Polyesterification Process Research Articles

Synthesis of Alkyd Resin Through Alcoholysis – Polyesterification Process from Used Cooking Oil Pretreatment Using Alkaline Activated Natural Bayah Zeolite

Waste cooking oil can be treated by an adsorption process using Bayah natural zeolite as raw material for alkyd resin synthesis. This study aimed to determine the optimum conditions for the equivalent ratio of OH:COOH and the temperature of the alkyd resin synthesis. The research was carried out by preparing used cooking oil and Bayah natural zeolite (BNZ), adsorption process, and alkyd resin synthesis through the alcoholysis-polyesterification process. The optimum addition of Bayah natural zeolite-activated NaOH 0.75 N in pretreatment waste cooking oil is 30% weight in terms of color, density, viscosity, and functional group characteristics of the resulting alkyd resin. The characteristics of the alkyd resin product at optimum conditions obtained light brown color with an OH: COOH equivalent ratio of 1.4, and the alcoholysis and esterification temperature at 190 oC with a density value is 1.112 g/cm3, FFA value is 0.1528%, viscosity value is 4808 cP. The ester functional group at wavelengths 1267 cm-1 and 1722 cm-1, the 1H NMR spectrum of the ester group at the peak of 3.5 ppm, and a functional group of 7.6 ppm.

A synergetic SnSb-amorphous carbon composites prepared from polyesterification process as an ultrastable potassium-ion battery anode

Combining the stability of amorphous carbon with the high-capacity contribution of metal alloys need explicit structural engineering design so that the beneficial contribution of each constituent material can lead to the desired synergistic electrochemical performance. Here, we report the synthesis of ultrafine SnSb embedded in meso/microporous amorphous carbon (SnSb@MAC) through a polyesterification strategy. As the anode of potassium ion batteries (PIBs), SnSb@MAC composite exhibits better electrochemical performance relative to that of SnSb nanocrystals (SnSb NCs) and MAC. In particular, the composite has an excellent cycle life, with a reversible capacity of ~200 mA h g−1 after 5000 cycles, being the longest life reported for the SnSb-C composites. The K+-transport mechanism of the composite is experimentally verified through in-situ X-ray diffraction, ex-situ TEM and selected area electron diffraction (SAED) and demonstrate the high synergy between SnSb and MAC resulted in the satisfactory storage performance. Finally, the full cell constructed by coupling the SnSb@MAC anode with an organic cathode (perylene-3,4,9,10-tetracarboxylic dianhydride, PTCDA) exhibits a maximum energy density of 228.9 W h kg−1 and a maximum power output of 6150 W kg−1 as well as 177 mA h g−1 along with a current density of 400 mA g−1 after 400 cycles.

Synthesis and characterization of neem (Azadirachta indica) seed oil-based alkyd resins for efficient anticorrosive coating application

Neem (Azadirachta indica) is a fast-growing and evergreen tree with various medicinal values. During a severe drought, it sheds off its leaves and also produces fruits. The available literature revealed that the seeds from neem fruits contained oil varying in the range of 25–45% oil load. Neem oil was extracted from the dried neem seeds by the soxhlet extraction method using petroleum ether as an efficient solvent. Neem seed oil-based alkyd resins were synthesized by the alcoholysis–polyesterification process. The progress of the reaction was examined by determining the acid value at various time intervals. Further characterization of the oil and resins for the determination of molecular weight, structure, fatty acid composition, surface morphology and thermal stability was carried out by gel permeation chromatography, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gas chromatography–mass spectrometry, scanning electron microscopy, thermogravimetry and differential scanning calorimetry, respectively. Attempts were made to study the effect of maleic anhydride content in the resins that changed the curing, anticorrosion, wettability and thermal properties of the resins and cured films. The curing of the alkyd resins was done by blending it with epoxy resin by gradually increasing the temperature from 60 to 210 °C. The coating of the alkyd resins over mild steel plates showed superior corrosion protection for several days. The wettability of the cured films was evaluated by measuring the water contact angle (WCA). The resin with the higher percentage of maleic anhydride showed better performance in different paints and surface coating applications. The synthesized alkyd resins from the neem seed oil possessed great application potential in beneath water marine vessel finish that opposed salt corrosion.

Modeling of reactive batch distillation processes for control

Reactive batch distillation (RBD) is a preferred process intensification technology to carry out equilibrium-limited reactions. It is a multicomponent, multiphase system. Appropriate process description requires dynamic modeling of coupled thermodynamics and transport phenomena including the chemical reactions. Such models are barely applicable to online model based operation technology such as model predictive control, real-time optimization and online process monitoring. Therefore, in this paper, the rigorous dynamic model of an RBD is transformed into a set of decoupled ordinary differential equations using linear transformation matrices, called extent transformation, that preserve the physical meaning of the transformed variables. The resulting model has a state space representation with a diagonal state matrix. This representation is suitable for control purposes and can be considered as a linear parameter varying system. Based on the final structure of the model, controllability conditions are stated, and model reduction scenarios are proposed. Finally, the model based on extent transformations is compared with the rigorous nonlinear model via the simulation of a polyesterification process.

Influence of CuO nanoparticle on palm oil based alkyd resin preparation and its antimicrobial activity

An alkyd resin has been synthesized from palm oil that reacted with glycerol and phthalic anhydride by alcoholysis-polyesterification process and co-catalyzed by CuO nanoparticle. The CuO nanoparticle was pre-prepared in the glycerol via sol gel method, which creates a new reaction condition for resin preparation. The resins were characterized by fourier transform infrared spectroscopy (FTIR), where a new ester linkage bond (C-O-C) was noticed for resin sample. The antimicrobial activity and the curing behaviour of the resin were determined by Kirby-Bauer and differential scanning calorimeter technique. It was found that, the addition of CuO speeded up the reaction rate and played antimicrobial role. Moreover, it shortens the reaction time of alcoholysis and polyesterification process.

The influence of CuO nanoparticle on non-edible rubber seed oil based alkyd resin preparation and its antimicrobial activity

Abstract In the present paper, bioresin was prepared from non-edible rubber seed oil via alcoholysis–polyesterification process over homogeneous base catalyst tailored by copper oxide (CuO) nanoparticles. CuO nanoparticles were synthesized in glycerol at room temperature and subsequently used in alkyd resin synthesis. The polyesterification process was monitored by determining the acid values as a function of time at different CuO nanoparticle concentrations. The formation of the alkyd resin was confirmed by FTIR with the presence of ester group (C O C). The antimicrobial activity of the pseudo–homogeneous additive was determined via Kirby–Bauer Method. The addition of CuO nanoparticle into the conventional homogeneous base catalyzed system explored a new catalytic route for the preparation of bioresin from vegetable oil while reducing the reaction time, as well as inducing the antimicrobial properties in the resin.

Development of Green Dual Polymers for Antibacterial Applications

In this article, we report on the antibacterial properties of a novel antimicrobial poly(citric acid-co-curcumin) polymer system that was prepared by a catalyst–free polyesterification process. The dual polymer of poly(citric acid-co-curcumin) was synthesized by varying the weight ratio of citric acid and curcumin monomers. Details of the synthesis, spectral (Fourier transform infrared, ultraviolet), thermal stability (Thermogravimetric analyses), and the morphological (Scanning electron microscopy/energy dispersive spectroscopy) characterization of dual polymers are presented in this scientific article. The UV–visible spectrometry was used to confirm the copolymerization of curcumin dispersion in the dual polymer systems. The presence of functional groups of copolymers was confirmed by Fourier transform infrared spectroscopy. The thermogravimetric analysis results indicated that poly(citric acid-co-curcumin) have a thermal stability up to 225°C. The ratios used were 1:0.25, 1:0.5, 1:0.75, and 1:1 and their antibacterial properties were studied with respect to their activity on gram-positive and gram-negative bacteria. This dual polymer was inoculated onto a Petri dish and its ability to inhibit the growth of Escherichia coli, Staphylococcus, Bacillus subtilis, Candida albicans (fungus), and Micrococcus luteus was evaluated using the bacterial disc method. Results indicated inhibition properties to increase with increasing curcumin content and the dual polymer with highest curcumin content showed excellent antimicrobial activities against both gram-negative and gram-positive microorganisms. Hence, it was clear that the developed dual polymers may be effectively used for antibacterial applications such as wound dressing.

Kinetic Study on the Polyesterification and Copolymerisation Process of Unstyrenated and Styrenated Palm Kernel Oil Based Alkyd Resin

The kinetics of the preparation of unstyrenated and styrenated palm kernel oil based alkyd resins were studied using polycondensation and copolymerization process. Three alkyd resins A, B, and C of medium oil length were prepared using phthalic anhydride, maleic anhydride, and glycerol at stipulated ratios. The prepared alkyd resins were copolymerized with styrene using benzyol peroxide as an initiator at 150°C for 3 hr. The kinetic behavior of the polyesterification and copolymerization process and the resulting alkyd resins and styrenated alkyd resins were studied as a function of viscosity and the reaction time using integral method of analysis. The results showed that the resins A and B followed the first order reaction while resin C followed the second order reaction with rate constants of 13 × 10-3 min-1, 30 × 10-3 min-1, and 3 × 10-3 (Pa.S)(min)-1 respectively. For styrenated alkyds, kinetic study confirmed that styrenated alkyd A followed the first order kinetics and styrenated alkyds B and C followed the second order kinetics with rate constants of 8 × 10-3 min-1, 6 × 10-4 (Pa.S)(min)-1, and 6 × 10-4 (Pa.S)(min)-1 respectively.

Tailoring base catalyzed synthesis of palm oil based alkyd resin through CuO nanoparticles

Palm oil based alkyd resin was synthesized by an alcoholysis–polyesterification process over a base catalyst tailored by copper oxide (CuO) nanoparticles.

Microwave-Assisted Polyesterification Process in Bulk and Aqueous Media

Microwave irradiation in polymer chemistry is an emerging research field. This type of heating can enhance the rate of reaction and improve the specific characteristics of the formed polymer. In this context, the present paper focuses on selective microwave (MW) heating and its influence on the polyesterification reaction. As a reaction model, the polyesterification of sebacic acid with decanediol, in bulk and in aqueous emulsion is investigated. The reaction was catalyzed by using 4-dodecylbenzenesulfonic acid (DBSA), which plays a catalytic and surfactant role. Both in bulk and in aqueous media, a polyester with higher molecular weight is obtained in MW heating compared to the conventional heating.

Optimization of polyesterification process for production of palm oil modified alkyd resin using response surface methodology

The optimization of polyesterification process of air drying alkyd resin from non-drying palm oil was studied. Response surface methodology (RSM) based on central composite rotatable design (CCRD) involving 30 experiments of four process variables at five levels was employed in view of its economical way of obtaining optimal response with fewest number of experiments. Self cured resin was obtained by modification of the saturated structure of palm oil with glycerol via alcoholysis, followed by unsaturated functional group of phthalic anhydride via polyesterification. The studied process parameters were reaction temperature, reaction time, catalyst concentration and PA:MGO ratio. Predictive model describing the fractional conversion in terms of process variables was derived from multiple regression analysis. Optimum fractional conversion of 97.28% was predicted at reaction temperature of 240.61°C, reaction time of 150min, catalyst concentration of 0.03% and PA:MGO ratio of 0.38:1, for the process. Extent of reaction at 120min of polycondensation of the monomers was more than 85%. Model validation experiment shows good correspondent between the actual (96.04%) and predicted (97.28%).

Thermal properties, curing characteristics and water absorption of soybean oil-based thermoset

Epoxidized soybean oil (ESO) was successfully thermal-cured by using methylhexahydrophthalic anhydride (MHHPA) curing agent, in the presence of tetraethylammonium bromide (TEAB) catalyst of varied concentration (0.3-0.8 phr). The polyesterification process of ESO thermoset was proven and supported by Fourier transforms infrared spec- troscopy (FTIR) and gas chromatography-mass spectroscopy analysis (GC-MS). A possible chemical reaction of the MHHPA, TEAB and ESO was proposed based on the experimental work. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed that there is a positive relationship between the degree of conversion and crosslink density of ESO thermoset with TEAB concentration. The kinetics of water absorption of the ESO thermoset were found to conform to Fickian law behavior.

Influence of microwave irradiation on a polyesterification reaction

The paper focuses on selective microwave heating and its influence on a polyesterification process. As a model reaction, the polyesterification reaction of adipic acid with neopentyl glycol is investigated. Non-catalyzed and tin (II) chloride catalyzed reaction experiments have been performed with microwave and conventional heating in an open, stirred vessel under a nitrogen atmosphere. Except faster heating times obtained under microwave heating, no different effects on the polyesterification reaction were found between the two heating modes. After 3-h experiments the conversion of the acid groups was similar under microwave heating and conventional heating. Particular emphasis was given on elucidating the important, though scarcely reported in the microwave literature, issues of energy consumption and efficiency. Approximately 20–30% of the electric energy consumed by the microwave oven is converted to thermal energy in the vessel during (non-reactive) heating of the individual components of the polyesterification process. This fraction drops to ∼5% in the event of isothermal reaction experiments. A vast amount of energy is lost in the magnetron and the multimode cavity; these losses do not hamper conventional (conductive) heating, which is currently more economical. Finally, different ways of improving the thermal efficiency and thus the economic prospects of microwave technology are discussed.

Development on polymeric precursor routes to produce superconducting nanoparticles

The well-known polymeric precursor route is a simple and low-cost sol–gel method based on the preparation of an aqueous precursor solution of metals followed by the addition of a water-soluble polymer. This method consists of a polyesterification process between a metal chelate complex by using a hydroxycarboxylic acid and a polyhydroxy alcohol. In this work, citric acid (CA), tartaric acid (TA) and ethylenediaminetetraacetic acid (EDTA) are used as the hydroxycarboxylic acid and ethylene glycol (EG) is used as the polyhydroxy alcohol. The effects of the precursor pH solution, time and temperature of polymerization step as well as the combination of different chelating agents in order to obtain nanoscopic YBa 2Cu 3O y samples were traced.

Polyester Polyols from Waste PET Bottles for Polyurethane Rigid Foams

This paper describes a modified process to produce polyester polyols from PET wastes derived from the “bottle fraction residue” of the German Dual System (DSD) [11] employing a waste oligoester condensate of the polyesterification process with the addition of some glycols of longer chain and occasional modification with further dicarboxylic acids to produce polyester polyols of a broad range of properties which are further reacted to form polyurethane or polyisocyanurate rigid foams for insulation, construction materials, or coatings.

Polyesterification catalyst and process

Polyesterification catalyst and process

Effect of chain length of dibasic acids on novel unsaturated polyesters synthesized by a ‘3-step’ polyesterification process

Novel unsaturated polyesters based on MEXDIOL (a mixed glycol), isophthalic acid, maleic anhydride and succinic acid/suberic acid/sebacic acid have been synthesized by a ‘3-step’ polyesterification process. The structures of these novel unsaturated polyesters have been established on the basis of the ‘process of synthesis’ and IR. Further, these novel unsaturated polyesters have been characterized for various properties. The data indicate that the increase in the chain length of dibasic acid results in increase in gel time, elongation, nitroglycerine (NG) absorption and thermal conductivity and decrease in exotherm peak temperature, tensile strength, bond strength with CMDB propellants, hardness and heat resistance. The trends in properties have been explained in terms of assigned structures.

Comparative study of unsaturated halo and nonhalo polyesters and inhibition of double‐base rocket propellants

AbstractUnsaturated halo and nonhalo polyesters, based on tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and phthalic anhydride with diethylene glycol and maleic anhydride, have been synthesized, using a “2‐step” polyesterification process. These were mixed with 35% styrene monomer and 0.02% hydroquinone. The structural aspects of halo and nonhalo polyesters have been studied by IR and NMR. Further, these polyesters have been characterized for various properties. A comparison of various properties suggests that tensile strength, bond strength, heat resistance, flame retardance, gel time, and oxygen index follow the order as BP‐35 > CP‐35 > NHP‐35, whereas the order for other properties, such as exotherm peak temperature, thermal conductivity, % elongation, and nitroglycerine absorption, is BP‐35 < CP‐35 < NHP‐35. Variation in the properties of cured halo and nonhalo polyesters has been discussed in terms of structural considerations. The nature of P‐t profile of inhibited double‐base (DB) rocket propellants on static evaluation suggests that CP‐35 is a potential inhibitor for DB propellants. © 1993 John Wiley & Sons, Inc.

PILOT PLANT STUDIES AND MODELLING OF A SEMI-BATCH POLYESTERIFICATION PROCESS

A novel unsaturated polyester formulation was developed recently in our laboratories. The polyester resin, which was designed as a green-house glazing material, exhibited excellent optical properties and superior resistance to weathering conditions. This study describes the scale-up procedure followed in preparing the resin in a 200 L pilot plant reactor starting from its preparation in a 1 L reactor. The paper analyzes the major variables affecting the polyesterification process and presents a semi-empirical model capable of predicting the pilot plant kinetic data from laboratory reactor data. The model is based on a recently developed third order kinetic equation for the reaction of non-stoichiometric amounts of hydroxyl and carboxylic groups. The model quantifies the effects of reaction temperature and inert gas flow rate on reaction rate and provides a basis for the polyesterification process scale-up. The reaction temperature dependence is assumed Arrhenius, whereas the gas flow rate dependence is em...

Application of a mathematical model for the polyesterification process based on mixtures of fumaric acid and adipic acid without catalyst

AbstractThe production of unsaturated polyesters based on mixtures of fumaric acid and adipic acid for different proportions without added catalyst was studied. The progress of the polyesterification was followed by determining the amount of water produced during the reaction. The kinetic parameters (reaction order n, activation energy E, frequency factor k0) of the polyesterification were determined and it was found out that n = 3 in all cases, while E and k0 increased by increasing amount of fumaric acid in the initial mixture of the reaction. A mathematical model for the polyesterification based on the production parameters (e.g. the heating program) and on the kinetic parameters was used and very good correlation was found between the corresponding pair of curves of water produced during the polyesterification, which were determined experimentally and theoretically (by calculating). With regard to the properties of the final product it was found out that its viscosity and its slight yellow colour increased by increasing the amount of fumaric acid in the initial mixture of raw materials. General prospects for practical application of this method were also discussed.