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 4: A study of model systems for reinforced vulcanizates

Summary Inverse gas chromatography with olefinic stationary phases, impregnated with silica gel or carbon black, and air as carrier gas has been found to yield characteristic shifts of retention data and concomitant changes in peak shape. The plots of retention index versus oxygen flow obtained indicate carbon black to have significant antioxidant properties, which are not altogether lost on solvent extraction. On the other hand, silica gel yields results consistence with the existence of a novel chain scission repair process.     

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.     

Inverse gas chromatography as a tool for investigation of nanomaterials

Inverse gas chromatography (IGC) is presented as a representative tool for the investigation of nanomaterials: Aerosil200V and two iron oxides (nanohematite and nanogoethite). IGC was used for characterization of the surface properties of materials. Parameters describing their surface properties are calculated from the retention data of test solutes injected into a column filled with the solid of interest. It is possible to determine the surface activity and the Hamaker constants of different nanomaterials.     

Inverse gas chromatography as a source of physiochemical data

Inverse gas chromatography (IGC) is presented as a useful method for the examination of physicochemical properties of various materials. The advantages of IGC are presented. However, the uncertainties and sources of possible errors are also indicated and discussed.     

Exploitation of a microporous organic polymer as a stationary phase for capillary gas chromatography

Microporous organic polymers (MOPs) have emerged as a new class of functional porous materials with unique characteristics and potential uses in diverse areas. However, the field of MOPs for gas chromatographic (GC) separations has not been well explored. Herein, a MOP namely KAPs-1 was dynamic coated onto a capillary column for the first time. The fabricated column exhibited a nonpolar nature and the column efficiency for n-dodecane was up to 7769 plates m⁻¹. The KAPs-1 coated column showed high GC separation performance for a series of volatile organic compounds (VOCs) including the challenging ethylbenzene and xylene isomers, which could not be resolved at baseline on the commercial 5% phenyl polysiloxane stationary phase. Moreover, the relative standard deviations for five replicate determinations of the studied analytes were 0.0–0.6%, 0.9–3.2%, 1.1–5.9%, 0.8–3.7% for retention time, peak area, peak height and peak width, respectively. To investigate the interaction between some analytes and the stationary phase, thermodynamic and kinetic parameters were also evaluated. The results of this study show it is very promising to utilize MOPs as stationary phases for capillary GC.     

Inverse gas chromatography for natural fibre characterisation: dispersive and acid-base distribution profiles of the surface energy

Inverse Gas Chromatography (IGC) is a gas sorption technique to determine the surface energy of natural fibres. The surface energy is directly related to the thermodynamic work of adhesion and it reflects the fibre adsorption capacity and its wettability. However, natural fibres have a complex surface chemistry of numerous organic species and present physical asperities that render the surface energetically heterogeneous. Since IGC is typically performed at infinite dilution where only the higher energetic sites interact with the solvent, a single measure of surface energy is likely to be misleading as the surface energy changes with changing chemical composition. Here we present the dispersive and acid-base surface energy profiles of flax and kenaf fibres as well as continuous filament fibres produced by a dry jet, wet spinning process (cellulose B). We injected a series of n-alkanes at finite dilution to obtain the dispersive energy distribution profile at \(30\,^{\circ }\hbox {C}\) and 0% RH. The acid-base contributions were determined by injection of mono polar probes (dichloromethane, ethylacetate) at the same surface coverages and applying the Van Oss method. The cellulose B fibres were the most energetically homogeneous, while the bast fibres were shown to have a higher polar component and much broader surface energy distributions than the cellulose fibres.     

Inverse gas chromatography in the examination of modified fillers

Dispersive and specific surface properties of silica modified with silanes, titanium and zirconium coupling agents were characterised by means of inverse gas chromatography. This method was also successfully applied in the examination of raw and modified silicates.     

Cation-modified silikalit-2 as a selective adsorbent for gas chromatography columns

A selective adsorbent was proposed on the basis of synthetic zeolite silikalit-2 modified with cadmium, tallium, and silver cations. It is intended for the gas chromatographic separation of some isomeric benzene derivatives. The adsorbent possesses pronounced retention properties to para isomers of aromatic compounds, which is due to the molecular sieve properties of the zeolite and the ability of benzene derivatives to form unstable complexes with cations entering the composition of the zeolite. Low selectivity to ortho and meta isomers is due to only the complexation effect.     

含氯橡胶制品中2-巯基咪唑啉的气相色谱法测定

建立了含氯橡胶制品中2-巯基咪唑啉的气相色谱分析方法.试样采用索氏提取,提取液经旋转蒸发浓缩、定容后,用Rtx-1701气相色谱毛细管柱分离,氢火焰离子化检测器(FID检测器)检测,外标法定量.2-巯基咪唑啉的平均回收率(n=7)为95.1％ ～100.6％,相对标准偏差(n=7)为4.4％ ～6.6％,检出限为1.0...     

Choice of preferred stationary phases for gas chromatography. Part II

Summary The regularities of changes of the polarity factors with the composition of mixed stationary phases are discussed. Values of the polarity factors of active solids, partitioning liquids and also colloidal stationary phases are compared. Part I: ref. [1].     

Low-molecular-weight model study of peroxide cross-linking of ethylene-propylene-diene rubber using gas chromatography and mass spectrometry II. Addition and combination reactions

The dicumyl-peroxide-initiated addition and combination reactions of mixtures of alkanes (n-octane, n-decane) and alkenes [5,6-dihydrodicyclopentadiene (DCPDH), 5-ethylidene-2-norbornane (ENBH) and 5-vinylidene-2-norbornane (VNBH)] were studied to mimic the peroxide cross-linking reactions of terpolymerised ethylene, propylene and a diene monomer (EPDM). The reaction products of the mixtures were separated by both gas chromatography (GC) and comprehensive two-dimensional gas chromatography (GCxGC). The separated compounds were identified from their mass spectra and their GC and GCxGC elution pattern. Quantification of the various alkyl/alkyl, alkyl/allyl and allyl/allyl combination products shows that allylic-radicals comprise approximately 60% of the substrate radicals formed. The total concentration of the products formed by combination is found to be independent of the concentration and the type of alkene. The total concentration of the products formed by addition to the alkene increases with increasing concentration of alkene. In addition, the total concentration of the formed addition products depends strongly on the type of the alkene used, viz. VNBH>ENBH approximately DCPDH, which is a consequence of differences in steric hindrance of the unsaturation. The peroxide curing efficiency, defined as the number of moles of cross-linked products formed per mol of peroxide, is 173% using 9% (w/w) 5-vinylidene-2-norbornane (VNBH). This indicates that the addition reaction is recurrent. All these findings are consistent with experimental studies on peroxide curing of EPDM rubber. In addition, the present results provide more-detailed structural information, increasing the understanding of the mechanism of peroxide curing of EPDM. The described approach to use low-molecular-weight model compounds followed by GC-mass spectrometry (MS) and GCxGC-MS analysis is proven to be a very powerful tool to study the cross-linking of EPDM.     

Chemical and spectroscopic methods for investigating polymer degradation and stabilization: Oxidative degradation of a hydrogenated nitrile rubber

The oxidation of a hydrogenated butadiene-acrylonitrile (2:1 mole ratio) rubber has been examined by infrared (IR) spectroscopy and the use of γ-initiation to give a controlled initiation step. The resolution and sensitivity of the IR technique was enhanced by the use of chemical derivatization in which carboxylic acids were measured as acid fluorides, hydroperoxides as nitrates and alcohols as nitrites. In all of these compounds, their spectra are sensitive to the precise substituents (primary, secondary or tertiary). Oxidation produced hydroperoxides from both tert. H-C-C=N and sec. H-C-H groups (≈︁1:1.1 mole ratio) as well as chain-end carboxylic acids [-CH₂-C(=O)OH]. From a comparison with measurements of peroxyl radicals produced at low temperature, average kinetic chain lengths for the various oxidation products were estimated and compared with these from other ethylene copolymers.     

Separation of pesticides by capillary gas chromatography. Part 2: Organophosphorus insecticides

This article considers the separation of 23 organophosphorus insecticides to which two metabolites have been added. The high resolution of the column permits detection of the Z and E isomers of three of these insecticides.     

Regulating the specificity of porous polymer sorbents used as the stationary phase in gas chromatography

Summary The main features of the retention of various homologous series on polymer sorbents with different functional groups, including typical ion-exchange resins, have been studied.Dedicated to ProfessorKiselev on the occasion of his seventieth birthday.