Unsaturated polyesters based on terephthalic acid: 3. Characterization of poly(propylene terephthalate) prepolymer by gel permeation chromatography

Oligomers in prepolymers prepared by the polyesterification of terephthalic acid (T) with excess 1,2-propylene glycol (P) have been separated by gel permeation chromatography (g.p.c.). The assignment of chromatogram peaks to oligomers according to the structure P (TP)_n where n is the number of 1,2-propylene terephthalate repeating units has been confirmed by a g.p.c. examination of bis(2-hyroxypropyl) terephthalate and by a ¹H nuclear magnetic resonance (n.m.r.) spectroscopic study of fractions isolated from a preparative separation. The infrared g.p.c. detector response has been interpreted quantitatively in order to deduce the concentration of each oligomer from the area of its chromatogram peak. Mol fraction distributions as a function of n have been determined for the prepolymer samples. Number average molecular weights have been calculated for the terephthalate-based components of the prepolymer and for all components including excess propylene glycol. These g.p.c. molecular weights are in excellent agreement with values previously reported in a study of prepolymers by ¹H n.m.r. spectroscopy. G.p.c. studies on prepolymers after reactions with a carbodiimide and diazomethane suggest a very minor quantity of carboxyl terminated species in the prepolymer samples.     

Liquefaction reaction of coal: 2. Structural correlation between coal and its liquefaction products

The structural correlation between coal and its liquefaction products has been examined using cross-polarization, magic angle spinning (CP/MAS) ¹³C n.m.r. and field ionization mass spectrometry (f.i.m.s.). The CH₂/aromatic carbon ratios of all solid products (asphaltene, preasphaltene and residue) were close to the corrected +CH₂/aromatic carbon ratio for the coal. This suggests that the ring structure of the structural unit of each solid product is essentially similar to that of the parent coal, except for a difference in the degree of polymerization of the structural units. The CH₂/aromatic carbon ratios of aromatic ring-type oil fractions also correlated with the corrected ratio for the coal, although they were larger. The z series distribution obtained from the f.i.m.s. of oil fractions revealed that coal with a higher CH₂/aromatic carbon ratio produced an oil rich in naphthenic structures.     

Aromatenstrukturtypenanalyse von raffinierten Erdölprodukten durch UV-Spektroskopie

Aromatic Structure Type Analysis of Hydrotreated Petroleum Fractions by U.V.-Spectroscopy 20 K boiling cuts were produced from hydrotreated petroleum products by means of distillation. From such close fractions, defined pure aromatic types can be separated by preparative elution adsorption chromatography (EAC) on dual-packed (Silicagel-Alumina gel) columns. The extinction coefficients of the various separated types are measured at suitable wave lengths and used for calculating the average extinction coefficients of aromatic types for wide boiling fractions. Utilizing these values on quantitative u.v.-analysis of technical hydrotreated products, the results correspond well with those of EAC and ¹H-n.m.r. spectroscopy.     

Combination of 13C- and 1H-n.m.r. spectroscopy for structural analyses of neutral,acidic and basic heteroatom compounds in products from coal hydrogenation

Polar compounds consisting of acidic, basic and neutral nonhydrocarbons were separated from the oil portion derived from coal hydrogenation by means of liquid chromatography. These polar compounds comprised a substantial amount of the oil portion, up to ≈ 60 wt%. Acidic and basic compounds were extracted subsequently by chemical methods, leaving the neutral nonhydrocarbons. The neutral nonhydrocarbons were derived further into eight subfractions, Fr-PP_n-1 to-8, using gel permeation chromatography. The fractions were analysed quantitatively using ¹³C- and ¹H-n.m.r.. Information on the distribution of functional groups containing heteroatoms, especially oxygen, which were present as phenolic, phenylether or heteroaromatic rings, was provided indirectly by ¹³C-n.m.r. spectra, utilizing the chemical shift of the carbon which can be distinguished by an adjacent oxygen. Simultaneous application of ¹³C-n.m.r. with ¹H-n.m.r. reduced considerably the number of assumptions required for estimating the average molecular structure of polar compounds.     

Analysis of upgraded SRC-11 and H-coal liquid products

Upgraded coal-derived liquids obtained from catalytic hydroprocessing of SRC-11 and H-coal syncrudes have been studied by i.r., p.m.r., g.c.-m.s., and silica gel chromatography. With increase in residence time, nitrogen, oxygen and aromatics decrease, while naphthenes increase substantially. All the upgraded liquids show low viscosity at 298 K (1.3–1.4 mN s m^?2), even though saturate and aromatic fractions varied with processing severity. In the aromatic-1 fraction, 1 -ring aromatics increase, and 3-ring aromatics decrease, with increase in severity of hydroprocessing. G.c.-m.s. analyses indicate a marked qualitative similarity for saturate and aromatic fractions irrespective of syncrude source. Only the heavier end of the aromatic-1 fraction is noticeably different. Tentative identifications based on m.s. and g.c. retention times are made for most of the significant components. 600 M Hz p.m.r. spectra of the upgraded SRC-11 and H-coal liquids appear identical, but the n.m.r. difference technique revealed slight differences between the two liquids in concentrations of certain species.     

Study of structural parameters on some petroleum aromatic fractions by 1H n.m.r./i.r. and 13C, 1H n.m.r. spectroscopy

¹H n.m.r. and i.r. spectroscopy were used to derive molecular parameters of petroleum fractions. Relative amounts are estimated of methylene and methyl groups in substituted alkyl side chains bonded to the aromatic ring system. The resolution of equation combinations leads to estimation of $\text{H}{}_{\mathrm{s}}\text{C}{}_{\mathrm{s}}\text{(=x)}$, which is an important parameter for structural analysis. Several petroleum fractions were characterized in terms of hypothetical average molecular structures using ¹H n.m.r./i.r. procedures, ¹³C coupled proton n.m.r. and Brown—Ladner methods. It is proposed that the ¹H n.m.r./i.r. method gives more precise average molecular parameters than the Brown-Ladner method with the most precise analytical procedure, up to date, being ¹³C coupled proton n.m.r. analysis. The Brown-Ladner method is especially suitable for structural analysis of low aromaticity molecular structures with long straight-chain alkyl substituents.     

An h.p.l.e. and m.s. analysis of distillate fractions of neutral oil from hydrogenated Akabira coal to elucidate chemical structures

Akabira coal-derived neutral oil was separated into 25 narrow boiling range fractions covering 183–423 °C, and subsequently separated into compound class fractions : alkanes, monoaromatics, naphthalene-type diaromatics, fluorene-type diaromatics and tri- and/or tetraaromatics, by high performance liquid chromatography (h.p.l.c.). The compound type analyses of the distillate/h.p.l.c. fractions were performed using electron impact mass spectroscopy (e.i.m.s.) or field ionization mass spectroscopy (f.i.m.s.). Aromatic/hydroaromatic compound types and the alkyl side-chain carbon distribution of the distillate/h.p.l.c. fractions were clarified, based on the separation behaviour of h.p.l.c. and the type analyses according to Z value by m.s. By the distillation/h.p.l.c./m.s. method, coal-derived oil was characterized in terms of the distribution of the numbers of aromatic rings, naphthenic rings and carbons of alkyl groups attached to these rings. The variations in chemical structure in a compound class with distillation temperature are discussed in terms of these chemical structural factors.     

Temperature Drop Turbidimetry as a Means for the Rapid Determination of the Polydispersity of Polymers Part III. Polyethylene

The molecular weight averages of narrow and broad distribution polyethylene have been determined by controlled precipitation from a mixed solvent of xylene/n-hexanol in the temperature range 433 to 33K. Estimates of the distribution (D) which compared unfavourably with and considerably under-estimated those determined by gel permeation chromatography (g.p.c.) were obtained by a calibration procedure between the temperature of initial onset of precipitation and the weight average molecular weight which have been used previously _1,2 to characterise turbidimetric curves. However, the calibration curves gave an accurate estimate of the weight average molecular weight. There was also an accurate correlation between the reciprocal of the breadth of the turbidity-temperature curves as measured by 1/T_max (dτ/dT) ^?1 i.e. (S)^?1, and the logarithm of the g.p.c. dispersity which enabled the breadth of distribution to be determined. With these two correlations molecular weight characteristics could be determined rapidly which compared favourably with g.p.c. data. The method has been applied to fractions obtained for 3 methods of fractionating polyethylene in order to compare their relative efficiencies.     

Graft copolymers of lignin with electron poor alkenes

The synthesis of copolymers between lignin and electron poor alkenes is described. Lignin from steam‐exploded pine, from steam‐exploded straw, and organosolv were used as starting materials. Beforehand, lignins were fully characterized by using elemental analysis, ultraviolet spectroscopy, gel permeation chromatography (GPC), Fourier transform infrared (FTIR), and both¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The synthesis of copolymers was performed using a previously described procedure utilizing calcium chloride and hydrogen peroxide as reagents. FTIR of copolymers showed absorptions due to the presence of both lignin and the electron withdrawing group on the alkene. GPC analysis showed the presence of fractions with high molecular weights: the M_z of lignin from pine was 3729 while the copolymer with methyl acrylate showed M_z = 383790. Differential calorimetry showed the presence of glass transitions in the range of ?9 to 4.5°C due to the presence of grafted polyalkene chains. When acrylonitrile was used as starting material DSC analysis of the product showed a glass transition at 119°C, which can be attributed to grafted polyacrylonitrile chain. Lignin from steam explosion could be a good raw material in the preparation of graft copolymers. Furthermore, lignin from pine gave better results than that from straw. Finally, lignin from steam explosion gave better results than organosolv lignin. These results can be explained on the basis of the structural properties of used lignins. Both UV and ¹³C NMR spectra showed that lignin from pine contained a consistent amount of double bonds. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1163–1171, 2003     

Characterization of high-boiling petroleum distillate fractions by proton and 13C nuclear magnetic resonance spectrometry

High-boiling (535–675 °C) distillate fractions of Wilmington (Calif. USA) and Gach Saran (Iran) crude oils were separated into saturate, monoaromatic, diaromatic and polyaromatic-polar fractions by passage through a silica-gel—alumina dual packed chromatography column. These fractions were further separated on the basis of molecular volume by gel-permeation chromatography (g.p.c.). Select g.p.c. fractions were then analyzed by ¹H and ¹³C n.m.r. spectroscopy. The fraction of aromatic carbons (Ar-C) of the total carbon content of a given series of g.p.c. fractions, obtained directly from the ¹³C n.m.r. spectra, showed a significant range of values (e.g. 13.2% to 29.2%) within each series. Furthermore, the values of %Ar-C within a series of g.p.c. fractions showed a maximum in each case. No such maximum was observed in the ¹H n.m.r. spectra for the fraction of aromatic proton (%Ar-H) content compared to the total proton content of any of the g.p.c. fraction series. Signals observed in the ¹³C n.m.r. spectra confirmed the presence of aliphatic chains attached to aromatic structures in the monoaromatic, diaromatic and polyaromatic-polar g.p.c. series of each distillate fraction. Well-defined signals, not attributable to straight-chain aliphatic material, were also observed in the ¹³C n.m.r. spectra. Comparison of the chemical shifts of these ¹³C n.m.r. signals with those spectra of model compounds obtained experimentally, and with appropriate systems in the literature, strongly suggested the presence of saturated terpenoid-like structures as well as the presence of methyl groups in sterically hindered positions on an aromatic ring system. Gated decoupling techniques and the use of a relaxation agent were used to overcome the deleterious effects of slow relaxation times and Nuclear Overhauser Enhancement (NOE) on the analytical quality of the ¹³C n.m.r. spectra.     

Differences in curing behavior of cocured and IPN materials

This study addressed the blending and cocuring of resole and epoxy, using NaOH and 4,4′‐diaminodiphenylmethane as curing agents. IR band shifts regarding the molecular interactions were investigated with FTIR. Exothermic peak shifts during cocuring reactions were studied with dynamic DSC. Viscosity increases were measured with a Brookfield LVT viscometer at 100°C. The dynamic mechanical properties of the cocured samples were investigated using rheometric dynamic spectroscopy (RDS). Experimental results revealed that the molecular interactions between resole and epoxy resulted in good compatibility as shown by the single damping peak in the RDS curve and the single glass transition for each cocured sample. Also apparent were accelerated curing rates, leading to shifts of the exothermic peaks to lower temperature and faster viscosity increases. Nevertheless, enhanced gel fractions and increased glass‐transition temperatures (T_g) of the samples were generally observed for this cocured system. The average molecular weight between crosslinked points calculated for the cocured materials also showed much less than the two components. These curing behaviors were quite different from those of the Interpenetrating Polymer Network (IPN) materials, which usually indicated lowered gel fractions, decreased T_g, and higher average molecular weight between crosslinkings than for components. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 963–969, 2001     

Biochemical activity of centipedegrass against fall armyworm larvae

Centipedegrass,Eremochloa ophiuroides (Munro) Hack, severely inhibits growth of the fall armyworm larva,Spodoptera frugiperda (J.E. Smith). Fresh centipedegrass extracts and extract fractions were deposited on Celufil, incorporated into meridic-based diets and bioassayed against neonate larvae of the fall armyworm in the laboratory. The methanol extract (F₁) caused the greatest reduction in larval weight. When F₁, was partitioned between méthylene chloride and water, the activity was transferred to the water-soluble fraction (F₅), which, when further fractionated using preparative C-18 reverse-phase chromatography, yielded active F₇ and F₈ fractions. Gas chromatograph-mass spectrometry and high-pressure liquid chromatography (HPLC) showed F₇ to be 95% caffeoylquinic acids with chlorogenic acid as the major constituent. HPLC analysis of F₈ revealed maysin [2-O- -L-rhamnosyl-6-C-(6-deoxy-Xylo-hexos-4-ulosyl)luteolin] and other luteolin derivatives. Chlorogenic acid and other caffeoylquinic acids, maysin, and other luteolin derivatives are the major factors responsible for the antibiotic resistance of centipedegrass to larvae of the fall armyworm.     

Chemical structure of heavy oil from coal hydrogenation 1. Hydrogenation with zinc chloride catalyst

Oil product from the hydrogenolysis of a high-volatile bituminous coal was separated by solubility, fractionated by gel permeation chromotography and characterized by structural analysis. The average structural unit in the hexane-soluble, aromatic oil fraction consists of 1–3 aromatic rings with 0.3-0.5 of the ring carbons substituted by alkyl groups and oxygen containing groups. Molecular weights vary from 200 to 500. The larger molecular weight fractions have longer alkyl chains and lower carbon aromaticities. The molecules are mainly of single unit structures. The average structural units in asphaltene fractions contain from 2.5-4 aromatic rings, are of higher carbon aromaticities and contain shorter alkyl groups. The asphaltene molecules consist of two or more structural units, crosslinked together, and have molecular weights of 300–1400. The oxygen content of the fractions decreases with decreasing molecular weight. Increasing the amount of ZnCl₂ catalyst during hydrogenolysis resylts in an increased yield of lower-molecular-weight material, but no change in the structural properties of the product. This is interpreted to mean that ZnCl₂ is active in the scission of covalent bonds between structural units during liquefaction and that the hydrogenolysis reaction is mostly cleavage of crosslinks between structural units with minimal reaction of the units themselves.     

Structural characterization of coal-hydrogenation products by proton and carbon-13 nuclear magnetic resonance

Heavy oil derived from coal hydrogenation was separated into saturated fractions, neutral aromatic oil, and asphaltene, and these materials were subsequently fractionated according to the magnitude of their respective molecular sizes by gel-permeation chromatography. These GPC subfractions were analysed by proton and carbon-13 n.m.r. spectroscopy and by an additional procedure using gas chromatography for the paraffinic GPC subfractions. ¹³C-n.m.r. spectra for the GPC subfraction of saturated material showed typical long straight-chain paraffin spectral patterns accompanied by iso-and cycloparaffinic carbon signals. The results from gas-chromatographic measurement for the paraffinic GPC subfractions agree fairly well with the trends of average carbon numbers and contents of straight-chain paraffins obtained by varying the fraction numbers, estimated from ¹³C-n.m.r. analyses. The ratios of aromatic carbon to total carbon (f_a) for aromatic oil and asphaltene GPC subfractions obtained directly from ¹³C-n.m.r. spectra are slightly lower than the results from the ¹H-n.m.r. method assuming x = y = 2 in the Brown—Ladner equation. Peak intensities of the respective carbon species in ¹³C-n.m.r. spectra were compared with the peak intensities of correspondingly bonded species obtained from ¹H-n.m.r. measurement. Some inadequacy was recognized in both measurements. It is assumed that there are two reasons for the discrepancy, one of which is the inaccuracy of ¹³C-n.m.r. results owing to the long relaxation times and the effect of Nuclear Overhauser Enhancement, and another is the application of unsuitable values of x and y for calculations from the Brown—Ladner equation. New analytical treatments for ¹³C-n.m.r. results in combination with ¹H-n.m.r. analyses are suggested in this study to avoid these uncertainties in structural analyses. From this procedure, it is believed that the actual contents of aromatic and aliphatic carbon and appropriate values of x and y can be derived.     

The Chemical and Physical Structure of Peat Bitumens

Peat bitumen obtained by solvent extraction of Irish high moor peat was subjected to chemical, structural and rheological characterisation. The bitumen was fractionated on the basis of solubility in n-heptane, toluene and ethyl acetate into wax, resin and asphaltene; each of these major constituent groups was further separated into sub-fractions by column chromatography using solvents of increasing polarity. All materials were chemically characterised by C, H, N and O content and infra-red spectroscopy. Molecular size distribution of the materials was determined by gel permeation chromatography and vapour pressure osmometry. Heats of fusion, measured using the differential scanning calorimeter, indicated that crystalline species were concentrated in the wax fraction. The rheological properties of the bitumen were investigated between 10 and 50°C, and the fractions were examined at 20°C. Following analysis as yield pseudoplastic fluids, flow behaviour was described in terms of yield stress, flow and consistency indices. The measured flow parameters were examined in the light of the structural implications of the calorimetry and the results of the chemical analysis. Carboxylic acids and esters which are found principally in the wax fraction are considered to be the dominating rheological influence in the bitumen, affecting physical behaviour through their ability to crystallise at low temperature and thus mechanically hinder flow, and through secondary bonding increasing viscosity in the liquid phase.     

Aromatic products of 340 °C supercritical-toluene extraction of two Turkish lignites: an n.m.r. study

Fractions of Elbistan and Seyitomer (Turkish) lignites, extracted with supercritical toluene at 340 °C and 8 MPa, have been separated by solvent extraction and silica-gel chromatography. Analyses by n.m.r. and i.r. spectroscopies and other methods have been combined in structural-analysis schemes to yield information about the average molecule in aromatic extracts. Carbon aromaticities, f_a, derived from 22.63 MHz ¹H-decoupled pulse Fourier-transform (PFT) ¹³C-n.m.r. are more widely spread for Elbistan (0.34–0.56) than for Seyitomer (0.40–0.43), and are lower than for supercritical-gas (SCG) products from bituminous coals. ¹³C-n.m.r. also reveals the presence of aromatic ether-O in polar fractions. Narrow aromatic signals in 100 MHz ¹H-n.m.r. spectra suggest the presence of single-aromatic-ring average structures. In the hexane-soluble aromatics, 27% (Elbistan) and 29% (Seyitomer) of the available sites are substituted by alkyI groups, some of which are at least eight carbon atoms long; the hexane-soluble polar and asphaltene/asphaltol fractions contain fewer such groups.     

Conversion of solvent-refined coal to liquid products in the presence of Lewis acids

The formation of liquid products from a solvent-refined coal (SRC) was studied using Lewis acid catalysts in the presence of either benzene or cyclohexane as an extracting solvent. The soluble products were characterized by elemental analysis, ¹H-n.m.r., and, in some experiments, by gel permeation chromatography. Only ZnCl₂ and SnCl₂, the weakest Lewis acids examined, enhanced the dissolution of SRC over that observed in the absence of a catalyst. Increases in solubility were accompanied by increases in $\text{H}\text{C}$ and aliphatic character and by decreases in average molecular weight. These changes are ascribed to the ability of ZnCl₂ and SnCl₂ to promote depolymerization and hydrogenation of the SRC. Alkylation with isopropanol was also found to enhance the solubility of SRC in benzene and cyclohexane.     

Compatibility and properties of alternating ethylene-tetrafluoroethylene copolymer and poly(methyl methacrylate) blends

Blends of an alternating ethylene-tetrafluorethylene copolymer (ETFE) and poly(methyl methacrylate) (PMMA) were prepared by melt mixing in a mixer. Compatibility, thermal behaviour and morphology of the blends of various compositions were investigated by using dynamic mechanical analysis (d.m.a.), Fourier transform infra-red spectroscopy (FTi.r.), solid-state nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.) and wide-angle X-ray diffraction. D.m.a. and d.s.c. results show that the glass transition temperature (T_g) of the ETFE in the blends increases as the PMMA content increases and the T_g of the PMMA moves to low temperatures when the ETFE content increases. In addition, d.s.c. results indicate an additional T_g, which is located between the T_g of PMMA and that of ETFE. The presence of this additional T_g suggests the existence of one semicrystalline phase and two amorphous phases—an ETFE/PMMA phase and a PMMA-rich phase. D.s.c. results also indicate that the melting temperature of ETFE decreases while the crystallinity of ETFE increases slightly as the PMMA content increases. FTi.r. results show that the absorption peak of the carbonyl group of the PMMA in the blends stays almost at the same position as in the pure component. Solid-state n.m.r. results reveal that the changes in chemical shift of the carbonyl group of PMMA in the blends are less than 0.5 ppm. These results confirm that only weak interactions exist between ETFE and PMMA. X-ray diffraction results reveal that no new crystal forms appear in the blends. © 1997 Elsevier Science Ltd.     

Equilibrium,kinetics, and thermodynamics of Pd(II) adsorption onto poly(m‐aminobenzoic acid) chelating polymer

This study describes the equilibrium, kinetics, and thermodynamics of the palladium(II) (Pd(II)) adsorption onto poly(m‐aminobenzoic acid) (p‐mABA) chelating polymer. The p‐mABA was synthesized by the oxidation reaction of m‐aminobenzoic acid monomer with ammonium peroxydisulfate (APS). The synthesized p‐mABA chelating polymer was characterized by FTIR spectroscopy, gel permeation chromatography (GPC), thermal analysis, potentiometric titration, and scanning electron microscopy (SEM) analysis methods. The effects of the acidity, temperature, and initial Pd(II) concentration on the adsorption were examined by using batch adsorption technique. The optimum acidity for the Pd(II) adsorption was determined as pH 2. In the equilibrium studies, it was found that the Pd(II) adsorption capacity of the polymer was to be 24.21 mg/g and the adsorption data fitted better to the Langmuir isotherm than the Freundlich isotherm. The kinetics of the adsorption fitted to pseudo‐second‐order kinetic model. In the thermodynamic evaluation of the adsorption, the ΔG° values were calculated as ?16.98 and ?22.26 kJ/mol at 25–55°C temperatures. The enthalpy (ΔH°), entropy (ΔS°), and the activation energy (E_a) were found as 35.40 kJ/mol, 176.05 J/mol K, and 61.71 kJ/mol, respectively. The adsorption of Pd(II) ions onto p‐mABA was a spontaneous, endothermic, and chemical adsorption process which is governed by both ionic interaction and chelating mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42533.     

In vitro and in vivo evaluation of poly(2-methoxyethyl methacrylate-co-acrylic acid)-based microhydrogels for pH-responsive targeted delivery of model drug

ABSTRACT

The study aimed to develop chemically crosslinked poly(2-methoxyethyl methacrylate-co-acrylic acid) (p(MEMA-co-AA)) microhydrogels as carriers for pH-responsive oral targeted delivery of therapeutics. p(MEMA-co-AA) microgels were successfully synthesized by simple free radical suspension polymerization technique confirmed through Fourier transform infrared spectroscopy, thermogravimetic analysis, powdered x-ray diffractrometry, and scanning electron microscopy. Chemically crosslinked spherical microhydrogels with an average size in the range of 4.1 µm ± 2.21 to 9.7 µm ± 3.21 exhibited pH-dependent controlled release of the model drug. Maximum swelling, drug loading, and release were observed at pH 7.4. The optimal formulation achieved good delayed and sustained release features with decreased C_max, prolonged T_max, and mean residence time in comparison to oral drug solution.