Two-dimensional n.m.r. characterization of cycloaliphatic epoxy resins

The cycloaliphatic epoxy resins were studied by various two-dimensional nuclear magnetic resonance (2D n.m.r.) spectroscopies. The ¹³C n.m.r. spectra of the epoxy resins were assigned by using DEPT and 2D INADEQUATE techniques and the ¹H n.m.r. spectra were assigned by using 2D ¹H---¹H and ¹H---¹³C COSY techniques. Complete characterization of the samples synthesized by the oxidation of cyclohexene derivatives not only revealed the existence of the stereochemical isomers resulting from the structural difference of the oxide rings in the samples but also provided the composition ratio of the isomers.     

Structure and properties relationships of epoxy resins part 1: Crosslink density of cured resin: (I) model resins synthesis

Two model epoxy resin precursors based on the N-glycidyl derivatives of 4.4'-diaminodiphenylene methane (DDM) were prepared: N,N bis-(2,3-epoxypropyl)-N′,N″-dimethyl-4.4'-diaminodiphenylene methane (G2A); N.N′ bis-(2,3-epoxypropyl)-N,N′-dimethyl-4,4'-diaminodiphenylene methane (G2S). To prepare these, aniline or N-methyl aniline was reacted with epichlorohydrin, using acetic acid as catalyst. The products were coupled via acid-catalysed condensations in the presence of formaldehyde or with N,N-dimethylaminobenzyl alcohol. The coupled chlorohydrins formed were then dehydrochlorinated to form the desired product. All reactions were monitored and purifications of the crude products were effected by high pressure liquid chromatographic techniques. The products were characterised by proton and carbon-13 nuclear magnetic resonance, infrared and mass spectroscopy, elemental and titrametric analysis. Results were compared with those obtained for tetra-N-glycidyl-4,4'-diaminodiphenylene methane (TGDDM). All the data confirmed the structures of the model resins. These, together with TGDDM. will be used to prepare epoxy resin networks of controlled crosslink density and chemical homogeneity.     

The radiation crosslinking and scission of ethylene-propylene copolymers studied by solid-state nuclear magnetic resonance

Methyl groups from chain scission and H-crosslinks have been identified by solid-state nuclear magnetic resonance in amorphous ethylene-propylene copolymers containing 23 and 36 mole % propylene after γ-irradiation to 10 MGy at 30°C. G (scission) and G (crosslink) values determined from the n.m.r. spectra and by extraction are in agreement, which suggests that the crosslinks are not clustered. This may differ from the situation in polyethylene where there is a substantial crystalline content. G(S). G(X) and the ratio G(S)/G(X) increase with increasing propylene content of the copolymers.     

Studies on copolymers of acrylonitrile with resins of furfuryl alcohol: 1. Preparation and thermal properties

Copolymers of acrylonitrile with a furfuryl alcohol resin have been prepared by a free radical reaction, and have been characterized by n.m.r. and i.r. spectroscopy. Their t.g.a. has been performed in air and in a nitrogen atmosphere, to permit the recognition of a number of stages in the weight loss process. D.s.c., also in air and in nitrogen, has identified a number of exothermic and one endothermic process in the copolymers. Solid state cross-polarization/magic angle spinning ¹³C n.m.r. spectroscopy and i.r. spectroscopy has been used to obtain some insight into the chemistry of the various chemical changes, which in air are completed by combustion and in nitrogen leave a carbon.     

High temperature and high pressure H n.m.r. and e.s.r. studies on coal liquefaction reactions

Changes in chemical reactions during coal liquefaction of Yallourn brown coal and Akabira bituminous coal were monitored by using high temperature and high pressure ¹H n.m.r. A simple high temperature and high pressure e.s.r. cell was constructed and the variation in concentration of free radicals during coal liquefaction reactions was monitored under the same experimental conditions as for n.m.r. With the liquefaction and coking reaction, typical spectra of n.m.r. and e.s.r. were obtained and could distinguish the reaction steps: swelling; liquefaction; coking. The combination of high temperature and high pressure n.m.r. and e.s.r. is promising to the chemistry of coal liquefaction reactions.     

1H and 13C nuclear magnetic resonance studies of the synthesis of linear segmented polyurethane elastomers

Linear segmented polyurethane elastomers have been prepared by reaction of polyethyleneoxide with 4,4′-diphenylmethanediisocyanate and the product was subsequently cured with diamines. Chemical analysis of the prepolymer formed using stoichiometric ratios of polyol and diisocyanate indicated that the product was deficient in ‘free’ isocyanate. A number of side reactions can lead to a reduction in the amount of isocyanate available for the chain extension reaction. Infrared, ¹H- and ¹³C-n.m.r. spectroscopy were used to follow the initial end-capping and subsequent chain extension reactions. In order that an unambiguous assignment of the weak peaks observed in the prepolymer and final elastomer spectra could be made, a number of model compounds associated with the side reactions were synthesized and their spectra characterized. It was concluded that the loss of ‘free’ isocyanate in the formation of the prepolymer can be predominantly attributed to the effects of traces of water in the initial reaction mixture.     

C cross-polarization n.m.r. examination of the Glen Davis oil shale deposit

The use of solid-state ¹³C cross-polarization n.m.r. for rapid analysis of bore cores is demonstrated by examination of subsections of a Glen Davis oil shale bore. The determined aromaticities, f_a, differ widely between subsections indicating large variability in potential oil yields. The variation does not correlate with depth of subsection but is shown to correlate well with maceral composition. The correlation found previously by Zilm and co-workers (Fuel 1981, 60, 717) between f_a, determined by solid-state ¹³C n.m.r., and wt% fixed carbon for a range of macerals is found to be supported by the data for Glen Davis subsections which are mixtures of all three maceral types.     

Effect of oxygen on the crosslinking and mechanical properties of a thermoset formed by free‐radical photocuring

In this article, we report on the formation of optically transparent photopolymer films from hexanediol diacrylate (HDDA) by inkjet printing, where droplets of monomer approximately 5 μm in diameter were deposited onto a surface. The films were cured by irradiation with a UV‐light‐emitting‐diode light source. It was found that the inkjet‐printed HDDA films picked up a considerable amount of absorbed O₂ during printing. Exposure to increasing amounts of O₂ during photocuring severely restricted both the degree of conversion and the UV dose required for gelation in proportion to the O₂ concentration. Viscoelastic property data indicated that exposure to reduced oxygen concentrations during thermal postcuring (dark reaction) resulted in linear trends of increasing modulus above the glass‐transition temperature (T_g) and increasing T_g itself. Thus, the final crosslink density was greater in fully cured samples that were exposed to atmospheres with increasing inert gas concentrations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A chemical demonstration of the randomness of epoxidation of natural rubber

During the development of chemical methods for determining the epoxide content of epoxidised natural rubber (ENR) two methods were found to give results which were identical but which showed a progressive divergence from values obtained by absolute instrumental methods as the level of epoxidation increased. Statistical analysis of the sequence distribution of the epoxide groups, based on a random epoxidation, showed a good correlation between the value obtained by chemical analysis and the number of epoxide blocks rather than the number of epoxide groups. Two further instrumental methods for measuring the total epoxide content, using infra red spectroscopy and differential scanning calorimetry, were developed. Analytical procedures and calibration data are supplied. A combination of one chemical and one instrumental method can thus provide the absolute level of epoxidation and indicate whether the reaction has proceeded randomly or not, a point of crucial importance in the large scale manufacture of this material.     

Preliminary studies on the aromaticity of Australian coals: Solid state n.m.r. techniques

The aromaticities of samples from nine Australian coal seams, including pairs of hand-picked vitrains and durains, have been determined by ¹³C cross-polarization n.m.r. spectroscopy with magic angle sample spinning. The results clearly show that the aromaticity (f_a) of the coals increases with increase in vitrinite reflectance and carbon content and decrease in atomic H/C ratio. For a given coal seam, durain (inertinite-rich coal) has a higher f_a value than vitrain (vitrinite-tich coal). The trends for carbon content and atomic H/C are in good agreement with results from North American coals, although the aromaticities of Australian coals obtained in this study appear to be slightly lower than some of those reported for North American coals of similar carbon content.     

Studies on the cure kinetics and networks properties of neat and polydimethylsioxane modified tetrafunctional epoxy resins

The cure kinetics of tetrafunctional epoxy resins with three different backbone structures and their modification by polydimethylsioxane (PDMS) were studied by means of differential scanning calorimetry with dynamic approach. The development of epoxy networks was characterized by dynamic viscoelastic measurements. Results showed that all the epoxy resins obeyed the autocatalytic reaction mechanism with a reaction order of about 3. Epoxy resin with softer aliphatic backbone demonstrated a higher cure reactivity and stronger tendency towards autocatalysis, as well as lower crosslinking density. The PDMS‐modified epoxy resins showed higher early cure reactivity and a lower crosslinking density due to the plasticization and restriction effect of the dispersed PDMS phase, respectively. Based on cure kinetics and dynamic viscoelastic results, the α_m was found to be an effective precursor for describing the developing of epoxy networks during the course of cure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterisation of some melamine-formaldehyde condensates and some cured resins by 1H, 13C and 15N n.m.r. spectroscopy

Some oligomeric species (condensates) in a melamine-formaldehyde adduct mixture have been isolated by preparative high performance liquid chromatography (h.p.l.c.) and partly identified by high field ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopy. The oligomers are shown most likely to be largely dimers, trimers and tetramers and to contain both methylene and methylene ether linkages. Some cured melamine-formaldehyde resins are shown by solid-state cross-polarisation magic angle sample spinning (c.p./m.a.s.) ¹³C and ¹⁵N n.m.r. to contain linear and branched methylene and methylene ether linkages but few free methylol groups. The relative proportions of the various linkages in both the oligomers and the cured resins appear to be controlled mainly by the melamine: formaldehyde ratio.     

Aspects of the molecular structure of a bituminous vitrinite. Nuclear magnetic resonance study of the effects of imbibed pyridine

The effects of imbibed pyridine on the molecular structure of a high-volatile bituminous vitrinite have been studied at room temperature by proton nuclear magnetic resonance pulse techniques. Both the free induction decay and nominal solid echo signals, recorded before and after addition of fully-deuterated and non-deuterated pyridine, could be decomposed into two or three components corresponding to protons with different degrees of mobility. The results confirm that pyridine produces substantial mobilization of the bituminous coal structure, thereby indicating the role of polar interactions in determining the molecular conformation of the coal. Analysis of the data indicates that two mobile proton populations can be distinguished in the presence of deuterated pyridine. Evidence is provided for strong coupling between protons and free-radical unpaired electrons in the vitrinite and for a reduction in this interaction due to the mobilizing and swelling effects of imbibed pyridine.     

Studies of the stereospecific polymerization mechanism of propylene by a modified Ziegler-Natta catalyst based on 125 MHz 13C n.m.r. spectra

The mechanism of stereospecific polymerization of propylene (catalysed by a modified Ziegler-Natta system, TiCl₄/MgCl₂/C₆H₅COOC₂H₅/Al(C₂H₅)₃), has been analysed using the values of triad and pentad tacticity determined using 125 MHz ¹³C n.m.r. spectroscopy. The well-known single active-site models, such as the Bernoullian, first- and second-Markovian, and enantiomorphic models, were found to be inadequate to describe the observed tacticity. A two-sites model, in which at one site the stereospecific polymerization proceeds in obedience to the Bernoullian model and at the other proceeds under the control of enantiomorphic-site model, is proposed. It was found that the pentad tacticities of both soluble and insoluble (in boiling heptane) fractions of polypropylene agreed well with the two-sites model.     

Carbonization behaviour of pitch in the presence of inert material

The influence of silica gel (< 45 μm) as an inert additive on the carbonization reactions of A240 pitch was investigated by optical microscopy, measurements of transferable hydrogen, high-temperature e.s.r. and high-temperature ¹H n.m.r. Additions of silica gel have the effect of reducing the size of the optical texture of mesophase which appears in the early stages of carbonization. The higher the concentration of silica gel, the smaller is the amount of transferable hydrogen. The spin concentration of pitch increases with increasing silica gel content. Measured values of $\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, using high-temperature ¹H n.m.r., suggest that the molecular motions in the pitch become restricted on addition of silica gel. The effect of silica gel on the physical properties and chemical reactivity of carbonizing pitch is discussed.     

Investigation of aromatic carbon sites in materials derived from petroleum and coal using 13C n.m.r. methods

Aromatic C and CH carbon sites in a variety of petroleum and coal derived materials have been investigated using a ¹³C n.m.r. technique termed spin echo broad band off-resonance decoupling (SEBBORD). Only resonances due to non-protonated aromatic carbon sites are observed in SEBBORD spectra such that comparison with conventional ¹³C n.m.r. spectra enables differentiation between aromatic C and CH group resonances. Relative abundances of non-protonated aromatic carbon sites calculated from SEBBORD data are in good agreement with values derived from a combination of conventional¹H n.m.r., ¹³C n.m.r. and elemental analysis data. The occurrence of significant proportions of aromatic C intensity to high field of 129–130 ppm and of aromatic CH intensity to low field of 129–130 ppm has been found to be quite common. Consequently attempts to determine aromatic C and CH group abundances by partitioning conventional ¹³C n.m.r. spectra in the vicinity of 129–130 ppm can lead to considerable quantitative errors. SEBBORD provides more detailed information about aromatic carbon sites than can be obtained from conventional ¹³C n.m.r. spectra.     

基于OH-PLIF的狭长受限空间油气爆炸中间基团浓度分布研究

为了精确测量狭长受限空间油气爆炸过程中的关键自由基团,从而实现对其爆炸流场、火焰传播的精确分析,基于先进的平面激光诱导荧光测量技术(PLIF),设计构建了油气爆炸PLIF测量系统,开展了不同工况下狭长受限空间汽油-空气混合气爆炸实验研究,获得了该爆炸中间基团OH基的浓度分布。实验结果表明,1.1%～2.4%(体积分数)油气浓度之间,OH基浓度先增大后减小;随火焰的传播发展,OH基浓度不断变大,表明爆炸不断强化;爆燃不同时期OH基分布情况不同,表明不同爆燃阶段的燃烧反应区域有较大差异;爆燃前期火焰与壁面之间有"隔离带",是由未燃气浓度增大导致火焰传播变慢的结果。主要创新点在于通过设计时序控制子系统,解决了非稳态预混燃烧中自由基分布瞬态测量。     

Study on concentration distribution of radical groups of gasoline-air explosion in long-narrow confined space based on OH-PLIF

To measure the key free radicals of the gasoline-air explosion in long-narrow confined space accurately, which is important to the accurate analysis of the explosion flow field and the flame propagation, an experimental study on the gasoline-air mixture explosion in a long-narrow confined space is designed based on the planar laser induced fluorescence system (PLIF),and the experiments in different conditions of the gasoline-air explosion in long-narrow confined space are carried out. The concentration distributions of the OH radical of those are obtained. The results of experiments show that the concentration of OH radical rises and then descends among the gasoline concentrations of 1.1%—2.4%(volume fraction); the concentration of OH radical rises steadily along with the development of flame propagation, which means the explosion is strengthen; the distributions of the OH radical are different in different explosion stages, which means the combustion reaction area in different explosion stages differs a lot; there is a "isolation belt" between the flame and the wall, which is the result of the slowing of the flame propagation caused by the concentration increase of unburned gasoline. The main innovation is to solve the transient measurement of free radical distribution in unsteady premixed combustion by designing the timing control subsystem.     

Optimum conditions for high resolution C n.m.r. of coal- and oil-derived products

Factors affecting the spin-lattice relaxation times T₁ of ¹³C resonances at 62.9 MHz were investigated for simple mixtures of tetralin, ethylbenzene, pentane and phenol and the prominent resonances of an anthracene oil and a coal-derived hydrogenation oil. Parameters varied were solvent temperature and nature—Cr(acac)₃, Cr(dpm)₃, Cr(hfac)₃, Fe(acac)₃, Fe(dpm)₃—and concentration of a paramagnetic relaxation agent (PARR). Effects of PARRs on relaxation rates are strongly dependent on neighbouring acidic or basic centres, but are much more uniform for Cr(hfac)₃ than for Cr(acac)₃. The presence of basic or acidic compounds does not significantly affect the relaxation of ¹³C of the neutral components. Optimum experimental conditions are characterized by nearly uniform T₁ values of all resonances to be detected. While 2D spectra allow disentanglement of overlapping lines, choosing optimum conditions for the neutral constituents may lead to a loss of signals from the acidic or basic compounds.     

Evaluation of the aromatic structure of coal tar pitch by solid and solution state n.m.r.

Rapid magic angle spinning has been used to obtain sideband-free high field ¹³C n.m.r. spectra of coal tar pitches in the solid state. However, the unfavourable cross-polarization and ¹H relaxation characteristics make it difficult to accurately estimate concentrations of quaternary aromatic carbon using the dipolar dephasing method. The concentrations of bridgehead aromatic carbon in the whole pitch and toluene-insoluble fraction investigated were deduced using a combination of solid and solution state n.m.r. and elemental analyses.