Activation of catalysts for the transesterification of dimethylterephthalate with ethylene glycol

Conclusions A possibility has been demonstrated of shortening the duration of the transesterification reaction between dimethyl terephthalate and ethylene glycol by preliminary treatment of the catalysts or by introducing investigated lower alcohols or acetone into the reaction mixture.Translated from Khimicheskie Volokna, No. 3, pp. 49–50, May–June, 1990.     

Transesterification of dmt with ethylene glycol catalyzed by amberlyst 15

The catalytic effects of the macroreticular cation exchange resin Amberlyst 15 (H+) on the transesterification of dimethyl terepbthalate with ethylene glycol have been investigated in a batch reactor and at the temperature of 146°C with the aid of extensive chemical analysis. The resin exhibited significant intraparticle diffusion effects for the disappearance of dimethyl terephthalate and promoted the dehydration and subsequent etherification and polymerization reactions of ethylene glycol to a very significant extent. The side reactions of ethylene glycol rendered the transesterification process in the presence of Amberlyst 15 (H+) inefficient.     

PET synthesis in the presence of lanthanide catalysts

Syntheses of poly(ethylene terephthalate), PET, by transesterification of dimethyl terephthalate with ethylene glycol in the presence of well-known catalysts and various lanthanide compounds were performed. Lanthanide catalysts appeared to be much more efficient in the first stage of the process (transesterification in the presence of an excess of ethylene glycol), and less active in polycondensation. PET produced with lanthanides was found to possess enhanced thermal and hydrolytic stability as compared to PET synthesized with well-known catalysts and commercial PET. © 1995 John Wiley & Sons, Inc.     

A modeling of semibatch reactors for melt transesterification of dimethyl terephthalate with ethylene glycol

A mathematical model of a semi batch reactor was developed to investigate the oligomerization reactions in the melt transesterification of dimethyl terephthalate with ethylene glycol catalyzed by metal acetate catalyst. The detailed kinetic scheme based on the molecular species model is used to estimate the conversion of methyl ester groups and the concentrations of various oligomeric species. The numerical simulation of the model shows that the oligomerization reactions lower the overall conversion of methyl ester end groups. Effects of ethylene glycol/dimethyl terephthalate mole ratios, reaction temperature and, catalyst concentration on the conversion, oligomer concentration, oligomer molecular weight, and molecular weight distribution were also analyzed.     

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.     

Study of the glycolysis of PET by oligoesters

A series of oligoesters was synthesized via the transesterification of dimethyl isophthalate with neopentyl glycol or tetraethylene glycol and the esterification of adipic acid with neopentyl glycol or tetraethylene glycol under diol/diester or diol/diacid molar ratios sufficient to limit molecular weight increasing.These oligoesters were used to depolymerize poly(ethylene terephthalate) (PET) in the presence of zinc acetate to yield new types of glycolysates. The oligoesters and the glycolysates are characterized by ¹H NMR, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analyses and matrix assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). These analyses revealed the structure of the different glycolysates.     

Acidity and corrosivity of the volatile distillates in the synthesis of polyethylene terephthalate from dimethyl terephthalate and ethylene glycol

Conclusions The acidity and aggressive properties of volatile distillates in the synthesis of polyethylene terephthalate from ethylene glycol and dimethyl terephthalate have been studied on industrial technological lines. It has been shown that the acidity of the distillates increases as the synthesis process approaches completion. The composition of some of the acidic impurities in the distillates has been identified. It has been shown that the aggressive properties of distillates are determined by their content of strong acids.The effect of the acidity of the original ethylene glycol on the aggressive properties of distillates has been described. It has been shown that the use of neutral ethylene glycol sharply reduces the aggressive properties of the distillates.Measures have been recommended for reducing the aggressive action of distillates and of their distillation products on apparatus and pipelines of nonalloyed steels or cast iron.Translated from Khimicheskie Volokna, No. 2, pp. 12–14, March–April, 1988.     

Unsaturated polyesters based on bis(2-hydroxyethyl)terephthalate

A series of unsaturated polyesters based on bis(2-hydroxyethyl)terephthalate, ethylene glycol, propylene glycol, diethylene glycol, maleic anhydride and styrene were prepared. Properties of these castings were investigated and compared with those analogues based on dimethyl terephthalate or polyester oligomers formed by depolymerization of poly(ethylene terephthalate). It is found that properties of castings based on bis(2-hydroxyethyl)terephthalate are superior to those based on polyester oligomer. When compared with those based on dimethyl phthalate, the castings have higher hardness and heat distortion temperature, but lower tensile strength and elongation; other properties are very similar.     

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%.     

新型共聚酯-PETG

PETG(聚对苯二甲酸乙二醇酯-1,4-环己二甲醇酯)是一种结晶度很低甚至是完全不结晶的共聚酯,具有优异的韧性、透明度、易加工和耐化学性能。它是由DMT(对苯二甲酸二甲酯)、EG(乙二醇)、CHDM(1,4-环己二甲醇)在通N2条件下发生酯交换反应,然后在高真空度下发生缩聚反应而制得。本文就PETG的制备、性能和应用等方面作一论述。     

酯交换法合成对苯二甲酸二环己酯

研究了以无水碳酸钾、自制的钛酸酯等化合物为催化剂,对苯二甲酸二甲酯和环己醇为原料,进行酯交换反应制取对苯二甲酸二环己酯,考察了催化剂用量、反应温度、反应时间、反应物摩尔配比等因素的影响.适宜的操作条件为:环己醇与对苯二甲酸二甲酯的摩尔配比为3:1、反应温度160～190℃、反应时间7 h、催化剂用茸为1.0%.此时,对苯二甲酸二甲酯转化率达93%以上,对苯二甲酸二环己酯的收率达92%以上.     

The characterisation of dope dyed poly (ethylene terephthalate)

By analysing the polycondensation of ethylene glycol with dimethyl terephthalate, the influence of 1,4-aminoanthraquinone dyestuffs on the chemical and molecular properties of dope dyed poly(ethylene terephthalate) has been determined. The results show that dope dyed poly(ethylene terephthalate) differs from the uncoloured polymer by a possession of a higher amount of -COOH end groups and diethylene glycol units. The shape and the position of molecular weight distribution curves determined by gel permeation chromatography are also influenced by the soluble dyestuffs used.     

Preparation and characterization of comb-shaped polyesters from 2,2-dioctadecyl-1,3-propanediol and phthalic acids

Summary New types of comb-shaped polyesters have been prepared by transesterification of 2,2-dioctadecyl-1,3-propanediol and the three isomeric diphenyl phthalates. Intrinsic viscosity and SEC analyses allowed determination of DPs (60–89) and molar masses; results compare well with absolute average weight molar masses (56,000–118,000) determined by low-angle laser light scattering. High-resolution ¹³C NMR reveals the characteristic aromatic and glycol polyester patterns; it resolves many side-chain methylene carbons, but shows no evidence of end-groups. All the polyesters are crystalline as shown by X-ray diffractometry and DSC, the crystallinity being exclusively due to the octadecyl side-group crystallization in the hexagonal form. The results indicate that the crystallinity decreases substantially when going from the ortho- to the terephthalate polyester.     

Network formation in poly(ethylene terephthalate) by thermooxidative degradation

Gelation of poly(ethylene terephthalate) by heating at 263°–300°C was investigated. Under nitrogen flow, crosslinks were scarcely formed. However in air, degradation and crosslinking were common, and these were accelerated by purging gaseous and sublimable degradation products out of the system with a stream of air. The main component of the sublimate was terephthalic acid. Infusible and insoluble gel was treated with methanol at 260°C, and then the methanolysis products were separated into two parts. The methanol-insoluble part exhibited a polyene structure with ester groups, and the methanol-soluble part contained dimethyl terephthalate, ethylene glycol, and some 1,2,4-butanetriol. To clarify the relation between the crosslinking and the formation of vinyl ester groups, the degradation of vinyl methyl terephthalate was studied. Thermoxidative degradation of linear polyesters other than poly(ethylene terephthalate) was also studied. Poly(ethylene isophthalate) and poly(ethylene sebacate) were easily gelated. However, poly(trimethylene terephthalate) and poly(neopentyl terephthalate) were scarcely gelated. The primary reaction leading to crosslinking is assumed as follows. At first, the random scission of polyester chain may take place forming carboxylic acids, vinyl esters, aldehydes, etc. After accumulation of vinyl esters to some extent, vinyl polymerization of the esters takes place and network structures are formed.     

Preparation and hydrolytic degradation of sulfonated poly(ethylene terephthalate) copolymers

A series of poly(ethylene terephthalate-co-ethylene 5-sodiosulfoisophthalate) copolyesters containing from 1 up to 50 mol% of sulfonated units was prepared by melt polycondensation from ethylene glycol and mixtures of dimethyl terephthalate and dimethyl 5-sodiosulfoisophthalate. The resulting copolymers had a random microstructure and contained oligo(ethylene glycol) units in amounts increasing with the content in sulfonated isophthalate units. Copolyesters with more than 20 mol% of 5-sodiosulfoisophthalic units were amorphous and easily soluble in water. The hydrodegradability of the copolyesters was very high as compared to poly(ethylene terephthalate), and increased with the content in sulfonated units. It was demonstrated that the susceptibility to acidic hydrolysis of these copolymers is mainly due to the presence of the sodium sulfonate groups, the influence of the oligo(ethylene glycol) units in this regard being noticeable but limited.     

Synthesis and Characterisation of Branched Poly(ethylene terephthalate)

Branched poly(ethylene terephthalate)s (PET) were synthesised with a variety of molar masses and with a large range of degree of branching by introduction of mono-, tri-(glycerol) and tetra-functional (pentaerythritol) comonomers to dimethyl terephthalate and ethylene glycol. The monofunctional alcohols, dodecanol and benzyl alcohol, were used as terminating agents to minimise gelation. The effect of various reaction parameters, such as percentage glycerol or pentaerythritol and polymerisation time, on limiting viscosity number [η] and weight average molar mass (M_w) were investigated. The thermal behaviour of branched PET was studied by differential scanning calorimetry; all samples showed a characteristic double endothermic melting peak and the glass transition temperature was not observed. Some branched PETs were subjected to solid-state polymerisation to increase the molar mass of previously prepared branched polymers. The solid-state polymerisation technique showed that the process not only promoted the molar mass but, more importantly, it increased the crystallinity of the polymer. Overall, the solid-state reaction rate was governed by initial molar mass, crystallinity, reaction temperature and time. © of SCI.     

Transesterification of dimethyl terephthalate with ethylene glycol. A kinetic model of the process

Conclusions The possibility of calculating and obtaining the values of the rate constants of reactions (4)–(6) in the process of transesterifying DMT with ethylene glycol over various catalytic systems at a 1.8 molar ratio of the starting components, EG:DMT, has been shown.The results presented permit one to solve the problem of optimizing the process of transesterifying DMT with ethylene glycol with the objective of reducing the molar ratio of the starting materials and cutting down energy outlays and starting material norms.Translated from Khimicheskie Volokna, No. 6, pp. 10–13, November–December, 1983.     

Sequence distribution and crystal structure of poly(ethylene/trimethylene terephthalate) copolyesters

The sequence distribution and the crystal structure of copolyesters synthesized from ethylene glycol, 1,3-propanediol, and dimethyl terephthalate with different molar volume ratios were investigated in this study. The triad sequence probabilities of ethylene/trimethylene terephthalate were characterized from the aromatic quaternary carbons by ¹³C NMR. The composition of the copolyesters was determined from the aromatic quaternary carbons by ¹³C NMR, and the methylene protons by ¹H NMR. Results show that 1,3-propanediol reacted faster with terephthalic acid in copolyester polymerization than ethylene glycol. The difference in monomer reactivity is significant in the polymerization. Although the constitutional units revealed a random distribution in the molecular chain by ¹³C NMR, crystallites formed across the full range of ethylene glycol/1,3-propanediol composition by use of differential scanning calorimetry, a hot stage polarizing microscope, and a wide angle X-ray diffraction method. The WAXD deconvolution results show that the major constitutional repeating unit in the molecular chain dominates the crystal structure as a host crystal. The crystal structure was examined by a scanning electron microscope after a solvent etching. Photomicrographs show that the random distribution of the third constitutional unit in the molecular chain of copolyester significantly disturbs the host crystal formation and lamellar orientation.     

Kinetics of transesterification of dimethyl terephthalate with poly(tetramethylene ether) glycol and 1,4-butanediol catalyzed by tetrabutyl titanate

The kinetics of tetrabutyl titanate catalyzed transesterification of dimethyl terephthalate with poly(tetramethylene ether) glycol of various molecular weight has been studied in the presence and absence of 1,4-butanediol. Detailed analysis of experimental data with a proposed kinetic model indicates that the equal reactivity hypothesis for functional groups is valid within a wide range of experimental conditions studied. It is also found that the reactivity of hydroxyl groups of macrodiols such as poly(tetramethylene ether) glycol is independent of the chain length of the polymer. Effect of various reaction parameters on the transesterification rate and the resulting product composition is also discussed.     

The Nature of the Reaction of Chromium(III) Complexes with Poly(Ethylene Terephthalate) Fibres

The effect of the nature of the ligands in chromium(III) complexes on the affinity of chromium(III) complexes for poly(ethylene terephthalate) fibre materials is demonstrated. It was found that donor-acceptor bonds with terminal groups (hydroxyl and carboxyl) and oxygen heteroatoms in the macromolecule of the polymer are formed in the reaction of chromium cations with poly(ethylene terephthalate) macromolecules.__________Translated from Khimicheskie Volokna, No. 1, pp. 38–39, January–February, 2005.