) is the theoretical molecular weight distribution for the assumed polymerization mechanism, and y_E(r) is the experimental molecular weight distribution which is a function of the chain length r. A form of the gradient method of optimization was used to solve the criterion function. The proposed method is particularly powerful since the whole molecular weight distribution is utilized.     

Solid-State coextrusion of high-density polyethylene. II. Effect of molecular weight and molecular weight distribution

The recently developed technique of solid-state coextrusion for ultradrawing semicrystalline thermoplastics has been applied in the preparation of self-reinforced high-density polyethylene extrudates. The extrudates consist of definite core and sheath phases composed of different molecular weights (M_w) in the range of 60,000–250,000 and different molecular weight distributions (M_w/M_n = 3.0–20). Concentric billets of two different phases were prepared for extrusion by in serting a polyethylene rod within a tubular billet of a different high-density polyethylene followed by melting the two phases to obtain bonding between them. The billet was then split longitudinally to increase extrusion speed and extruded at 120°C, 0.23 GPa through a conical die of extrusion draw ratio 25. Extrudates of high tensile modulus (38 GPa) and strength (0.50 GPa) could be produced in a steady state process at a rate near 0.25 cm/min. The tensile properties of the extrudates from either the single or concentric billets increased with average molecular weight and were insensitive to the molecular weight distribution of the constituent phases. Thermal analysis indicated a high deformation efficiency for the sheath and core phases of the extrudates by the coextrusion technique.     

Effect of total degree of substitution on molecular parameters of cellulose acetate

An attempt was made to establish for cellulose acetate (CA) the relationship between the molecular properties, the total degree of substitution 〈〈F〉〉 and the degree of solvation. For this purpose, the comprehensive solution data for CA with 〈〈F〉〉 = 0.49-2.92 in previous papers were analyzed. In addition, the strength of the solvation was estimated from the chemical shift of O-acetyl- and hydroxyl-protons in NMR spectra and the number of the solvated solvent molecules at infinite dilution (s_o) was determined from the adiabatic compressibility. The strength of solvation and s_o increased with the dielectric constant ? of the solvent. The close correlation between s_o, the unperturbed chain dimension A and the free draining effect was demonstrated; these three quantities and the exponent a in the Mark-Houwink-Sakurada equation attained their maximum at $\text{〈〈F〉〉 ? 2.5}$, if CA is dissolved in dimethylacetamide. The characteristic variation of the chain rigidity, estimated from A, and of the draining effect with ? of the solvent and 〈〈F〉〉 can be reasonably explained by the solvation. The cellulose molecule dissolved in a hypothetical non-polar (? = 1) solvent was shown to be a freely rotating chain, by duplicated extrapolation A for CA to 〈〈F〉〉 = 0 and to ? = 1.     

Molecular weight distribution of cellulose esters by gel permeation chromatography and fractional precipitation

Fractional precipitation and gel permeation chromatography yield comparable information on the molecular weight distribution of various cellulose esters. The GPC technique applied to samples obtained by fractional precipitation gives a much more definitive analytical tool than either method used independently. One practical application of this work showed the same molecular weight distribution of two cellulose acetates prepared by different methods.     

Determination of molecular weight distribution of cellulose by conversion into tricarbanilate and fractionation

Two samples of cellulose (molecular weight 2.97 × 10⁵ and 1.25 × 10⁵) were transformed into carbanilates (CTC) which were then fractionated by the elution method at a constant composition of the acetone-water elution mixture with the column temperature gradually increasing from ?30°C to 30°C, and by the GPC method in acetone and tetrahydrofuran. Tetrahydrofuran appeared to be a more suitable solvent. The molecular weights of fractions obtained by the elution fractionation were determined by the light-scattering method in tetrahydrofuran. The width of fractions was determined by the GPC method (average M _w/M _n = 1.37); the [η] values and the Mark-Houwink constants (K = 5.3 × 10^-3, a = 0.84) for tetrahydrofuran at 25°C were determined. The calibration curve for the GP method was constructed by means of the fractions thus obtained; it was demonstrated that the universal calibration curve according to Benoit can also be used. It was demonstrated that the molecular weight distribution of cellulose can be conveniently determined by conversion into CTC followed either by the elution fractionation (for preparative purposes) or by fractionation by the GPC method (for analytical purposes).     

Molecular weights and molecular weight distribution of polymers by equilibrium ultracentrifugation. Part I. Average molecular weights

From the sedimentation-diffusion equilibria of some polymer solutions the average molecular weights M?_n, M?_w, M?_z, and M?_z+1 have been determined in different ways. In particular, the applicability of Fujita's method, which utilizes concentration gradient values at the midpoint of the solution column at a number of rotor speeds, was examined. It appears that if the gradients at some other places in the column are also used, a smaller range of rotor speeds suffices. This method is generally applicable for determining the average molecular weights specified above.     

Gel permeation chromatography—I. The effect of flow rate and molecular weight on separation efficiency

Gel Permeation Chromatography experiments have been performed to determine the effect of flow rate on polymer elution volumes and the widths of the chromatographic peaks. Using a single polystyrene gel column, nominal porosity 1 x 10⁵ Å, a series of polystyrenes, having a narrow molecular weight distribution, has been chromatographed at a series of flow rates. Significantly lower flow rates have been used than have been previously reported. Corrections were made to account for the finite molecular weight distribution of the samples and instrumental broadening. Comparisons with the theoretical predictions for the effect of flow rate on the chromatogram have been made. The efficiency of the chromatography process is discussed in terms of the theoretical plate concept and the peak widths measured at the base. Under the conditions used, the elution volume was found to be independent of flow rate. The efficiency of the separation process was found to be highly dependent on flow rate in the range 0·05–1·5 ml/min.     

Unimodal molecular weight distribution of commercial polymers from viscoelastic data

This article presents a method that provides the molecular weight distribution (MWD) of polymeric material from rheological data. The technique has been developed to deal with linear polymers with a log‐normal molecular weight distribution. The rheological data must include the shear storage modulus, G′(ω), and the shear loss modulus, G″ (ω), ranging from the terminal zone to the rubberlike zone. It was not necessary to achieve the relaxation spectrums via the extremely unstable problem of inverting integral equations. The method has been tested with different polymers (polydimethylsiloxane, polyisoprene, random copolymer of ethylene and propylene, and polystyrene) and the calculated MWDs were in good agreement with experimental data. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1539–1546, 2000     

Interfacial and foaming properties of prolylenglycol alginates. Effect of degree of esterification and molecular weight

In the present work we have studied the characteristics of propylene glycol alginates (PGA) adsorption at the air–water interface and the viscoelastic properties of the films in relation to its foaming properties. To evaluate the effect of the degree of PGA esterification and viscosity, different commercial samples were studied—Kelcoloid O (KO), Kelcoloid LVF (KLVF) and Manucol ester (MAN). The temperature (20 °C) and pH (7.0) were maintained constant. For time-dependent surface pressure measurements and surface dilatational properties of adsorbed PGA at the air–water interface an automatic drop tensiometer was used. The foam was generated by whipping and then the foam capacity and stability was determined. The results reveal a significant interfacial activity for PGA due to the hydrophobic character of the propylene glycol groups. The kinetics of adsorption at the air–water interface can be monitored by the diffusion and penetration of PGA at the interface. The adsorbed PGA film showed a high viscoelasticity. The surface dilatational modulus depends on the PGA and its concentration in the aqueous phase. Foam capacity of PGA solutions increased in the order KO > MAN > KLVF, which followed the increase in surface pressure and the decrease in the viscosities of PGA solutions. The stability of PGA foams monitored by the drainage rate and collapse time follows the order MAN > KLVF > KO. The foam stability depends on the combined effect of molecular weight/degree of esterification of PGA, solution viscosity and viscoelasticity of the adsorbed PGA film.