Effect of the Sb2O3 catalyst on the solid-state postpolycondensation of poly(ethylene terephthalate)

The effect of Sb₂O₃, which is used as the main catalyst in the production of poly(ethylene terephthalate) (PET) by melt polymerization, was studied on solid-state postpolycondensation. It was observed that the catalyst works efficiently even in the solid state. The number-average molecular weight of a PET prepolymer with an Sb₂O₃ content of 2000 ppm was increased from 18,350 to 40,800 after heating at 210°C for 8 h under vacuum (2–3 Pa), whereas when the catalyst was absent, the molecular weight of the same prepolymer under the same conditions was just increased to 22,500. The activation energies and the frequency factors of the esterification and ester interchange reactions, which take place simultaneously during solid-state postpolycondensation, were determined. © 1995 John Wiley & Sons, Inc.     

Design of multiple flame‐retardant polymers

Two polyphosphonates having multiple flame‐retardant actions were synthesized by interfacial polycondensation of a bisphenol and dichlorophenylphosphine oxide using cetyl trimethyl ammonium chloride as a phase transfer catalyst (PTC) at 0°C. The polyphosphanates thus prepared were characterized by viscometry, elemental analysis, IR, ¹H‐NMR, ³¹P‐NMR, and X‐ray diffraction studies. These polymers are highly soluble in polar solvents such as DMF, DMAc, DMSO, etc., as well as in chlorinated hydrocarbon solvents such as CH₂Cl₂, CHCl₃, etc. The thermal study of polymers was carried out by TGA and DTA analyses. The flammability of the polymers was studied by the limiting oxygen index measurements. The polymers are self‐extinguishing, and begin to lose weight at around 252°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 785–792, 2001     

Development of Fe‐, Sb‐, Bi‐ and Al‐impregnated silica catalysts using rice husk silica as a support for Friedel–Crafts benzylation of arenes

The milling by‐product of rice, rice husk, constitutes a major waste of the agricultural industry. It is mainly used as a fuel additive for various purposes, leaving behind residual ash which is rich in silica (Biogenic silica). In the present project, rice husk silica was impregnated with Fe³⁺, Sb³⁺, Bi³⁺ and Al³⁺ from both their aqueous and organic solutions. The resultant catalysts were activated at 120 °C and 550 °C and used for the Friedel–Crafts benzylation of benzene using benzyl chloride. Copyright © 2003 Society of Chemical Industry     

Structural characterization and thermal behaviour of block copolymers of polydimethylsiloxane and polyamide having trichlorogermyl pendant groups

Block copolymers having a pendant trichlorogermyl group as a part of polyamide segment? (CO? R′? CO? NH? Ar? NH? )_xCO? R′? CO? and polydimethylsiloxane of general formula [(? CO? R′? CO? HN? Ar? NH)_x? CO? R′? CO? NH(CH₂)₃SiO(CH₃)₂ ((CH₃)₂SiO)_ySi(CH₃)₂(CH₂)₃ NH? ]_n (where R′ = CH₂CH(GeCl₃), CH(CH₃)CH(GeCl₃), CH(GeCl₃)CH(CH₃); Ar = C₆H₄, (? C₆H₃? CH₃)₂, (? C₆H₃? OCH₃)₂, 2,5‐(CH₃)₂? C₆H₂, C₆H₄? O? C₆H₄) were prepared by a polycondensation reaction and characterized using CHN and Ge analysis, Fourier transform infrared (FTIR) and ¹H NMR spectroscopy, thermogravimetric analysis (TGA) and molecular weight determination. They have a lamellar structure with weight‐average molecular weight in the range 1.21 × 10⁵–4.79 × 10⁵ g mol^?1. These copolymers display two glass transition temperatures and have an average decomposition temperature of 489 °C. TGA, FTIR and gas chromatography/mass spectrometry studies indicate that degradation of these block copolymers results in carbon monoxide, oligomeric siloxanes and polyamide fragments. They are thermally stable due to the hydrogen bonded interlinked chains of polyamide, while they absorb water due to the presence of Ge? Cl bonding. Copyright © 2010 Society of Chemical Industry     

Melt polycondensation of L‐lactic acid to poly(L‐lactic acid) with Sn(II) catalysts combined with various metal alkoxides

Melt polycondensation of L ‐lactic acid (LA) was examined in the presence of binary catalyst systems consisting of SnCl₂·2H₂O and metal alkoxides as co‐catalysts. Among the co‐catalysts examined, viz (Al(O ⁱPr)₃,Ti(O ⁱPr)₄,Y(O ⁱPr)₃,Si(OEt)₄ and Ge(OEt)₄), Ge(OEt)₄ was found to be the most effective in enhancing the catalytic activity of Sn(II). With an optimized composition of SnCl₂·2H₂O–Ge(OEt)₄, the molecular weight (M_n) of PLLA reached 40 000 Da in a short reaction time (<15 h) at the optimum reaction conditions of 180 °C and 10 Torr. This catalyst system was also superior to the conventional single metal ion catalysts such as Sn(II) in terms of racemization and discolouration of the resultant polymer. The metal alkoxides, added as co‐catalysts, should work as oxo acids that can effectively control the catalytic activity of Sn(II) ion in the direct polycondensation of LA, in a manner similar to that of proton acids. © 2003 Society of Chemical Industry     

Synthesis and characterization of thermostable polyamides from unsymmetrical diamines containing flexible ether linkage and different diarylimidazole pendants in ionic liquids

A series of aromatic poly(amide-ether) (PAE)s containing derivatives of imidazole heterocyclic ring and flexible ether linkages was synthesized from polymerization reaction of three new diamines with commercially available aromatic diacids by using two different methods of direct polycondensation: (1) By using triphenyl phosphite (TPP) as activating agent, NMP, pyridine (Py) and LiCl, and (2) by using combination of an ionic liquid (IL) and TPP which allowed to carry out PAEs synthesis without using Py, LiCl and NMP. Room temperature ILs bearing anions such as BF ₄ ^- , Br^-, Cl^-, and PF ₆ ^- with symmetrical 1,3-dialkylimidazolium cations have been prepared and used as polycondensation media. The polymers were obtained in good yields with moderate viscosity (0.47?C0.68 dL/g) in a shorter time of reaction (2.5?h) in comparison with the PAEs obtained in NMP (12?h). All of these polymers were amorphous in nature, showed excellent solubility in amide-type polar aprotic solvents. These polymers showed good thermal stability with glass transition temperatures (T_g) between 212?C355?°C and 10?% weight loss temperatures were recorded around 421?°C and 460?°C in air and N₂, respectively. These polymers showed blue flourescence emission in the range of 460?C505?nm and can be candidate for applications in photoluminescent devices.     

In‐situ synthesis of poly(ethylene terephthalate)/clay nanocomposites using TiO2/SiO2 sol‐intercalated montmorillonite as polycondensation catalyst

A novel organic montmorillonite, which could act as both polycondensation catalyst of poly(ethylene terephthalate) (PET) and filler of PET/clay nanocomposites, was prepared. Original montmorillonite was first treated with different amounts of poly(vinylpyrrolidone) (PVP), and then intercalated by TiO₂/SiO₂ sol to gain polycondensation catalytic activity. The acquired clay possessed excellent thermal stability and would not degrade during the polycondensation step. PET/clay nanocomposites were prepared via in‐situ polymerization using the organo‐clay as polycondensation catalysts. The morphologies of the nanocomposites were characterized by X‐ray diffraction and transmission electron microscope. The results indicated that the amount of PVP and TiO₂/SiO₂ sol strongly affected the dispersion state of the clay, and finally, partially exfoliated PET/clay nanocomposites were obtained. The nanocomposites had better properties than pure PET due to the incorporation of the delaminated clay layers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Analysis of a reactor with surface renewal for poly(ethylene terephthalate) synthesis

A mathematical model of a polycondensation reactor that can be used in the final stage for poly(ethylene terephthalate) (PET) is established and compared with experimental data obtained from a laboratory scale reactor with film renewal. Detailed side reactions are considered along with the diffusional removal of the small molecules through thin film. Among several kinetic constants, the polycondensation reaction rate constant k₁(= k₈) and diester group degradation reaction rate constant k₇ have an influence over the degree of polymerization. The values of k₁(= k₈) and k₇ for 0.05 wt% Sb₂O₃ were obtained as curve-fit values: (1) k₁(= k₈) = 3.4 × 10⁶ exp(? 18.500/RT′) (L/mol-min); (2) k₇ = 1.3 × 10¹¹ exp(? 37,800/RT′) (min^?1). Effects of the film exposure time, reduced pressure of vacuum, temperature, the initial terephthalic acid (TPA)/ethylene glycol (EG) mole ratio, the initial degree of polymerization, and catalysts were well explained by the model.     

Oxidative coupling of methane and oxidative dehydrogenation of ethane over strontium-promoted rare earth oxide catalysts

Sr-promoted rare earth (viz. La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er and Yb) oxide catalysts (Sr/rare earth ratio = 0·1) are compared for their performance in the oxidative coupling of methane (OCM) to C₂ hydrocarbons and oxidative dehydrogenation of ethane (ODE) to ethylene at different temperatures (700 and 800°C) and CH₄ (or C₂H₆)/O₂ ratios (4–8), at low contact time (space velocity = 102000 cm³ g⁻¹ h⁻¹). For the OCM process, the Sr–La₂O₃ catalyst shows the best performance. The Sr-promoted Nd₂O₃, Sm₂O₃, Eu₂O₃ and Er₂O₃ catalysts also show good methane conversion and selectivity for C₂ hydrocarbons but the Sr–CeO₂ and Sr–Dy₂O₃ catalysts show very poor performance. However, for the ODE process, the best performance is shown by the Sr–Nd₂O₃ catalyst. The other catalysts also show good ethane conversion and selectivity for ethylene; their performance is comparable at higher temperatures (≥800°C), but at lower temperature (700°C) the Sr–CeO₂ and Sr–Pr₆O₁₁ catalysts show poor selectivity. © 1998 SCI.     

Conversion of methane on catalysts obtained via self-propagating high-temperature synthesis

Monolith metalloceramic catalysts for the selective oxidation of methane are prepared via self-propagating high-temperature synthesis (SHS) from NiO, ZrO₂, MgO, Al, Ni and other powders. Catalytic tests of monolith samples are performed in a flow reactor at 800°C using a methane-air mixture (methane, 29.6 vol %). SHS catalysts are shown to attain the level of platinum and platinum/rhodium catalysts through the yield of syngas (CO + H₂) and to surpass them in the case of Ni 52.9 ZrO₂ 9.5 composition. The latter is used as a catalyst to develop a pilot autothermal syngas generator with a capacity of 30 m³/h. Syngas is generated via carbon dioxide methane conversion (CDMC) on SHS platinum-modified Ni₃Al powder catalysts. The samples are tested in a flow fixed-bed reactor at a catalyst volume of 1 cm³, a grain size of 600–1000 μm, temperatures of 600–900°C, and a volumetric flow rate of 100 cm³/min (CH₄ : CO₂ : He = 20 : 20 : 60 vol %). The catalysts developed for converting natural gas into syngas are shown to be highly active and stable in a high-temperature redox medium. This work is the first step in the synthesis of dimethyl ether, which could compete successfully with diesel fuel.     

Catalytic Synthesis of Methanethiol from H2S-rich Syngas Over Sulfided SiO2-supported Mo-based Catalysts

The synthesis of methanethiol from H₂S-rich syngas was investigated over sulfided Mo-based catalysts supported on SiO₂. At CO/H₂/H₂S = 1/1/2, 0.2 MPa, 3,000 h⁻¹, and 300 °C, mainly CH₃SH, COS, and CO₂ were formed, along with small amounts of hydrocarbons and thioethers over potassium-promoted Mo-based catalysts. Studies of the reaction pathway show that COS is a primary product, which is hydrogenated to CH₃SH and H₂O. Most of CO₂ originates from water-gas shift reaction. The hydrocarbons and thioethers originate from the hydrogenation of CH₃SH.     

INFLUENCE OF GLASS COMPOSITION ON REDUCIBILITY OF Ag+, Bi3+, Sb3+, AND PP+*

The reducibility of a number of ions by dry hydrogen was studied in various glass compositions. Reduction temperatures with dry hydrogen were about 75° C, lower than with wet hydrogen. The glasses contained 5.0% of Sb₂O₃, Bi₂O₃, or PbO or 0.1% of Ag₂O. In all of the glasses, silver ions were reduced at lower temperatures as basicity was increased, while an increased ratio of B³⁺ to O^2- or Si⁴⁺ to O^- increased stability. The reducibility of Bi³⁺, Sb³⁺, and Pb²⁺ are not easily interpreted. Silver showed reduction at approximately 130°C., bismuth at 200°C., lead at 350°C., and antimony at 400°C.     

1‐Allyl‐3‐methylimidazolium halometallate ionic liquids as efficient catalysts for the glycolysis of poly(ethylene terephthalate)

Series of 1‐allyl‐3‐methylimidazolium halometallate ionic liquids (ILs) were synthesized and used to degrade poly(ethylene terephthalate) (PET) as catalysts in the solvent of ethylene glycol. One important feature of these new IL catalysts is that most of them, especially [amim][CoCl₃] and [amim][ZnCl₃], exhibit higher catalytic activity under mild reaction condition, compared to the traditional catalysts [e.g., Zn(Ac)₂], the conventional IL catalysts (e.g., [bmim]Cl), Fe‐containing magnetic IL catalysts (e.g., [bmim][FeCl₄]), and metallic acetate IL catalysts (e.g., [Deim][Zn(OAc)₃]). For example, using [amim][ZnCl₃] as catalyst, the conversion of PET and the selectivity of bis(hydroxyethyl) terephthalate (BHET) reach up to 100% and 80.1%, respectively, under atmospheric pressure at 175°C for only 1.25 h. Another important feature is that BHET can be easily separated from the catalyst and has a high purity. Finally, based on the experimental phenomena, in ‐situ infrared spectra, and experimental results, the possible mechanism of degradation with synthesized IL is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,Characterization, and Reactivity of trans-Ru(X)(Cl)(nbd)(dppb) (X = H,Cl; nbd = 2,5-norbornadiene; dppb = 1,4-bis(diphenylphosphino)butane), Including the X-ray Crystal Structure of the Dichloride

The ruthenium (II) diene complexes [Ru(X)(Cl)(nbd)(dppb)] (X = Cl, H; nbd = 2,5-norbornadiene; dppb = PPh₂(CH₂)₄PPh₂) have been prepared and characterized spectroscopically. The X-ray crystal structure of RuCl₂(nbd)(dppb) (crystal data at 22°C: space group P1, a = 10.896 (1) Å, b = 15.168(2) Å, c = 10.829 (1) Å, α = 103.02(1)°, β = 107.08(1)°, γ = 81.65(1)°, Z = 2, R = 0.054 for 6420 reflections) shows an octahedral geometry at Ru, with the chloro ligands slightly distorted from a trans configuration (Cl)(1)-Ru-C1(2) = 168.4°); the unit cell contains two molecules of the complex and one molecule of benzene. Reaction of this complex with H₂, in presence of Proton Sponge (PS, 1,8-bis(dimethylamino)naphthalene) as base, is complicated by initial dissociation of nbd, and [Ru₂Cl₅(dppb)₂]⁻-PSH⁺ is the major product. A minor product, the hydrido(diene) complex trans-RuCl(nbd)(dppb) 5 , characterized spectroscopically, is more effectively synthesized from (a) trans-Ru(H)Cl(nbd)(PPh₃)₂, 1 , and dppb, or (b) reaction of RuCl₂(dppb)-(PPh₃) with H₂ in presence of nbd and PS. Complex 5 is unreactive toward H₂ or CO while 1 has been shown previously to give η²-H₂ and norbornenoyl derivatives, respectively; the differences in reactivity are discussed.     

High-temperature in situ FTIR spectroscopy study of LaOF and BaF2/LaOF catalysts for methane oxidative coupling

In situ FTIR spectroscopy was used to characterize the oxygen adspecies and its reactivity with CH₄ over LaOF and 15 mol% BaF₂/LaOF catalysts at OCM temperature (750-800°C). It was found that gas-phase oxygen was activated on the surface of LaOF and 15 mol% BaF₂/LaOF, which had been pretreated under vacuum at 750 or 800°C, forming O ₂ ^- species at high temperature (750-800°C). At 750°C, the adsorbed O ₂ ^- species can react with pure CH₄ accompanied by formation of gas-phase C₂H₄ and CO₂, and there is a good correlation between the rate of disappearance of surface O₂and the rate of formation of gas-phase C₂H₄. The O ₂ ^- species was also observed over the catalysts under working condition, and it reacted with CH₄ in a manner that was consistent with its role in a catalytic cycle. These results suggest that O ₂ ^- may be the active oxygen species for OCM reaction over these catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and Characterization of Ethylene‐Bridged Copolycarbosilazane as Precursors for Silicon Carbonitride Ceramics

An ethylene‐bridged copolycarbosilazane precursor of copolysilylethylenediamine (co‐PSDA) is synthesized by polycondensation of ethylenediamine with the mixture of vinylmethyldichlorosilane and methyldichlorosilane in the presence of triethylamine as acid absorbing agent. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR, ¹H NMR and ¹³C NMR) spectral analysis of the as‐synthesized co‐PSDA suggests a structure of ethylene‐bridged polycarbosilazane having –Si–N–C–C–N– as backbone chain with –CH=CH₂, –H and –CH₃ attached to Si as side groups. Co‐PSDA can be cross‐linked at 80°C using 2, 2‐azobisisobutyronitrile as initiator through the polyaddition of the vinyl group and dehydrogenation/deamination of Si–H and N–H. Then the cross‐linked co‐PSDA precursor is pyrolyzed at 1000°C in argon, giving out amorphous silicon carbon nitride (SiCN) ceramics with a high ceramic yield of 76 wt%. The obtained SiCN ceramics consist of nitrogen‐rich silicon sites of SiN₄ as predominant component and some SiCN₃ sites, which should arise from the breaking of N–C bonds below 600°C and the formation of active N–Si bonds.     

Nickel(II) complexes bearing the bis(β‐ketoamino) ligand for the copolymerization of norbornene with a higher 1‐alkene

A novel bis(β‐ketoamino)Ni(II) complex catalyst, Ni{CF₃C(O)CHC[N(naphthyl)]CH₃}₂, was synthesized, and the structure was solved by a single‐crystal X‐ray refraction technique. The copolymerization of norbornene with higher 1‐alkene was carried out in toluene with catalytic systems based on nickel(II) complexes, Ni{RC(O)CHC[N(naphthyl)]CH₃}₂(R?CH₃, CF₃) and B(C₆F₅)₃, and high activity was exhibited by both catalytic systems. The effects of the catalyst structure and comonomer feed content on the polymerization activity and the incorporation rates were investigated. The reactivity ratios were determined to be r_1‐octene = 0.009 and r_norbornene = 13.461 by the Kelen–Tüdõs method for the Ni{CH₃C(O)CHC[N(naphthyl)]CH₃}₂/B(C₆F₅)₃ system. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of ¹H‐NMR and ¹³C‐NMR. The thermogravimetric analysis results showed that the copolymers exhibited good thermal stability (decomposition temperature, T_dec > 400°C), and the glass‐transition temperature of the copolymers were observed between 215 and 275°C. The copolymers were confirmed to be noncrystalline by wide‐angle X‐ray diffraction analysis and showed good solubility in common organic solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Screening ionic liquids as candidates for separation of acid gases: Solubility of hydrogen sulfide,methane, and ethane

The solubility of the major constituents of natural gas in ionic liquids (ILs) can be used to identify their potential for acid gas removal from a producing gas stream. We have developed models for the solubility of H₂S, CH₄, and C₂H₆ in ILs at typical conditions encountered in natural gas treatment. In this work, a conductor‐like screening model for realistic solvation was used to predict the activity coefficients for solutes in ILs and a cubic EOS was used for vapor‐phase corrections from ideality. Empirical correlations were developed to extrapolate solubilities where experimental data are not available at desired conditions; targeted in this study at 298.15 K and 2000 kPa. Over 400 possible ILs were ranked based on the higher selectivity of absorption of CO₂ and H₂S over CH₄ and C₂H₆. The best 15% (58) of promising ILs for sour gas treatment predominantly contain the anions BF₄, NO₃, and CH₃SO₄ and the cations N₄₁₁₁, pmg, and tmg. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2993–3005, 2013     

Vinyl‐addition copolymerization of norbornene and polar norbornene derivatives using novel bis(β‐ketoamino)Ni(II)/B(C6F5)3/AlEt3 catalytic systems

Copolymerization of norbornene (NBE) and polar norbornene derivatives undergoes vinyl polymerization by using novel catalyst systems formed in situ by combining bis(β‐ketoamino)Ni(II) complexes {Ni[R₁C(O)CHC(NR₃)R₂]₂ (R_l = R₂ = CH₃, R₃ = naphthyl, 1 ; R₁ = R₂ = CH₃, R₃ = C₆H₅, 2 ; R₁ = C₆H₅, R₂ = CH₃, R₃ = naphthyl, 3 ; R_l = R₂ = CH₃, R₃ = 2, 6‐(CH₃)₂C₆H₃, 4 ; R₁ = R₂ = CH₃, R₃ = 2, 6‐′Pr₂C₆H₃ 5 ; R₁ = C₆H₅, R₂ = CH₃, R₃ = 2, 6‐′Pr₂C₆H₃, 6 )} and B(C₆F₅)₃/AlEt₃ in toluene. The 1 /B(C₆F₅)₃/AlEt₃ catalytic system is effective for copolymerization of NBE with NBE OCOCH₃ and NBE CH₂OH, respectively, and copolymerization activity is followed in the order of NBE CH₂OH > NBE OCOCH₃ > NBE CN. The molecular weights of the obtained poly(NBE/NBE CH₂OH) reached 5.97 × 10⁴ to 2.07 × 10⁵ g/mol and the NBE CH₂OH incorporation ratios reached 7.0–55.4 mol % by adjusting the comonomer feedstock composition. The copolymerization of NBE and NBE CH₂OH also depend on catalyst structures and activity of catalyst followed in the order of 2 > 1 > 3 > 5 > 4 > 6 . The molecular weights and NBE CH₂OH incorporation ratios of poly(NBE/NBE CH₂OH) were adjustable to be 1.91–5.37 × 10⁵ g/mol and 9.5–41.1 mol %  OH units by using catalysts 1 – 6 . The achieved copolymers were confirmed to be vinyl‐addition type, noncrystalline and have good thermal stability (T_d = 380–410°C). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of diantimony trioxide on direct esterification between terephthalic acid and ethylene glycol

Experiments at various Sb₂O₃ concentrations were made in a pilot plant and the effect of Sb₂O₃ on continuous esterification between terephthalic acid (TPA) and ethylene glycol (EG) was obtained. Reaction rate constants of the previously reported reaction scheme were determined to fit with the experimental data obtained. It was found that the effect of Sb₂O₃ on reaction rate constant (k_i) can be expressed as follows.

• k₁ = (3.75 × 10^?4Sb + 1.0) × 1.5657 × 10⁹exp(?19,640/RT)
• k₂ = (4.75 × 10^?4Sb + 1.0) × 1.5515 × 10⁸exp(?18,140/RT)
• k₃ = (6.25 × 10^?4Sb + 1.0) × 3.5165 × 10⁹exp(?22,310/RT)
• k₄ = (4.50 × 10^?4Sb + 1.0) × 6.7640 × 10⁷exp(?18,380/RT)
• k₅ = (3.50 × 10^?4Sb + 1.0) × 7.7069 × exp(?2810/RT)
• k₆ = (1.75 × 10^?4Sb + 1.0) × 6.2595 × 10⁶exp(?14.960/RT)
• k₇ = (3.75 × 10^?4Sb + 1.0) × 2.0583 × 10¹⁵exp(?42,520/RT)

Simulation of esterification with these reaction rate constants at various Sb₂O₃ concentrations was made and the following results were obtained.

• 1 Sb₂O₃ accelerates the esterification reaction between TPA and EG.
• 2 Sb₂O₃ accelerates the main reaction and its effects on side reactions are minor. The higher the addition rate of Sb₂O₃, the lower the carboxyl end-group concentration (AV) and diethylene glycol content (DEG).
• 3 The comparison between simulation with potassium titanium oxyoxalate (PTO) in the previous report and with Sb₂O₃ in the present report shows that the acceleration of polycondensation reaction by Sb₂O₃ is higher. DEG formation rate is lower with PTO than Sb₂O₃.