High temperature gas chromatography: The development of new aluminum clad flexible fused silica glass capillary columns coated with thermostable nonpolar phases: Part 1

With the simultaneous development of blank aluminum clad flexible fused silica glass capillary tubing capable of withstanding temperatures up to 500°C, coincident with a series of special high temperature methyl polysiloxane polymers, it was possible to produce for the first time, long lived fused silica capillary columns containing thin films of thermostable stationary phases which could be maintained isothermally at 400425°C and temperature programmed to 425–440°C. The “bleed rate” here for a well conditioned column was 5 picoamperes or less. Under these circumstances, alkanes with carbon numbers in the C-90 to C-100 area were rapidly and efficiently eluted from these columns. By extrapolation here, one can easily detect certain compounds with boiling points in the 750°C range. Since this type of capillary column was found to possess certain favorable properties, it was thought that it will soon replace the packed column and will probably be more popular than the borosilicate capillary column for many high temperature applications. Moreover, evidence has now accumulated which leads us to further believe that the majority of analyses of “high molecular weight” compounds performed by Supercritical Fluid Chromatography (SFC), utilizing very narrow bore fused silica capillary columns at several hundred atmospheres, can be much more simply, much more rapidly, much more economically, and much more efficiently accomplished by gas chromatography utilizing this new generation of high temperature capillary columns.     

Study on the determination of the molecular weight of polyethylene with ultrahigh temperature GPC

Ultrahigh or high molecular weights of polyethylenes (PE) and their distributions are for the first time determined at 160° or 170°C by gel permeation chromatography (GPC). The thermostability of PE at high temperatures is discussed. In order to calculate the real molecular weight of PE, a new calibration curve is established. For PE with high molecular weight more reliable and accurate results can be obtained by GPC measurements at these temperatures. The application of ultrahigh temperature GPC for polymer characterization is demonstrated in this paper.     

High oven temperature — cold on-column injection for the automated CGC analysis of high molecular weight compounds such as triglycerides

Modification of the Carlo-Erba cold on-column injector for (automated) analysis of high molecular compounds at high oven temperature is described. The secondary cooling tube of the cold on-column injector is replaced by a lengthened tube through which a high air flow is directed. The injection site is maintained at 65–70 °C while the oven is at high temperature (? 300 °C). For automated injection, a short deactivated precolumn of 22 to 30 cm × 0.53 mm i.d. is coupled to the analytical column via a butt connector with make-up gas supply. For a triglyceride mixture, automatically injected at 300 °C, the mean % deviation for all peak areas was 1.8% and the mean % deviation for all retention times was 0.09 % for five consecutive runs.     

Main-chain,syndioregic, high-glass transition temperature polymer for nonlinear optics: Synthesis and characterization

A new main-chain syndioregic (head-to-head) NLO polymer was synthesized. The glass transition temperature of high molecular weight polymer was found to be 208°C, and the polymer has minimal weight loss at temperatures to at least 250°C owing to the incorporation of hydrogen bonding moieties and rigid bridging groups. The polymer was further characterized using nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The study of the nonlinear optical properties of this polymer are in progress. © 1993 John Wiley & Sons, Inc.     

Thermal degradation of copolymers of styrene and acrylonitrile. III. Chain-scission reaction

The chain-scission reaction which occurs in copolymers of styrene and acrylonitrile has been studied at temperatures of 262, 252, and 240°C. Under these conditions volatilization is negligible, and chain scission can be studied in virtual isolation. At 262°C three kinds of chain scission are discernible, namely, at weak links which are associated with styrene units, “normal” scission in styrene segments of the chain and scission associated with the acrylonitrile units. The rate constants for normal scission and scission associated with acrylonitrile units are in the ratio of approximately 1 to 30. The molecular weight of the copolymer has no effect on the rates of scission. At 252°C the same general behavior is observed for the copolymers containing up to 24.9% acrylonitrile. The 33.4% acrylonitrile copolymer is anomalous, however. At 240°C the trends observed at 262°C appear to break down completely although individual experiments are quite reproducible. This behavior at the lower temperatures is believed to be associated with the fact that the melting points of the various copolymers are in this temperature range. Thus the viscosity of the medium, which should be expected to have a strong influence on the chain scission reaction, will be changing rapidly with temperature, copolymer composition, and molecular weight in this temperature range.     

Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VII. Effect of pretreatment temperature of silica gel on styrene–silica gel system

To investigate the reaction mechanism of radiation-induced polymerization of styrene adsorbed on silica gel, the effect of pretreatment temperature of silica gel was studied. Preheating of silica gel was carried out at 200, 500, and 800°C. The number of silanol groups of silica gel surface decreased as preheating temperature increased. The rate of polymerization on the silica gel preheated at 500°C was faster than that at 200°C, but the polymerization rate on the silica gel preheated at 800°C was the lowest. These results suggest that rate of polymerization on the silica gel is affected by the conditions of silica gel surface such as the number of silanol groups and the pore size. At the same monomer conversion, percent grafting decreased as preheating temperature of silica gel increased. The GPC spectra of both graft polymers and homopolymers have two peaks at all preheating temperatures. The monomer conversion of low molecular weight peaks of graft polymers decreased as preheating temperature of silica gel increased. This result suggests that there is a probability that the grafting sites of low molecular weight peaks of graft polymers somehow interact with silanol groups.     

Quantitative determination of fluorine in toothpastes

The quantitative CE analysis of fluorine and monofluorophosphate in toothpastes is described. Separation is performed using a Waters CIA-Pak chemistry kit with Waters Electro Osmotic Flow Modifiers on a CE instrument from Spectra Physics (Spectra-phoresis 500) at elevated temperatures up to 40 °C and at a low temperature of 10 °C. The quantitative results and the simplicity are compared for the CE method, the existing standard GC procedure described in the Official Journal of the European Communities, and the procedure employing a fluoride-ion-specific electrode.     

Structural evolution of an ABA poly(styrene-b-isoprene) block copolymer with temperature

The structural evolution with temperature of an anionically synthesized ABA poly(styrene-b-isoprene) (SIS) lamellar block copolymer (total molecular weight 45,000; isoprene content 38% by weight) was studied by melt-rheological measurements, electron microscopy, and x-ray and light diffraction. Above 225°C, the dynamic viscosity was found to be independent of frequency up to a critical frequency. The variation of the elastic modulus confirmed the occurence of a transition between 215 and 225°C. For the temperature range considered, all results superimposed well on a two-branch master curve. It was concluded that above 225°C, our SIS behaves like a Newtonian material, whereas for lower temperatures and/or higher frequencies classical non-Newtonian behavior is found. The melt-rheological properties were explained by microscopy and diffraction investigations, which allowed us to follow morphological changes as the temperature was raised. It was found that the two-phase lamellar structure is progressively destroyed, and the transition temperature of 225°C corresponds to the temperature above which complete mixing occurs.     

Frequency and temperature dependence of the dynamic mechanical properties of poly-4-methylpentene-1

The dynamic mechanical properties of poly-4-methylpentene-1 have been measured in torsion in the temperature range from 25 to 160°C. at frequencies from 10^?3 to 10 cps. Two transitions are found. The first, with a peak at 40°C. at 1 cps, appears as a normal glass transition. A broad high temperature peak appears at 130°C. The dynamic compliance-frequency data can be superposed by the conventional method of reduced variables for temperatures up to 100°C. The temperature dependence of the shift factors follows the WLF equation. Above this temperature, superposition can be achieved by applying horizontal and vertical shifts to both components of the dynamic compliance. When the vertical shift is permitted, the range of applicability of the WLF equation is extended to 160°C.     

Thermally stable polymers derived from 2,3,5,6-tetraaminopyridine

The stable trihydrochloride salt of 2,3,5,6-tetraaminopyridine (TAP) has been found to be a versatile intermediate to a variety of thermally stable polymers such as polybenzimidazoles (PBI), polyimidazopyrrolones (pyrrones), and polybenzimidazobenzophenanthroline (BB polymer). The controlled reactivity of two of the four amino sites of TAP · 3HCl towards diacid halides and dianhydrides makes possible the preparation of high molecular weight, soluble polyamide prepolymers at mild temperatures. PBI, pyrrones, and BB polymer are obtained from the linear polyamide precursors by heating at 150–375°C. Unoptimized cyclized polymers were aged isothermally in air at 600°F (316°C) and found to be superior to analogous polymers described in the literature. Weight retentions of up to 97% were observed after 500 hr in air at 600°F.     

The effect of structural variations on aromatic polyethers for high‐temperature PEM fuel cells

Three series of new aromatic polyether sulfones bearing phenyl, p‐tolyl or carboxyl side groups, respectively, and polar pyridine main chain groups were developed. Most of the polymeric materials presented high molecular weights and excellent solubility in common organic solvents. More importantly, they formed stable, self‐standing membranes that were thoroughly characterized in respect to their thermal, mechanical and oxidative stability, their phosphoric acid doping ability and ionic conductivity. Particularly, the copolymers bearing side p‐tolyl or carboxyl groups fulfill all necessary requirements for application as proton electrolyte membranes in high temperature fuel cells, which are glass transition temperatures higher than 220 °C, thermal stability up to 400 °C, oxidative stability, high doping levels (DLs) and proton conductivities of about 0.02 S/cm. Initial single fuel cell results at high temperatures, 160 °C or 180 °C, using a copolymer bearing p‐tolyl side groups with a relatively low DLs around 200 wt % and dry H₂/Air feed gases, revealed efficient power generation with a current density of 0.5 A/cm² at 500 mV. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

High pressure ethylene polymerization with a post‐metallocene bis‐phenyl phenoxy catalyst

The use of post‐metallocene bis‐phenylphenoxy catalysts to polymerize ethylene under high ethylene pressures (>25,000 psi) results in some remarkable catalytic properties. The high ethylene pressure produces molar ethylene concentrations in the reactor as much as 40 times higher than in typical low pressure ethylene polymerizations. This high ethylene concentration results in high catalyst efficiency at high temperatures and low reactor residence time, between 180 °C and 240 °C the catalyst efficiency surprisingly increases with increasing temperature, allowing for use of these catalysts at temperatures much higher than can be utilized in the low pressure processes. It has further been demonstrated that under these conditions increasing hydrogen levels up to 0.5 mol% does not significantly affect the polymer molecular weight; however, polymer molecular weight control can be realized with varying reactor temperature. The polymer produced is shown to be high density polyethylene made from a single site catalyst and not free radical initiated low density polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 861–866     

Cationic polymerization of isobutylene coinitiated by AlCl3 in the presence of ethyl benzoate

<正>The cationic polymerizations of isobutylene(IB) coinitiated by AlCl_3 were carried out in solvent mixture of n-hexane /methylene dichloride(n-hex/CH_2Cl_2) of 60/40 V/V in the presence of ethyl benzoate(EB) at various temperatures range from-80℃to-30℃.The effects of EB concentration([EB]) and polymerization temperature on monomer conversion,weight-average molecular weight(M_w) and molecular weight distribution(MWD,M_w/M_n) of polyisobutylene (PIB) products were investigated.The rate of polymerization decreased while M_w of PIB products increased with increasing [EB].The polymers with high molecular weight could be prepared in the presence of a suitable amount of EB.Significantly, the polymers with high M_w of 80.2×10~4 and 65.4×10~4 could be produced at-80℃and-70℃at[EB]=0.24×10~(-3) mol/L respectively,which were much higher than that(M_w=57.9×10~4) of PIB prepared at-100℃in the absence of EB.A simple but effective method for preparing the high molecular weight polyisobutylenes was developed in this work.It has been also found that the activation energy for propagation(E_p) depended on the polymerization temperature range in the presence of EB.An obvious inflection of the linear plots of lnX_n versus 1/T_p occurred at the temperature range from-60℃to-50℃at four different concentrations of EB from 0.19×10~(-3) mol/L to 0.33×10~(-3) mol/L,and thus the inflection temperature(T_(inf)) was in the range of-60℃to-50℃.When[EB]was in the range of 0.24×10~(-3) mol/L to 0.33×10~(-3) mol/L,E_p was determined to be around-12 kJ/mol when the polymerization was carried out at temperatures from-80℃to T_(inf) and to be around-28 kJ/mol at temperatures from T_(inf) to-15℃respectively.     

The effect of temperature and solvent on the synthesis and properties of nylon 610 made from sebacyl bisketene

Polyamides were synthesized at ?60°, ?40°, ?20°, and 0°C from sebacyl bisketene and 1,6-hexamethylenediamine in either acetone or methylene chloride. At the lower reaction temperatures oligomers predominated in solution but at 0°C the product was crosslinked. The polyamides were subjected to m-cresol extraction at elevated temperatures for up to 14 days. The m-cresol soluble and insoluble fractions were characterized by weight, infrared spectroscopy, dilute solution viscosity, and gel permeation chromatography. Infrared analysis of the soluble and insoluble portions showed the degree of branching of the polyamide, identified the branching point at the secondary amide proton position, and gave an indication of the degree of branching required before insoluble products resulted. Dilute solution viscosity and gel permeation chromatography were used to demonstrate the existence of low molecular weight (M_w) oligomer species in the soluble portion. Differential scanning calorimetry experiments revealed that polyamides synthesized below their glass transition temperature would not crystallize which resulted in abnormal thermal characteristics. Annealing at elevated temperatures allowed crystallization to occur and the expected thermal character to develop.     

Ethylene-vinyl acetate semi-batch emulsion copolymerization: Use of factorial experiments for process optimization

The application of factorial experiments to optimize the ethylene-vinyl acetate emulsion polymerization process is described herein. A prior extensive experimental phase identified those variables that are most important for ethylene-vinyl acetate emulsion copolymer production. The effects of temperature, pressure, added co-solvent, vinyl acetate feed rate and emulsifier type, and concentration on the rate of polymerization, cumulative copolymer composition, molecular weight averages, and particle size and number are described in this article. The primary objectives of this research were to increase the amount of ethylene that could be incorporated into the copolymer at reduced temperatures and pressures (our target was a copolymer with an ethylene content of 30% by weight at 500 psig and 20°C versus the commonly employed industrial conditions in excess of 1000 psig), to achieve an improved process understanding, and to accumulate reliable data for modelling purposes. A copolymer containing 34% by weight of ethylene has been achieved at a pressure of 500 psig and a temperature of 20°C. The confusion present in the literature surrounding emulsifier effects has also been clarified. A discussion of hydrolysis, experimental reproducibility, and glass transition temperatures is also included. The sequential nature of the experimental process is illustrated throughout these optimizing experiments. © 1994 John Wiley & Sons, Inc.     

Radiation-induced ionic polymerization of isobutyl vinyl ether in bulk

The radiation-induced ionic polymerization of isobutyl vinyl ether was investigated under conditions where the monomer was dried with molecular sieves. The investigation covered the temperature range from ?16°C to 90°C, and the dose-rate range from 10¹⁵ to 10²⁰ eV/g-sec, using both γ-rays and electrons. A very high overall activation energy of 15.9 kcal/mole was found for the process below 30°C. Above 30°C, however, the value of the overall activation energy dropped to 4.9 kcal/mole, a phenomenon which is ascribed to the solvation of the propagating carbonium ion below 30°C. The dose-rate dependence of the rate of polymerization was found to be 0.58 over the entire dose-rate range investigated. The molecular weight of the polymer was found to be far less sensitive to trace amounts of water than the rate of polymerization. The molecular weight of the polymer depended strongly on the irradiation temperature, reaching a maximum value of about 120,000 at 35°C. It is shown that at temperatures above 20°C regenerative chain transfer processes play an important role in determining the molecular weight of the polymer.     

RADIATION CROSSLINKING OF BIODEGRADABLE POLY(BUTYLENE SUCCINATE) AT HIGH TEMPERATURE

Poly(butylene succinate), (PBS) with different molecular weight was γ-irradiated at different temperatures and various doses. PBS with high molecular weight and smaller peak area of crystal melting gave the highest gel content at the same temperatures and dose. A two-step irradiation (irradiation in molten state after irradiation at room temperature) gave the highest gel content in different conditions. This is due to the formation of network structure by pre-irradiation at room temperature that leads to less degradation. PBS prepared by two step irradiation was effective for improvement of heat stability because of high gel content formation. Unirradiated PBS sheets broke immediately at 110°, while the irradiated sample (gel fraction, 50%) by a two step-method, did not break even up to 200 minutes at 130°C. The PBS sheets are biodegradable even after crosslinking.     

Micro-pyrolysis of technical lignins in a new modular rig and product analysis by GC–MS/FID and GC × GC–TOFMS/FID

A new offline-pyrolysis rig has been designed to allow multifunctional experiments for preparative and analytical purposes. The system conditions can be set and monitored, e.g. temperature, its gradients and heat flux. Some special features include (1) high heating rates up to 120 °C/s with pyrolysis temperatures up to 850 °C at variable pyrolysis times and (2) the selection of different atmospheres during pyrolysis. A complete mass balance of products and reactants (gas, liquids and solids) by gravimetric methods and sequential chromatographic analyses was obtained.The pyrolytic behaviour and the decomposition products of lignin-related compounds were studied under different conditions: heating rates (from 2.6 °C/s up to 120 °C/s), pyrolysis temperatures at 500 °C and 800 °C in different atmospheres (N₂, H₂, and mixtures of N₂ and acetylene). Kraft lignin, soda lignin, organosolv lignin, pyrolytic lignin from pine bio-oil, residues from biomass hydrolysis and fermentation were studied.The obtained pyrolysis products were classified into three general groups: coke, liquid phase and gas phase (volatile organic compounds (VOC) and permanent gases). The liquid fraction was analysed by GC–MS/FID. In addition, comprehensive two-dimensional GC was applied to further characterise the liquid fraction. VOCs were semi-quantified by a modified headspace technique using GC–MS/FID analysis. The micro-pyrolysis rig proved to be an efficient and useful device for complex pyrolysis applications.     

Uncertainty budget for high temperature heat flux DSCs

This study addresses the lack of published information regarding uncertainty for high temperature heat flux differential scanning calorimeters. No data were found in the existing literature stating an uncertainty budget for temperatures above 1,000 °C. The presented results identify the main influencing factor for uncertainty with the instruments used—measurement repeatability—up to a temperature of 1,400 °C. Results show findings from analyzing a series of repeated baseline and sapphire measurements and the influence from different working equations. The uncertainty budget for temperature calibration of DSCs is crucial in cases where accuracy in temperature is significant. Data are also provided from repeated temperature calibrations on the melting point of pure metals from a supplied standard set that comes with the instrument. In addition, carbon eutectics have been used to address an issue resulting from the lack of available calibration materials for high temperatures up to 1,500 °C (above the melting point of gold).