Poly(ethylene naphthalate) formation 1. transesterification of dimethylnaphthalate with ethylene glycol

The transesterification of dimethyl naphthalate (DMN) with ethylene glycol (EG) was kinetically investigated in the presence of various catalysts at 185 °C. The transesterification was assumed to obey first-order kinetics with respect to DMN and EG, and a rate equation was derived. The rate constant of transesterification which calculated from the quantity of methanol distilled from the reaction vessel was used to evaluate each metal compound in its activity. The first-order dependence on the catalyst concentration is valid below a critical concentration which was found to be dependent on the catalyst type. The order of decreasing catalytic activity of various metal ions was found to be: Pb Zn > Co > Mg > Ni Sb. But in the case of highly basic metal salts, the rate constants were found to be extremely large at the initial stage of the reaction, and then rapidly decreased with the progress of the reaction. Effects of reaction temperature were also discussed. The activation energies for zinc acetate and lead acetate were 97.84 and 97.2 KJ/mol, respectively, which were calculated from Arrhenius equation.     

Kinetics of transesterification of dimethylene terephthalate with ethylene glycol

There is a disagreement about the order of reaction of transesterification of DMT with EG. The reactivity of the two ester groups is not compared yet. The transesterification of DMT and MHET is studied to establish the kinetics of the process. Attempts are made to treat the kinetic data on a mathematical model for third-order reaction.     

Studies on the formation of poly(ethylene terephthalate): 3. Catalytic activity of metal compounds in transesterification of dimethyl terephthalate with ethylene glycol

The rate constant of transesterification of dimethyl terephthalate (DMT) with ethylene glycol (EG) in the presence of various metal compounds as catalysts at 197°C, calculated from the quantity of formed methanol, was used to evaluate each metal compound in its catalytic activity. First, in the case of highly basic metal salts the rate constants were found to be extremely large in the initial stage of the reaction. These values depended on the basicity of the metal salts, but decreased rapidly with the progress of the reaction, and reached values which were not appreciably dependent on the basicity. Secondly, in the case of metal salts of lower basicity such a phenomenon was not observed, and single rate constants were recognized throughout the reaction period. These rate constants were logarithmically correlated by a straight line (mountain-shaped) in a plot vs. stability constants (logβ₁) of dibenzoyl methane (DBM) complexes of the corresponding metal species. Also in the case of highly basic metal salts, the rate constants in the latter stage followed the same straight line. Consequently, the stability constant of DBM complex of each metal species was found very useful as a forecast of catalytic activity of the metal compound. The compound of metal species with values of logβ₁ ranging from 9 to 11 was most active as the catalyst.     

Transesterification in poly(ethylene terephthalate) and poly(ethylene naphthalate 2,6-dicarboxylate) blends: model compounds study

Kinetics of transesterification reaction in poly(ethylene terephthalate)-poly(ethylene naphthalate 2,6-dicarboxylate), PET-PEN, blends resulting from melt processing was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). The exchange reaction between BEB and NEN was followed by ¹H NMR spectroscopy using signals from the aliphatic protons of ethylene glycol moieties at 4.66 and 4.78 ppm, respectively. The first-order kinetics was established under pseudo-first-order conditions for both reactants. Thus, the overall transesterification reaction was second order reversible. The reversibility was confirmed experimentally by heating a mixed sequence of 1-benzoate 2-naphthoate ethylene (BEN) under similar conditions. Both forward reaction of the equimolar amounts of the reagents and reverse reaction came to equilibrium at the same molar ratio of the reactants and reaction products of roughly 0.25:0.50:0.25 for BEB, BEN, and NEN, respectively. The rate equation for the transesterification reaction in the model system was modified using half-concentration of BEN, which is the only effective in the intermolecular exchange. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied, and the values of equilibrium and rate constants, as well as other basic thermodynamic and kinetic parameters were determined. The use of Zn(OAc)₂ as a catalyst resulted in a significant decrease in the activation enthalpy of transesterification, which might be due to the partial switch of the reaction mechanism from primarily pseudo-homolytic to more heterolytic where Zn^II acts as a Lewis base which binds to the ester carbonyl oxygen.     

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.     

Steady-state and transient behavior of a continuous polyethylene terephthalate condensation polymerization process. I. Melt transesterification stage

The steady-state and transient behavior of a continuous stirred-tank reactor for melt transesterification of dimethyl terephthalate with ethylene glycol in the presence of metal acetate catalyst is presented. The kinetic model includes the main transesterification reactions and side reactions leading to diethylene glycol and carboxylic acid end groups. The effect of various reactro operating parameters such as [EG]/[DMT] mole ratio and feed catalyst concentration on the product distribution under steady-state reactor operating conditions is analyzed. The dynamic process model has also been solved and the reactor transients to step changes in various reactor parameters are reported.     

Kinetic and thermodynamic study of methanolysis of poly(ethylene terephthalate) waste powder

Depolymerization of poly(ethylene terephthalate) waste (PETW) was carried out by methanolysis using zinc acetate in the presence of lead acetate as the catalyst at 120–140 °C in a closed batch reactor. The particle size ranging from 50 to 512.5 µm and the reaction time 60 to 150 min required for methanolysis of PETW were optimized. Optimal percentage conversion of PETW into dimethyl terephthalate (DMT) and ethylene glycol (EG) was 97.8% (at 120 °C) and 100% (at 130 and 140 °C) for the optimal reaction time of 120 min. Yields of DMT and EG were almost equal to PET conversion. EG and DMT were analyzed qualitatively and quantitatively. To avoid oxidation/carbonization during the reaction, methanolysis reactions were carried out below 150 °C. A kinetic model is developed and the experimental data show good agreement with the kinetic model. Rate constants, equilibrium constant, Gibbs free energy, enthalpy and entropy of reaction are also evaluated at 120, 130 and 140 °C. The methanolysis rate constant of the reaction at 140 °C (10.3 atm) was 1.4 × 10^?3 g PET mol^?1 min^?1. The activation energy and the frequency factor for methanolysis of PETW were 95.31 kJ mol^?1 and 107.1 g PET mol^?1 min^?1, respectively. © 2003 Society of Chemical Industry     

Kinetics of glycolysis of poly(ethylene terephthalate) under microwave irradiation

The glycolysis of poly(ethylene terephthalate) (PET) was carried out using excess ethylene glycol (EG) in the presence of zinc acetate as catalysts under microwave irradiation. The effects of particle size, microwave power, the weight ratio of EG to PET, the weight ratio of catalyst to PET, reaction temperature and stirring speed on the yield of bis(hydroxyethyl terephthalate)(BHET) were investigated. The experimental results indicated that the glycolysis rate was significantly influenced by stirring speed and initial particle size. The optimal parameters of glycolysis reactions were the weight ratio of catalyst to PET of 1%, the weight ratio of EG to PET of 5, 500 W and 196°C, the yield of BHET reached to 78% at only 35 min. The glycolysis products were analyzed and identified by FTIR, differential scanning calorimetry, and elemental analysis. The kinetics of glycolysis of PET under microwave irradiation could be interpreted by the shrinking core model of the film diffusion control. The apparent activation energy was evaluated using the Arrhenius equation and it was found to be 36.5 KJ/mol, which was lower compared to the same process using conventional heating. The experimental results also showed that the reaction time was significantly decreased under microwave irradiation as compared with it by conventional heating. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚对苯二甲酸丙二醇酯合成研究

研究了以对苯二甲酸二甲酯(DMT)与1,3 丙二醇(PDO)为原料,采用酯交换、缩聚反应路线合成聚对苯二甲酸丙二醇酯(PTT)。动力学分析表明:酯交换反应在转化率为95%之前,符合二级反应动力学模型。实验结果指出,采用传统催化剂体系当原料配比n(PDO)/n(DMT)=2.2/1时,1gDMT的酯交换催化剂醋酸锌为400～600μg,反应温度为220℃时,酯交换反应速率较快;1gDMT的缩聚催化剂三氧化二锑为500μg,反应温度为265℃,在高真空下,可得较高摩尔质量的PTT。     

Kinetics of transesterification of dimethyl terephthalate with 1,4-butanediol catalyzed by tetrabutyl titanate

The kinetics of tetrabutyl titanate catalyzed transesterification of dimethyl terephthalate (DMT) with 1,4-butanediol (BD) is investigated. Detailed analysis of experimental data indicates that equal reactivity hypothesis for functional groups is valid for [BD]/[DMT] molar ratios greater than 2 up to 75% conversion. Effects of reaction temperature and catalyst concentration are also discussed.     

Mechanism and kinetics of transesterification in poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalene dicarboxylate) polymer blends

In a previous work [L. Alexandrova, A. Cabrera, M.A. Hernández, M.J. Cruz, M.J.M. Abadie, O. Manero, D. Likhatchev, Polymer 43 (2002) 5397. [1]], a model compounds study on the kinetics of a transesterification reaction in poly(ethylene terphthalate)-poly(ethylene naphthalene 2,6-dicarboxylate), PET-PEN blends, resulting from melt processing, was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). A first-order kinetics was established under pseudo first-order conditions for both reactants, and thus the overall transesterification reaction was second-order reversible. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied.In this work, the actual PET-PEN system was melt processed by mixing the polymers below the critical reaction temperature in a twin-screw extruder. Thereafter, the reaction was induced by temperature in open glass ampoules. A second order reversible kinetics was measured, in agreement with the kinetics established in the previous model compounds study. The equilibrium constant value corresponds to a forward rate constant which is four times larger than the reverse rate constant. The activation thermodynamic parameters confirmed the direct ester-ester exchange mechanism for the reaction.     

PEN合成中NDC与EG酯交换反应工艺及动力学研究

以2,6-萘二甲酸二甲醇酯(NDC)和乙二醇(EG)为原料,以金属盐类为催化剂,在一定条件下,研究了NDC与EG的酯交换反应,探讨了NDC与EG的酯交换反应工艺及动力学规律,不同反应温度下,NDC与EG酯交换反应遵循二级反应动力学规律,反应表观活化能为92.89 kJ/mol。     

Kinetics of diethylene glycol formation from bishydroxyethyl terephthalate with proton catalyst in the preparation of poly(ethylene terephthalate)

This research focused on the kinetics of diethylene glycol (DEG) formation from the bishydroxyethyl terephthalate (BHET) monomer with a proton catalyst. In this study, the effect of proton concentration and of reaction temperature on DEG formation are discussed. Also, the rate equation of DEG formation from the BHET monomer with a proton catalyst is described. It was found that, as far as kinetics is concerned, the reactivity of the hydroxyl end groups of BHET with protons is greater than that of ethylene glycol (EG) with protons in DEG formation. In addition, the activation energy of BHET with protons is much lower than that of BHET with itself, that is, as protons emerge during the process of PET synthesis from BHET, they catalyze DEG formation. This study provides additional kinetics data to that described in our studies previously published (J Polym Sci Polym Chem Ed 1998, 36, 3073; 1998, 36, 3081). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1221–1228, 2000     

Kinetics of glycolysis of poly(ethylene terephthalate) waste powder at moderate pressure and temperature

The reaction of poly(ethylene terephthalate) waste (PETW) powder with ethylene glycol (EG) was carried out in a batch reactor at 2 atm of pressure and a 220°C temperature. The particle size range of 50–512.5 μm and the reaction time of 40–180 min that are required for glycolysis of PETW were optimized. To avoid the carbonization and oxidation of reactants and reaction products and to reduce corrosion, the reaction was undertaken below 250°C using a lower reaction time. To increase the yield of dimethyl terephthalate and EG, an external catalyst was introduced during the reaction. The degree of depolymerization of PETW was proportional to the reaction time. The reaction rate was found to depend on the concentrations of liquid EG and of ethylene diester groups in the polyester. A kinetic model was used for the reaction was found to be consistent with experimental data. The rate constant was inversely proportional to the reaction time, as well as the particle size, of PETW. The degree of depolymerization of PETW was inversely proportional to the particle size of PETW. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1569–1573, 2003     

Effects of the carboxyl concentration on the solid‐state polymerization of poly(ethylene terephthalate)

There are two types of polycondensation reactions in the solid‐state polymerization (SSP) of poly(ethylene terephthalate) (PET), namely, transesterification and esterification. Transesterification is the reaction between two hydroxyl ends with ethylene glycol as the byproduct, and esterification is the reaction between a carboxyl end and a hydroxyl end with water as the byproduct. The SSP of powdered PET in a fluid bed is practically a reaction‐controlled process because of negligible or very small diffusion resistance. It can be proved mathematically that an optimal carboxyl concentration for reaction‐controlled SSP exists only if k₂/k₁ > 2, where k₂ and k₁ are the forward reaction rate constants of esterification and transesterification, respectively. Several interesting observations were made in fluid‐bed SSP experiments of powdered PET: (1) the SSP rate increases monotonously with decreasing carboxyl concentration, (2) k₂ < k₁ in the presence of sufficient catalyst, (3) k₁ decreases with increasing carboxyl concentration if the catalyst concentration is insufficient, and (4) the minimum catalyst concentration required to achieve the highest SSP rate decreases with decreasing carboxyl concentration. In the SSP of pelletized PET, both reaction and diffusion are important, and there exists an optimal carboxyl concentration for the fastest SSP rate because esterification, which generates the faster diffusing byproduct, is retarded less than transesterification in the presence of substantial diffusion resistance. The optimal prepolymer carboxyl concentration, which ranges from 25 to 40% of the total end‐group concentration in most commercial SSP processes, increases with increasing pellet size and product molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1288–1304, 2002     

Kinetics measurement of ethylene-carbonate synthesis via a fast transesterification by microreactors

High-purity ethylene carbonate (EC) is widely used as battery electrolyte, polycarbonate monomer, organic intermediate, and so on. An economical and sustainable route to synthesize high-purity ethylene carbonate (EC) via the transesterification of dimethyl carbonate (DMC) with ethylene glycol (EG) is provided in this work. However, this reaction is so fast that the reaction kinetics, which is essential for the industrial design, is hard to get by the traditional measuring method. In this work, an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst. The effects of flow rate, microreactor diameter, catalyst concentration, reaction temperature, and reactant molar ratio were investigated. An activity-based pseudo-homogeneous kinetic model, which considered the non-ideal properties of reaction system, was established to describe the transesterification of DMC with EG. Detailed kinetics data were collected in the first 5 min. Using these data, the parameters of the kinetic model were correlated with the maximum average error of 11.19%. Using this kinetic model, the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%, suggesting its satisfactory prediction performance.     

The conformational changes,crystal structure and melting behavior of poly(ethylene/ trimethylene terephthalate) copolyesters

The conformational changes, crystal structure and melting behavior of poly(ethylene/trimethylene terephthalate) (ET) copolyesters were investigated using in situ Fourier transform infrared (FTIR) spectroscopy, wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) under isothermal crystallization conditions. The results show that the minimum melting temperature was observed in ET53, in which the relative amount of ethylene glycol (EG) to 1,3‐propanediol (PDO) was 52.68/47.32 and the PDO‐dimethyl terephthalate (DMT)‐PDO segments in the molecular chain dominated the crystal formation. The minimum crystallinity of ET copolyesters was found in ET66, in which the relative amount of EG/PDO was 65.91/34.09 and the EG‐DMT‐EG segments in the molecular chain dominated the crystal formation. A rapid and continuous conformational transition in ET copolyesters was observed using in situ FTIR in the first 10 min under isothermal crystallization conditions. The continuously adjusting conformation in the molecules reflects the crystallization of ET copolyesters. Based on the DSC and the X‐ray analyses of the crystallization behavior in the ET copolyesters, crystalline conformation transitions of molecules in ET copolyesters take place rapidly and early. Copyright © 2012 Society of Chemical Industry     

Transesterification reaction kinetics of poly(ethylene terephthalate/poly(ethylene 2,6‐naphthalate) blends

The transesterification reaction of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends during melt‐mixing was studied as a function of blending temperature, blending time, blend composition, processing equipment, and different grades of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate). Results show that the major factors controlling the reaction are the temperature and time of blending. Efficiency of mixing also plays an important role in transesterification. The reaction kinetics can be modeled using a second‐order direct ester–ester interchange reaction. The rate constant (k) was found to have a minimum value at an intermediate PEN content and the activation energy of the rate constant was calculated to be 140 kJ/mol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2422–2436, 2001     

PEN合成的酯交换反应工艺及动力学研究

讨论了使用 (CH3COO) 2 Zn·2H2 O作为催化剂 ,2 ,6 萘二甲酸二甲酯 (DMN) 乙二醇 (EG)的酯交换反应。该酯交换反应遵循二级反应动力学。反应活化能为 14 7.9kJ mol。较高的反应活化能使得该酯交换反应速率对反应温度比较敏感。     

Solid-state polycondensation of poly(ethylene terephthalate) modified with isophthalic acid: kinetics and simulation

The kinetics for the solid-state polycondensation (SSP) of poly(ethylene terephthalate) modified with isophthalic acid at the protection of nitrogen gas was studied in the paper. A kinetic model controlled by the reversible chemical reactions and the three dimension diffusions of small molecule by-products has been established. The kinetic parameters of the SSP of PET at different temperatures, including the forward rate constants of transesterification reaction (k₁) and esterification reaction (k₂), the diffusion coefficients of EG (D₁) and water (D₂), the concentrations of EG (g_s) and water (w_s) on the surface of PET chips in SSP, and the activation energies of these kinetic parameters were obtained by experiments and solution of the model. Using the model and the kinetic parameters, the SSP of poly(ethylene terephthalate) modified with isophthalic acid can be simulated with good accuracy. In addition, the influences of nitrogen gas flow rate, the chip dimension and the carboxyl end-group concentration of the PET prepolymer on the molecular weight of PET after SSP, and the change of the EG concentration of PET chips with reaction time were also studied by simulation.