Analysis of Block and Statistical Copolymers by Gel Permeation Chromatography: Estimation of Mark-Houwink Constants

Abstract

A method is introduced for the estimation of Mark-Houwink constants of block and statistical copolymers. The homopolymer Mark-Houwink constants and copolymer composition are required. Use of estimated Mark-Houwink constants in GPC analyses gives results which agree well with those calculated with experimentally determined constants. Comparisons between this method and those of Runyon and coworkers (11) and Chang (12) are made for block copolymers. Chang's method was also extended to statistical copolymers, and where it compared closely with the one introduced here. The use of copolymer Mark-Houwink constants as a qualitative measure of polymer compatibilities in different solvents is also discussed.     

Characterization of Bituminous Compounds by Gel Permeation Chromatography (GPC)

Abstract

Gel permeation chromatography is applied to the qualitative and quantitative characterization of asphalt, asphaltenes and maltenes. The nature of their molecular size distributions, micellar dimensions, and degree of aromatic polycondensation are described. The resultant data are used to provide insight into the nature of associative processes involving these materials.     

Characterization of Hydrocarbon Waxes by Gel Permeation Chromatography and Differential Scanning Calorimetry

Abstract

An integral part of many elastomer compounding recipes is the wax since it contributes significantly to the performance characteristics of the vulcanizate. Frequently the only quality control tests applied by the user are a simple melting point range and a percent insolubles. This work demonstrates two analytical techniques that can provide much improved quality control monitoring of waxes. Differential scanning calorimetry and gel permeation give not only data on the melting characteristics but also supply information on the chemical structure and size distribution of the waxes. Using these methods replacement waxes can be selected on a technically sound basis.     

Quantitative Analysis of Mixed Polymer Systems by the Use of Gel Permeation Chromatography

Abstract

The use of gel permeation chromatography for the quantitative analysis of composition in mixed polymer systems is presented. The advantages of this method in determining the compositions of conjugate phases in polymer 1-polymer 2-solvent systems is discussed with typical examples.     

高效液相色谱法和凝胶色谱法对钨酚醛树脂的表征

应用高效液相色谱法（ＨＰＬＣ）和凝胶色谱法（ＧＰＣ）对不同合成阶段的钨酚醛树脂进行表征,以合成体系的极性和分子量的变化为依据,提出合成反应的重要控制阶段以及含钨化合物在合成反应中的行为。     

Preparative Gel Permeation Chromatography

Abstract

This Chapter is devoted to a particular mode of liquid chromatography: Gel Permeation Chromatography (G.P.C.). The field of G.P.C. mainly concerns polymers but can also be applied to small organic molecules where, as well see later, the technique is more closely related to classical liquid chromatography.     

Gel Permeation Chromatography of Polyelectrolytes

Abstract

The mechanisms are discussed which control the GPC elution of ionic solutes, both the polyelectrolytes and the low molecular salts. The processes involved are quite general and valid in organic and in aqueous solvents. The conclusion is that gel permeation chromatography is a powerfull method to characterize poly-electrolytes; and it is shown that the correct data on molecular weight distribution can be obtained when the ionic content in the eluent is larger than 5.10^?2 M and when the concentration injected is lower than the critical overlapping concentration. The interpretation of chromatograms can be performed using the universal calibration and a viscosimetric detector.     

Gel Permeation Chromatography of Insulin

Abstract

Aquas gel permeation chromatography of insulin under denaturating conditions has been successfully performed on three different chromatographic supports. The separation pattern was identical to that obtained on soft gels (Sephadex, BioGel). The elution time was 10-20 min, recovery 98-100%.     

Bimodal Gel Permeation Chromatogram of Acrylonitrile-Styrene Copolymers

Abstract

Gel permeation chromatograms were recorded for an acrylonitrile-styrene copolymer in both dimethylforamide (DMF) and DMF-LiBr-H₂O as solvents. In the DMF solvent, a bimodal chromatogram was observed, while in the DMF-LiBr-H₂O solvent, monomodal behavior was observed for the same sample. In order to investigate the cause for such behavior, the molecular weight averages of the copolymer were determined in these solvents. Further, the chromatogram in the former solvent was corrected for observed nonlinearity of the calibration curve. We concluded that apparent differences in the chromatograms are due, at best in part, to the nonlinearity. General conditions for the appearance of bimodal chromatograms were examined based on this idea, using simulation techniques.     

Characterization of Polyethylene in Dibutoxymethane by High-Temperature Gel Permeation Chromatography with Triple Detection

This study presents the possibility of replacing the 1,2,4-trichlorobenzene (TCB) recommended by ASTM D 6474 for the analysis by gel permeation chromatography (GPC) of linear polyethylenes with dibutoxymethane (DBM, butylal), a halogen-free and less toxic solvent. The molecular weight distributions as well as the K and alpha parameters of the Mark-Houwink-Sakurada relationship were measured for polyethylene solutions in TCB and DBM, using a GPC system with triple detection (light scattering, differential refractive index, and viscometer). For commercial metallocene polyethylene resins typically used for film and packaging applications, the GPC method in DBM provided results comparable to those obtained in TCB.     

Characterization of Polypropylene in Dibutoxymethane by High-Temperature Gel Permeation Chromatography with Triple Detection

This study presents the possibility of replacing the 1,2,4-trichlorobenzene (TCB) recommended by ASTM D 6474 for the analysis by gel permeation chromatography (GPC) of polypropylenes with dibutoxymethane (DBM, butylal), a halogen-free and less toxic solvent. The molecular weight distributions as well as the K and alpha parameters of the Mark-Houwink-Sakurada equation were measured for different types of commercial polypropylene samples solubilized in TCB and DBM, using a GPC system with triple detection (light scattering, differential refractive index, and viscometer). For the analyzed resins, covering typical applications of polypropylene, the GPC method in DBM provided results similar to those obtained in TCB.     

Characterization of Polyphenylene Sulfide Using Gel Permeation Chromatography with Triple Detection

The increasing world demand for polyphenylene sulfide (PPS) due to its unique properties has augmented the pressure on development of analytical methods to evaluate its molecular weight distribution and structure. Whilst gel permeation with triple detection (GPC3D) has been considered for PPS analysis, its development and effectiveness has been impaired because of, firstly, the high temperature needed to maintain solubility (>205°C), and, secondly, a very low dn/dc for the polystyrene calibration standards in 1-chloronaphthalene. This article presents practical recommendations to overcome these early difficulties by discussing the results obtained on PPS samples analyzed with a commercially available GPC3D instrument.     

Atypic Gel Permeation Chromatography of Alcohols

Abstract

The elution behaviour of alcohols in the systems Bio Beads SX-8/dichloromethane and Sephadex LH-20/dichloromethane is investigated. On Bio Beads SX-8 the elution volumes are lower than expected for normal GPC behaviour, which is perhaps due to hydrogen bonding in solution. On Sephadex LH-20 adsorption takes place by means of hydrogen bonding, which can be used for very selective separations.     

Gel Permeation Chromatography of Polyethylene Terephalate

Abstract

This paper describes the development of the gel permeation chromatography (GPC) technique for the measurements of cyclic trimer content, molecular weights, and molecular weight distribution of polyethylene terephthalate (PET), utilizing a solvent system of o-chlorophenol-chloroform. Mark-Houwink constants for this solvent system are also described.

The GPC technique was applied to the study of the cyclic trimer content, molecular weights and molecular weight distribution of a variety of commercial PET resins. The results indicate that the cyclic trimer content in PET is dependent on molecular weight, polycondensation process and catalyst system. Solidstate polymerized PET contains less cyclic trimer than PET made by the melt-phase process of the same molecular weight. The cyclic trimer content in solid-stated PET appears to be dependent on the conditions of solid-state polymerization.

The polydispersity index determine for a variety of PET samples is higher than the theoretically predicted value of 2.0; however, there is no systematic dependence on molecular weight or polycondensation process.     

High-Performance Gel Permeation Chromatography of Pectins

Abstract

A high-performance gel permeation chromatographic (GPC) method was developed to determine the molecular weight distribution of pectins. The chromatographic system consisted of a hydrophilic coated silica (SynChropak) as the packing and a pH 3.7 acetate buffer as the mobile phase. By use of this system, high-methoxy, low-methoxy, and amidated pectins could be analyzed within fifteen minutes. By determining partition coefficients (K_d) of pectins as a function of mobile phase composition, K_d values were found to be independent of ionic strength from 0.055 to 0.7 M using pH 3.7 acetate buffers, which was in agreement, with intrinsic viscosity data.     

Characterization of Nylons by Gel Permeation Chromatography and Low Angle Laser Light Scattering in 2,2,2-Trifluoroethanol

Abstract

A GPC method was developed for the analysis of several commercial nylons in trifluoroethanol + 0.05M LiBr using a styrene-divinylbenzene column custom-packed by Jordi Associates.

A broad molecular weight standard method was developed by interfacing GPC with LALLS to give the absolute molecular weight for each data point or elution volume along the chromatographic peak from a nylon sample of known molecular weight. The integrity of the interface was verified by static LALLS measurements; no loss or adsorption of solute was found in the chromatographic system.

A strong ionic effect was observed for nylon samples and the method to alleviate it was described. The molecular weights and distribution of the following nylons were determined by this method: nylon 6, nylon 4,6, and nylon 6,6. Much higher than quoted molecular weights were obtained for nylons when polymethyl methacrylates and ethylene glycols were used as standards; this necessitated the use of this broad molecular weight method for column calibration. The ambient operating conditions offered several advantages over the conventional m-cresol solvent which required operation at higher than 100 C in order to reduce the viscosity, possessed a strong odor, and occasionally resulted in degradation of polyamides.     

Gel Permeation Chromatography of Polymers from Wood

Abstract

Polymers from wood, including cellulose via the methylol derivative, are soluble in dimethyl sulfoxide (DMSO). To perform gel permeation chromatography of these high polymers, a packing material was sought which combined adequate pore size with stability in DMSO. Contrary to recommended practice, it was discovered that gel permeation chromatography in DMSO can be performed on prepacked, high-performance columns of μ-Styragel without adverse effects from bead swelling. When using the methylol derivative of cellulose, it is necessary to freeze dry the reaction mixture to obtain a product which gives reproducible results from gel permeation chromatography.     

Solvation and Adsorption Effects in Gel Permeation Chromatography

Abstract

Saturated hydrocarbons are generally eluted according to molecular volumes in gel permeation chromatography (GPC). Other compounds, containing polar groups such as hydroxyl and carbonyl groups, deviate from the molecular volume/elution count relationship which is prepared using saturated hydrocarbons. The deviation is more or less observed regardless of the kinds of eluents. In this paper, this problem is investigated in detail with respect to infrared(IR) and proton magnetic resonance(NMR) spectra, and concentration dependences of peak heights and elution volumes in GPC. IR and NMR spectra reveal that alcohols, ketones and esters are strongly solvated by eluent molecules such as chloroform and tetrahydrofuran(THF). The solvation effect leads to faster elution for these compounds than expected for aliphatic hydrocarbons. On the other hand, the concentration dependences of elution counts and peak heights prove the adsorption of amines on polystyrene gel in chloroform. In fact, the elution rates of amines and polychlorides are retarded. In the case of aliphatic carboxylic acids, the elution mechanism is more complicated: association and adsorption effects would be overlapped.     

Recent Advances in Aqueous Gel Permeation Chromatography

Abstract

The recent literature on aqueous gel permeation chromatography is reviewed. The chromatography of charged and uncharged solutes has been considered. A major emphasis has been to document the newer types of column packings for use in aqueous systems and their typical applications.