Curing of poly(furfuryl alcohol) resin catalyzed by a homologous series of dicarboxylic acid catalysts: Kinetics and pot life

Curing kinetics and pot life are two vital characteristics for the application of poly(furfuryl alcohol) (PFA) resin because of the complexities both in the resin composition and curing mechanisms involved. However, few reports have provided a complete picture of PFA curing behavior. In this research, the effect of the addition of catalysts on the pot life and curing behavior of a PFA resin were evaluated. A homologous series of dicarboxylic acids [i.e., oxalic acid (OX), succinic acid (SU), and adipic acid (SA)] were used as the catalysts. Rheometric and nonisothermal differential scanning calorimetry (DSC) measurements and headspace gas chromatography/mass spectrometry analysis were carried out at 0, 6, and 24 h after the addition of the catalyst. The relaxation exponent (n), gel stiffness (S), and gel strength (A_F) of the prepared compositions were calculated with the Winter and Chambon and Gabriele rheological models. Furthermore, the curing kinetics were evaluated by the fitting of nonisothermal, multiple‐heating‐rate models. The DSC measurements showed a higher curing degree for samples containing OX catalyst compared to their counterparts containing either SU or AD. The rheometric findings supported an increased stiffness, gel strength, and curing development of the resin in the presence of OX compared to samples containing SU or AD. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44009.     

The effect of acid content on the poly(furfuryl) alcohol/cellulose composites

Cellulose/poly(furfuryl alcohol) (PFA) composites were prepared via in situ polymerization process using p‐toulene sulfonic acid as a catalyst. Cellulose was extracted from cotton fibers using chemical treatments with basic media of NaOH, NaClO₂ and KOH. Acid hydrolysis at different concentrations (30, 40 and 50%) of sulphuric acid was used and the final suspended cellulose was incorporated in PFA. The treatments of the cotton fibers ensued to higher crystalline cellulose which was proportional to sulphuric acid contents. Scanning electron microscopy studies (SEM) results showed a poor interfacial interaction when 50% acid content was used for hydrolyses. The effect of fiber reinforcement on thermal and dynamic mechanical properties of the composites was investigated using thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMTA). The TGA results showed higher thermal stability of cellulose/PFA composites as compared to the neat PFA. The DMA results showed that the incorporation of the cellulose fibers imparts significant enhancement in the storage modulus of the PFA matrix. There was also the clear decrease in intensity of the tan peak of the composites compared to the neat PFA. POLYM. COMPOS., 37:2434–2441, 2016. © 2015 Society of Plastics Engineers     

Rheokinetics in curing process of polyfurfuryl alcohol: effect of homologous acid catalysts

Curing reaction of polyfurfuryl alcohol (PFA) resin was investigated using rheological measurements in the presence of different acid catalysts. A homologous series of dicarboxylic acid catalysts with even number of carbons of 2, 4 and 6 were chosen, i.e., oxalic acid (OX, 2 carbon), succinic acid (SU, 4 carbon) and adipic acid (AD, 6 carbon). Acidity of these catalysts in terms of pK _a was in the range of 1.25–4.43. Firstly, non-isothermal curing kinetics were investigated, and then, isothermal studies were performed at three different temperatures using 3 and 5 wt% of each acid catalyst. Isothermal cure behavior was best described by an empirical Arrhenius model of viscosity. An isoconversional method was applied to compute the changes in the effective activation energy as a function of degree of conversion. The change in activation energy at 50–10 kJ mol^?1 was observed for PFA/3 wt% OX system due to the vitrification and diffusion-controlled processes. Gel time, t _gel, was determined as a function of curing temperature, acid catalyst type and its concentration. The gelation time was consistent for all the formulations with an extent of conversion of about 0.7. Significant differences were observed in the curing behavior of resins in the presence of different acid catalysts. Increasing of the curing temperature significantly accelerated the curing process and increased curing rate constant of the PFA resin.     

Selectivity and kinetics of epoxy resin–bisphenol a reaction catalyzed by certain guanidine derivatives

The reaction of bisphenol A with a diglycidyl ether of bisphenol A may lead to linear polymers if a selective catalyst is used. Selective catalysts promote linear polymer formation while nonselective catalysts increase the rate of crosslinking. Selectivity in epoxy resin–bisphenol A reactions depends upon the nature of the catalyst used. In order to understand these catalyst–structure relationships better, we measured the effects of catalysts on the rate of polymerization (k₁) and the rate of crosslinking (k₂) during epoxy resin cures. The knowledge of the ratio k₁/k₂ aids in the selection of catalysts specific for the linear polymerization of epoxy resins. We related this specificity to catalysts basicity. We found that less basic catalysts tend to give large k₁/k₂ values, indicating that little crosslinking occurs with these highly selective catalysts. We demonstrated that the linear polymer obtained from epoxy resin polymerized by triethanolamine, a very selective catalyst, and the linear polymer prepared using 3-p-chlorophenyl-1,1-dimethylurea, a catalyst with low selectivity, are essentially the same. Finally, we caution that quantitative comparisons of selectivity should be restricted to those reactions whose kinetic reaction orders are the same.     

The effects of MCM-41’s calcination temperature on the structure and hydrodenitrogenation over NiW catalysts

MCM-41 was calcined at 500, 560, 600 or 650 °C. It was used as support for NiW catalysts of hydrodenitrogenation (HDN) for quinoline in order to investigate the influences of the MCM-41’s calcination temperature on the structure and the HDN performance of NiW catalysts. The NiW catalysts were characterized by XRD, N₂ adsorptiondesorption, XPS, Raman, HRTEM and Py-IR techniques. The results showed that the surface area (S _BET ), the average pore diameter (Dp) and the pore volume (Vp) of the MCM-41 increased with increase of the MCM-41’s calcination temperature. The high S _BET , Dp and Vp were beneficial for the high dispersion of W species, the formation of appropriate nature of W species and acid sites on the catalysts. The HDN activity followed the order of NiW-650≈NiW-600>NiW-560>NiW-500, while the relative selectivity of HDN pathways was similar for all the catalysts.     

Production of conjugated linoleic acid isomers by dehydration and isomerization of castor bean oil

The possibility of combining dehydration and isomerization of castor bean oil as a means to obtain CLA as TAG forms was studied. First, dehydration was carried out using various catalysts and reaction parameters. Best results were obtained using phosphoric acid (0.1% w/w) at 280°C for 5 h. Under such conditions, satisfactory proportions of CLA were obtained (54% of total FA) with a majority of 9-cis, 11-trans isomer (61% of total CLA). Other catalysts such as bisulfate-bisulfite, sulfuric acid, tungstic and phosphotungstic acids, or resins and zeolites were also tested. With the exception of resins and zeolites, these catalysts also led to CLA production but in limited amounts in comparison with phosphoric acid. In a second step, an isomerization reaction was carried out to transform the residual nonconjugated linoleic acid also produced during dehydration into CLA. Using Wilkinson catalyst [RhCl(PPh₃)₃] in ethanol solvent, dehydrated castor bean oil was isomerized in high yields (>98%), allowing a complete disappearance of nonconjugated linoleic acids. The resulting dehydrated/isomerized oil contained more than 87% CLA with the 9-cis, 11-trans isomer being predominant (40% of CLA fraction). Finally, urea fractionation was also applied on dehydrated/isomerized castor bean oil FA to obtain FFA products containing about 93% CLA.     

Effects of polymerization conditions on the properties of poly(furfuryl alcohol) composite membranes

Poly(furfuryl alcohol) (PFA) composite membranes were prepared by polymerization of furfuryl alcohol (FA) using sulfuric acid (H₂SO₄) as the catalyst and polysulfone ultrafiltration membrane as the substrate. The membrane samples were characterized by ATR‐IR, TGA, SEM, and gas permeation technique. The effects of synthesis conditions including the FA/H₂SO₄ molar ratio, polymerization temperature, and the type of solvent on the chemical structure, surface morphology, and gas permeation properties of PFA composite membranes were studied. Our results showed that the suitable synthesis conditions for the preparation of PFA composite membranes with smooth surfaces and uniform structure include (1) FA/H₂SO₄ molar ratios: 74‐300, (2) polymerization temperatures: 80–100°C, and (3) solvents: ethanol and acetone. The PFA composite membrane prepared with a FA/H₂SO₄ molar ratio of 250, a polymerization temperature of 80°C and ethanol as the solvent exhibited the highest H₂/N₂ ideal selectivity ( $ {\rm{\alpha }}_{{\rm{H}}_{\rm{2}} {\rm{/N}}_{\rm{2}} } = 24.9 $ ), and a H₂ permeability of 206 Barrers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the surface area of cobaltic oxide on carbon monoxide oxidation

Various surface area (S_BET) of cobaltic oxide (Co₃O₄) are prepared by different methods, i.e., precipitation–oxidation, impregnation and hydrothermal. The effect of S_BET of Co₃O₄ on the catalytic property toward CO oxidation is investigated. The results indicate that the optimum S_BET of Co₃O₄ could increase the catalytic activity. Characterization of the cobaltic oxide using X-ray diffraction (XRD), N₂-adsorption at –196 °C, infrared (IR) and temperature-programmed reduction (TPR) reveals that the increase of S_BET on Co₃O₄ can weaken the bond strength of Co–O and promote more lattice oxygen desorption from Co₃O₄ to cause the reduction become easy. We conclude that the S_BET effect, caused by various prepared methods and refined conditions, are responsible for the activity enhancement of Co₃O₄. The T₅₀ (the conversion of CO reached 50%) is decreased significantly when the S_BET is increased, i.e., PO-R230 > PO-C400 > I-C550 > H-150 ~D-Strem.     

Optimization of Epoxidized Methyl Acetoricinoleate Synthesis by Response Surface Methodology

Epoxidized methyl acetoricinoleate (EMAR) was generated by epoxidation of methyl acetoricinoleate (MAR) in the presence of formic acid and hydrogen peroxide by using ionic liquids as catalysts, and the product was characterized by means of infrared spectroscopy and mass spectrometry. The efficiencies of four different catalysts, 1‐methylimidazole hydrogen sulfate salt ([Hmim]HSO₄), 1‐methylpyrrolidone hydrogen sulfate salt ([Hnmp]HSO₄), phosphoric acid, and sulfuric acid, were compared. The effects of the formic acid/MAR molar ratio, hydrogen peroxide/MAR molar ratio, reaction temperature, reaction time, and catalyst dosage on the epoxy value of EMAR were investigated by single‐factor experiments.     

生物质甘油制备环氧氯丙烷的研究

研究了以生物质甘油为原料通过氯代与环化2步制备环氧氯丙烷。考察了磺酸树脂、硫酸、磷酸、乙酸和己二酸等为催化剂时,时间、温度和催化剂用量对中间产物二氯丙醇的收率以及反应速率的影响,并对其催化机理进行了探讨。结果表明：以己二酸和乙腈组合为催化剂的催化效果最好。在环化反应生成环氧氯丙烷中,考察了水、甲苯、正丁醚、正辛醇和二氯...     

Kinetic study of hydrogen peroxide decomposition at high temperatures and concentrations in two capillary microreactors

On the background of the direct adipic acid synthesis from cyclohexene and H₂O₂, a kinetic model was derived for the H₂O₂ decomposition catalyzed by sodium tungstate at high H₂O₂ concentrations and high temperatures. A perfluoroalkoxy (PFA) and a stainless steel micro‐flow capillary match commonly used microreactor materials. In the PFA capillary, the decomposition of hydrogen peroxide increased with residence time, reaction temperature and catalyst loading. The reaction order with respect to hydrogen peroxide and sodium tungstate was zero and one, respectively. Simulated data fit well with experimental data in the PFA capillary. While showing a similar trend as that in the PFA capillary, the stainless steel capillary exhibited much higher reaction rates. The steel surface participated in the decomposition process as a heterogeneous catalyst. Key influencing factors of the H₂O₂ decomposition provided some clues on the reaction mechanism of the adipic acid synthesis and its process optimization. © 2016 American Institute of Chemical Engineers AIChE J, 63: 689–697, 2017     

Combustion products from polydiallylamine

Crosslinked polydiallylamine (Sirorez Au¹) was prepared by the redox-initiated (K₂S₂O₈/TiCl₃) polymerization of freshly distilled diallylamine [containing 2% 1,6-bis(N,N-diallylamino)hexane] as a 30% solution in 80% phosphoric acid at 0°C. The resulting crosslinked resin is thoroughly washed with water and then sodium hydroxide solution (10%) before a final distilled water washing and air drying. Polydiallylamine resin containing ? 50% by weight gold was prepared by soaking the above resin in a three fold molar excess of gold cyanide solution (2 g/L at pH 8.5) overnight and then filtering the resin, washing with distilled water, and air drying. The samples were dried for 24 h over P₂O₅ before combustion.     

Effect of alkaline earth promoters (MgO,CaO, and BaO) on the activity and coke formation of Ni catalysts supported on nanocrystalline Al2O3 in dry reforming of methane

Ni/Al₂O₃ promoted catalysts with alkaline earth metal oxides (MgO, CaO, and BaO) were prepared and employed in dry reforming of methane (DRM). The catalysts were prepared by impregnation method and characterized by XRD, BET, TPR, TPO, and SEM techniques. The obtained results showed that the addition of MgO, CaO, and BaO as promoter decreased the surface area of catalysts (S_BET). The catalysis results exhibited that adding alkaline earth promoters (MgO, CaO, and BaO) enhanced the catalytic activity and the highest activity was observed for the MgO promoted catalyst. TPR analysis showed that addition of MgO increased the reducibility of nickel catalyst and decreased the reduction temperature of NiO species. The TPO analysis revealed that addition of promoters decreased the amount of deposited coke; and among the studied promoters, MgO has the most promotional effect for suppressing the carbon formation. SEM analysis confirmed the formation of whisker type carbon over the spent catalysts.     

Solution polymerizations of epoxytetrahydrophthalic anhydride and its utilization in various epoxy systems

Solution polymerization of epoxytetrahydrophthalic anhydride (ETHPA) has been thoroughly studied by using numerous solvents and catalysts. Products have been obtained in high yields, particularly when triethanolamine was the catalyst. This suggests that this catalyst should be considered for further applications utilizing ETHPA. However, the solution polymerization method cannot be used alone to define the effects of various catalysts on standard nonsolvated resin systems, because polymerization is greatly affected not only by the addition of solvent but also by the type of solvent. In addition, the action of the catalyst seems to depend greatly upon what solvent is employed. The reason for this dependence has not been established. The effects of the addition and reaction of ETHPA with commercial epoxy resin formulations have been investigated by means of heat distortion tests and differential thermal analyses. In most cases, although a moderate improvement was found in the thermal properties of the resins, occasional excellent results were obtained. A 10°C. increase in HDT is observed with a 2 wt.-% addition of ETHPA for bisphenol A epoxy resin–bicyclic anhydride mixture. The degree of elevation of T_g and HDT with the addition of ETHPA obviously depends not only on the composition of the resin system but also on its cure temperature. A good correlation occurs between heat-distortion temperatures and glass transition temperatures. Some few anomalous data, however, are found which point to the fact that further investigation is required before HDT and T_g can be interchanged without prior evidence of a definite relationship.     

MoO3—Fe2O3 catalysts: Characterization and activity for isopropyl alcohol decomposition

The vapour-phase dehydration and dehydrogenation of isopropyl alcohol (IPA) have been carried out over pure MoO₃ and Fe₂O₃, produced by calcination of ammonium heptamolybdate and of iron (III) nitrate respectively, as well as MoO₃ mixed with 0·5 and 50 mol% Fe₂O₃, prepared from the same materials. All catalysts were calcined in air, in the temperature range 200–600°C for 5 h, and were characterized by thermal analysis (TG, DTA), XRD, IR and S_BET. Surface areas decreased with increasing calcination temperature, and the catalytic activity of the pure oxides MoO₃ and Fe₂O₃, as well as of MoO₃–0.5 mol % Fe₂O₃, increased with their S_BET. The activity of MoO₃–50 mol % Fe₂O₃, which was independent of its S_BET, could be attributed to the increased intensity of terminal Mo—O bonds as shown by IR spectra. The activation energies for the decomposition of IPA over catalysts calcined at 250 and 500°C are tabulated.     

Selectivity and competitive mechanism of cation exchange resin for Fe,Mg, and Al ions in phosphoric acid

The presence of iron, magnesium, and aluminum elements as the primary impurities in wet-process phosphoric acid (WPA) adversely affects the industrial phosphoric acid and subsequent phosphorus chemical products. This study aims to investigate the selectivity and competition mechanism of Sinco-430 cation exchange resin for Fe, Mg, and Al ions in phosphoric acid solution. By studying the effects of different process conditions on the removal efficiency, the suitable conditions for the static removal of metal ions from Fe-Mg, Al-Mg, and Fe-Al binary systems were determined: solid–liquid mass ratio (S/L) of 0.3, phosphoric acid concentration of 27.61 wt.%, system temperature of 50°C, and rotational speeds of 200, 400, and 200 rpm, respectively. By calculating the selectivity coefficients of the resin for metal ions under different experimental conditions and mutual replacement experiments, the semi-empirical formulas for the selectivity coefficients were derived and order of selectivity was determined as follows: Mg²⁺ > Fe²⁺ > Al³⁺. Visual MINTEQ 3.1 software and density functional theory (DFT) calculations demonstrated that at low pH, the main forms of Fe, Mg, and Al present in phosphoric acid were FeH₂PO₄⁺, Mg²⁺, and AlH₂PO₄²⁺, respectively. This finding explained the differences in selectivity of the resin for Fe, Mg, and Al. The dynamic removal of metal ions from phosphoric acid was investigated. The order of metal ion selectivity of the resin by the dynamic method is the same as that of the static method, and the dynamic exchange behaviour was most consistent with the Yan model.     

Porous versus novel compact Ziegler–Natta catalyst particles and their fragmentation during the early stages of bulk propylene polymerization

The effect of the porosity of Ziegler–Natta catalyst particles on early fragmentation, nascent polymer morphology, and activity were studied. The bulk polymerization of propylene was carried out with three different heterogeneous Ziegler–Natta catalysts under industrial conditions at low temperatures, that is, with a novel self‐supported catalyst (A), a SiO₂‐supported catalyst (B), and a MgCl₂‐supported catalyst (C), with triethyl aluminum as a cocatalyst and dicyclopentyl dimethoxy silane as an external donor. The compact catalyst A exhibited no measurable porosity and a very low surface area (<5 m²/g) by Brunauer–Emmet–Teller analysis, whereas catalysts B and C showed surface areas of 63 and 250 m²/g, respectively. The surface and cross‐sectional morphologies of the resulting polymer particles at different stages of particle growth were analyzed by scanning electron microscopy and transmission electron microscopy. The compact catalyst A showed homogeneous and instantaneous fragmentation already in the very early stages of polymerization, which is typically observed for porous MgCl₂‐supported Ziegler–Natta catalysts. Moreover, the compact catalyst particles gave rise to almost perfectly spherical polymer particles with a smooth surface. In contrast, the silica‐supported catalyst B gave rise to particles having a cauliflower morphology, and the second reference catalyst C produced fairly spherical polymer particles with a rough surface. All of the three catalysts exhibited similar activities of 450 g of polypropylene/g of catalyst after 30 min of polymerization, and most interestingly, the comparative kinetic data presented indicated that the reaction rates were not influenced by the porosity of the catalyst. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Optimization of mesoporous alumina sol-gel synthesis by Taguchi and response surface methodology

Taguchi method (TM) and response surface methodology (RSM) have been employed to optimize three parameters, including the amounts of P123, the amounts of nitric acid and calcination temperature, in order to define an optimal setting for sol-gel synthesis of high surface area mesoporous alumina powder (MA). Herein, the comparison of the both statistical approaches has been examined and discussed considering the nitrogen adsorption as the response variable because this important character for mesoporous materials is exceedingly sensitive to the synthesis parameters. The BET surface area (S_BET) and pore volume of MA under Taguchi optimal condition were 323.5 m² g⁻¹ and 0.551 cm³ g⁻¹, respectively, by conducting confirmation test. Furthermore, the confirmation test showed high S_BET of MA (363.4 m² g⁻¹), which was in a good agreement with calculated S_BET result (431.25 m² g⁻¹) by a quadratic model under RSM optimal condition. Moreover, 3D response surface plots and 2D contour plots of desirability have been discussed to visualize the influence of input factors on response variable. It is also concluded that RSM shows more appropriate (12.33% higher S_BET than TM) and efficient optimal condition with determining a quadratic function as the relationship between S_BET and synthesis parameters.     

Influence of epichlorohydrin content on structure and properties of high‐ortho phenolic epoxy fibers

The high‐ortho phenolic epoxy fibers (HPEFs) were prepared by the crosslinking of heat‐meltable spun filaments derived from melt‐spinning of the novolac epoxy resins copolymerized among phenol, formaldehyde, and epichlorohydrin (ECH) in the presence of zinc acetate and sulfuric acid catalyst, and cured in a combined solution of formaldehyde and hydrochloric acid. The resulting fibers were heat‐treated in N₂ at elevated temperature. Infrared (IR) spectrometer, thermogravimetric analysis (TGA), scanning electron microscope (SEM), and electrical tensile strength apparatus were employed to characterize the change of functional groups, thermal performance, microstructure of fibers, and mechanical properties. The results show that the addition of ECH in the precursor resin can increase the content of long alkyl ether linkage, and gain the peak of thermal stability and mechanical strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43375.     

In situ preparation of N,N-dimethyl-n-butylamine for 2,6-dimethylphenol polymerization

2,6-Dimethylphenol (2,6-DMP) polymerization with a catalytic complex of Cu₂O/HBr/N,N'-di-tert-butylethylene diamine (DBEDA)/N,N-dimethyl-n-butylamine (DMBA)/dibutylamine (DBA) was studied, in which DMBA was prepared in situ from the methylation of n-butylamine over four different solid acid catalysts (two different γ-alumina, one silica-alumina, and one zeolite). The effectiveness of the unpurified methylation product solutions for promoting the 2,6-DMP polymerization was strongly dependent on the type of solid acid catalysts used. The performance of the best one (untreated product solution from the methylation reactor with Condea γ-alumina catalyst) was very similiar to that of the reagent grade DMBA. Infrared spectrum studies showed that DMBA acted as the external base for the 2,6-DMP polymerization catalyst system to neutralize the excess hydrobromic acid and to increase the polymerization rate. © 1995 John Wiley & Sons, Inc.