Inverse gas chromatography in the study of polymer degradation. Part 3. Study of the inhibited oxidation of squalene as a model for antioxidant protected,natural rubber vulcanizates

Summary Inverse gas chromatography with olefinic stationary phases, containing oxidation inhibitors, and air as carrier gas is shown to yield characteristic plots of retention index versus time, which may be explained in terms of the present knowledge of antioxidant action. A new technique for the evaluation of antioxidant efficiency is described that is sensitive to loss of antioxidant due to vaporization. Further evidence of the role of the support phase in inverse gas chromatography is presented and the adsorption of a hindered phenol used to give an estimate of the concentration of active sites on diatomaceous supports.     

Inverse gas chromatography in the study of polymer degradation. Part 2. Oxidation of sulphurated squalene as a model for the oxidative degradation of natural rubber vulcanizates

Summary Inverse gas chromatography with sulphurated olefinic stationary phases and air as carrier gas has been found to yield characteristic shifts of retention data. The resulting plots of retention index versus reaction time obtained for a range of squalene vulcanizates have been found to be similar to those given by oxygen absorption measurements. Furthermore the chromatographic oxidation curves have been found to be consistent with the known oxidation behaviour of the various sulphur networks formed on vulcanization. This paper is dedicated to the memory of Dr.Graham Moore (1924–1968).     

A study of the oxidation of vegetable oils by inverse gas chromatography

Summary Inverse gas chromatography is shown to be suitable for the study of the oxidation of vegetable oils. With air as carrier gas characteristic plots of retention index versus time are obtained for hydroxylic test solutes that are consistent with the oxidation behaviour of vegetable oils. Shifts of retention are found to be accompanied by changes of column efficiency due to the oxidative crosslinking of polyunsaturated vegetable oils. The technique also leads to useful information concerning the oxidation of antioxidant inhibited systems. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Inverse gas chromatography for the study of one phase and two phase polymer mixtures

Experiment finds that, for a chlorinated polyethylene (chlorine content 62.1% by weight)/poly(ethyl methacrylate) blend, a negative value of χ′_{2 3} is obtained, which indicates compatibility. With increasing temperature, χ′_{2 3} increases towards zero as required by the lower critical solution temperature behaviour of polymer blends. For chlorinated polyethylene/poly(butyl acrylate) blends however the specific retention volume is a linear function of composition and a positive χ′_{2 3} results if calculated by the conventional theory. The magnitude of χ′_{2 3} is determined by the difference between the retention volumes of the pure polymers and decreases with temperature. This effect is assumed to be a result of phase separation during coating the blend onto the support. A theoretical treatment is developed to explain this behaviour.     

A new model for the kinetic analysis of thermal degradation of polymers driven by random scission

In this paper, a series of f(α) kinetic equations able to describe the random scission degradation of polymers is formulated in such a way that the reaction rate of the thermal degradation of polymers that go through a random scission mechanism can be directly related to the reacted fraction. The proposed equations are validated by a study of the thermal degradation of poly(butylene terephthalate) (PBT). The combined kinetic analysis of thermal degradation curves of this polymer obtained under different thermal pathways have shown that the proposed equation fits all these curves while other conventional models used in literature do not.     

Inverse gas chromatography. Relationship between mass activity coefficient and flory-huggins interaction parameter in the examination of petroleum pitches

Summary The use of the basic relations for the calculation of the weight fraction activity coefficient Ω ₁ ^∞ and the Flory-Huggins interaction parameter ϰ ₁₂ ^∞ requires the knowledge of the density and the molecular mass of the stationary phase. As these data are often inaccessible the use of a simplified equation is examined. The errors generated during the calculation of ϰ ₁₂ ^∞ and solubility parameter δ₂ are presented and discussed. All experimental data were collected for the series of fractions separated from high-boiling vacuum distillation residues of petroleum.     

Application of inverse gas chromatography in the surface characterization of diethanol amine modified polystyrene based polymer

In the present work, diethanol amine modified polystyrene based polymer (PVBC-Diethanol amine) was synthesized and characterized, then surface properties of the polymer were examined by inverse gas chromatography method at infinite dilution. The retention diagrams obtained based on the interaction of polar and nonpolar probes with the polymer were drawn over a temperature range from 30 to 55 °C. Through the diagrams, the dispersive component of the surface free energy, g _S ^D of the polymer surface, and the specific enthalpy of adsorption, DH _A ^S , of probes on the polymer were also calculated. Lewis acid, K _A , and Lewis base, K _D , parameters of PVBC-Diethanol amine surface were determined. The values of K _A and K _D indicated that PVBC-Diethanol amine surface exhibited a basic behavior.     

Microcolumn chromatography for the analysis of detergents and lubricants. Part 1: High temperature capillary gas chromatography (HT-CGC) and capillary supercritical fluid chromatography (CSFC)

High Temperature Capillary GC and Capillary SFC have been applied to the analysis of non-ionic lubricants, i.e. alkylphenol polyethoxylates (APnEO), ethoxylated alcohols (nEOAIc), polyethylene glycols (PEG), and ethoxylated triethanolamines (nEOEA); to the analysis of anionic lubricants, i.e. alkylbenzene-sulfonates (ABS), alkylsulfonates (AS), and ethoxylated phosphoric acids (nEOPhA); and to the analysis of cationic lubricants, i.e. quaternary ammonium salts (Quats). Both techniques are compared in terms of resolution and analysis time. The importance of derivatization in HT-CGC and CSFC is illustrated.     

A CP-MAS NMR study of some deactivation methods in capillary gas chromatography

The effect of temperature, water content, and the type of reagent on the silylation of fused silica capillaries was studied by ²⁹Si and ¹³C CP-MAS NMR. Fumed silica (Cab-O-Sil M5), which is essentially a highly dispersed vitreous quartz with a surface comparable to that of fused silica capillary columns, was selected as a model material. Hexamethyldisilazane (HMDS) and 1,2-diphenyl-1,1,3,3-tetraphenyldisilazane (DPTMDS), which were used as silylation reagents, yielded trimethyl- and dimethylphenylsilyl surface groups respectively at lower temperatures (< 350°C and <250°C respectively). At higher temperatures, increasingly more dimethylsilyl groups are formed, with the silicon bound to two oxygen atoms. This process occurs for DPTMDS at a considerably lower temperature than for HMDS. The formation of silyl groups on the surface and the disappearance of hydroxyl groups are followed independently. The ¹³C NMR and GC-MS of the reaction products showed that with DPTMDS, the formation of two Si-O-Si links is accompanied by a loss of phenyl groups rather than of methyl groups. After the Cab-O-Sil had been dried over P₂O₅, the formation of these double links occurred for HMDS only at temperatures above 460°C and for DPTMDS at 400°C. Thus we concluded that water supplies oxygen atoms for double Si-O-Si links (possibly crosslinks) necessary for efficient deactivation. This may explain the less successful silanization of fused silica capillaries because their water content is lower than that of glass capillaries.     

Glass capillary gas chromatography of C1−C4 mononitroalkanes. Pre-calculation of the relative retention

Summary The separation of C₁–C₄ mononitroalkanes on four wall-coated glass open tubular (capillary) columns (liquid phases: OV-101, Ucon-LB-550X, NPGS and Carbowax 20M) was investigated. Retention indices were determined and the influence of the different factors (analysis temperature, method of determining the gas holdup time and the nature of the stationary phases) on their reproducibility were studied. Linear regression equations permit the pre-calculation of the retention indices of C₁–C₄ mononitroalkanes from their properties on all liquid phases studied.     

Inverse gas chromatographic study of supramolecular organization in microheterogeneous systems for the example of polyblock copolymers

The potentialities of inverse gas chromatography for studying microheterogeneous polymer systems are analyzed. For the first time this method is applied to examination of the microstructure of multiblock copolymers obtained by condensation. A procedure for evaluation of the partial contribution of the dissolution to the total retention volume is suggested.     

Comparative study of differential flow and cryogenic modulators comprehensive two-dimensional gas chromatography systems for the detailed analysis of light cycle oil

The modulator is the key point of comprehensive two-dimensional gas chromatography (GC×GC). This interface ensures the sampling and transfer of the sample from the first to the second dimension. Many systems based on different principles have been developed. However, to our knowledge, almost only cryogenic modulators are used in the petroleum industry. Nevertheless cryogenic fluids represent some disadvantages in term of safety, cost and time consuming. This paper reports a comparative study between differential flow and cryogenic liquid modulators for the detailed analysis of hydrocarbons in middle distillates type light cycle oil (LCO). Optimization of geometrical dimensions of a set of columns was carried out on the differential flow modulator system in order to reproduce the quality of separation of cryogenic modulation. Then a comparative study was investigated on sensibility and resolution (separation space and peak capacity) between the two systems.     

A study of some deactivation methods for fused silica capillary columns by CP-MAS NMR and capillary gas chromatography

The effect of deactivating a fused silica surface by silylation with 1,1,3,3-tetraphenyl-1,3-dimethylilazane (TPDMDS), triphenylsilylamine (TPSA), and octamethylcyclotetrasiloxane (D4) and by polydimethylsiloxane degradation (PSD) is studied. Rehydrated, dried, and deactivated Cab-O-Sil M5 samples are used as model materials for ²⁹Si CP-MAS NMR analysis. At about 350 °C, TPDMDS yelds mainly diphenylmethylsiloxysilane, dimethyldisiloxysilane, and triphenylsiloxysilane groups. TPSA yields phenyltrisiloxysilane, diphenyldisiloxysilane, and triphenylsiloxysilane groups. At 400°C, the products formed initially are eventually replaced by methyltrisiloxysilane or phenyltrisiloxysilane groups, while a substantial number of silanol groups still remains. The possible consequences for wettability are discussed. D4 reacts with Cab-O-Sil even at 200°C, but a large number of silanol groups remains. This number decreases gradually at higher temperatures and becomes negligible above 400°C. The formation of methyltrisiloxysilane groups, which starts at 425°C, is predominant at 490°C.     

Dielectric relaxation in polymer solids Part 2: Application of the new model to polyurethane systems

Measurements of the complex permittivity of crosslinked polyurethanes at different temperatures in the frequency range 1–10⁵ Hz are discussed with respect to shape of relaxation curves. Using a new model (published in preceding paper) the shape parameters are related to small and large scale interaction.     

High temperature gas chromatography for the analysis of fossil fuels: A review

For the past two or three decades geochemists have been concerned with the analyses and characterization of compounds, generally hydrocarbons, ranging from C₁? C₄₀. Significant amounts of information have resulted from these studies which have been extremely useful in many geochemical and environmental studies. However, in the past two or three years the commercial development and availability of high temperature gas chromatography columns has lead to the investigation of the occurrence and distribution of high molecular weight hydrocarbons (HMWHC), and other compounds, in the carbon number range C₄₀? C₁₀₀, present in oils, waxes, bitumens and rock extracts. The ability to study these compounds represents a major advance in organic geochemistry. In some samples these compounds may represent the bulk of the organic components but prior to development of the high temperature columns it was impossible to study their distributions. This paper will review advances that have occurred in terms of the application of high temperature gas chromatography (HTGC) to the analyses of fossil fuel samples and discuss the possible origin and significance of these compounds that have been identified. In addition, some of the potential problems involved in the analyses of these compounds will also be discussed.     

Cyclodextrins as chiral stationary phases in capillary gas chromatography. Part VII: Cyclodextrins with an inverse substitution pattern – synthesis and enantioselectivity

Transferring the site of specific substitution of dipentylated cyclodextrins with methyl or acyl residues from the secondary 3-hydroxyl group to the primary 6-hydroxyl group was expected to provide new information on the mechanism of chiral recognition. The 3-position points towards and the 6-position points away from the cyclodextrin cavity which via inclusion complex formation is supposed to play a major role in chiral separation. The “inverse” 6-O-acyl-2,3-di-O-pentyl-cyclodextrins displayed almost no enantioselectivity but the corresponding 6-O-methyl derivatives are a versatile supplement to the chiral capillary GC phases nowadays available. Among the compounds that could be enantiomerically resolved are alcohols, amino acids, alkyl halides, bicyclic ethers, acetals, olefins, other hydrocarbons and chiral pharmaceuticals.