Modeling of solid-state polymerization of poly(ethylene terephthalate)

A mathematical model for solid-state polymerization of poly(ethylene terephthalate) was developed. The effects of temperature and chain entanglement on chain mobility were considered to estimate the rate constants of chemical reactions. The diffusivities of volatile byproducts could be determined using the free volume theory.^13,14 The model predictions were validated with experimental data reported in the literature. In addition, assuming that the concentration profiles of volatile byproducts in spherical particles are described by a sinusoidal function, the mass transfer rate of the byproducts at a given time could be derived as an ordinary differential equation that can be easily treated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:837–846, 1998     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Raman spectroscopy of flowing poly(ethylene terephthalate) melts

Studies have been made of the Raman spectrum of a poly(ethylene terephthalate) melt being extruded through a glass die. The effects observed in the spectrum are interpreted in terms of changes in molecular shape which vary with shear rate and melt temperature.     

Volatile products of poly(ethylene terephthalate) thermal degradation in nitrogen atmosphere

Thermal degradation of PET was studied in a nitrogen atmosphere at 200–700°C. The experiments were carried out in a tubular furnace under isothermal conditions. The volatile substances evolved from PET were identified and quantified. Weight losses of PET during the thermal degradation in different temperatures were determined. The results are presented on plots as a function of the degradation temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1894–1901, 2000     

Effects of pH and Neutral Salts on the Adsorption of the Poly(ethylene glycol terephthalate) Condensates Toward Poly(ethylene terephthalate) Fiber

This study deals with the effects of pH and neutral salts on the adsorption of PET fiber with four kinds of poly(ethylene glycol terephthalate) condensated from dimethyl terephthalate (DMT) and poly(ethylene glycol) (PEG). The surface properties of the aqueous solution, the contact angle of polyol‐treated PET fabrics, and its parameters were also discussed. The pH of the solution or the adding of neutral salt in the polyol solution largely affected the contact angle of polyol‐treated PET fabrics as well as the surface tension of the solution. A lower pH of the polyol solution or adding neutral salts in the solution showed a lower surface tension and a lower contact angle that resulted in a better adsorption between polyol and poly(ethylene terephthalate) fibers. The lower pH of the solutions and a higher valence of the added neutral salt in the solution showed a largely positive effect on the adsorption parameters, and the order of effectiveness is Al₂(SO₄)₃ > MgSO₄ > Na₂SO₄.     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

A review on the potential biodegradability of poly(ethylene terephthalate)

This paper reviews the state of the art in the field of the hydrolytic degradation of poly(ethylene terephthalate) (PET) under bio-environmental conditions. Most of the papers published so far on this subject have been focused on the hydrolysis of PET at high temperatures. Although some authors claim to enhance the biodegradation properties of this aromatic polyester by copolymerization with readily hydrolysable aliphatic polyesters, no clear and satisfying conclusions can yet be formulated. Poly(ethylene terephthalate-co-lactic acid), poly(ethylene terephthalate-co-ethylene glycol), and poly(ethylene terephthalate-co-ε-caprolactone) block and random copolymers are the modifications mainly investigated for biodegradable applications. The hydrodegradability and biodegradability of PET, PET copolymers and PET blends are detailed in this review. A total of 89 references including 16 patents are cited. © 1999 Society of Chemical Industry     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Studies of temperature influence on volatile thermal degradation products of poly(ethylene terephthalate)

The temperature influence on the thermal degradation products evolved from poly(ethylene terephthalate) (PET) was investigated. The experiments were carried out within the temperature range of 200–700°C in air. The main volatile toxic products and weight losses during thermal degradation of PET were determined. The results are presented on plots as a function of the degradation temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2377–2381, 1998     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

A preliminary study of blends of bisphenol a polycarbonate and poly(ethylene terephthalate)

The microstructure of blends of bisphenol A polycarbonate (PC), and poly(ethylene terepthalate) (PETP) has been studied by solvent extraction, infrared spectrophotometry, differential scanning calorimetry and dynamic mechanical thermal analysis. The blends appear to contain two amorphous phases over the whole composition range. The tensile behaviour and the Charpy impact strength of some of the blends have been determined, before and after heat treatment at 125°C for 18 hours. Improved performance of the blends, compared with that of the homopolymers PC and PETP, has been demonstrated.     

Glycolysis of poly(ethylene terephthalate) wastes in xylene

To reclaim the monomers or prepare intermediates suitable for other polymers zinc acetate catalayzed glycolysis of waste poly(ethylene terephthalate) (PET) was carried out with ethylene or propylene glycol, with PET/glycol molar ratios of1 : 0.5–1 : 3, in xylene at 170–245°C. During the multiphase reaction, depolymerization products transferred to the xylene medium from the dispersed PET/glycol droplets, shifting the equilibrium to glycolysis. Best results were obtained from the ethylene glycol (EG) reaction at 220°C, which yielded 80 mol % bis-2-hydroxyethyl terephthalate monomer and 20 mol % dimer fractions in quite pure crystalline form. Other advantages of employment of xylene in glycolysis of PET were improvement of mixing at high PET/EG ratios and recycling possibility of excess glycol, which separates from the xylene phase at low temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2311–2319, 1998     

Aspects of the chemistry of poly(ethylene terephthalate): 5. Polymerization of bis(hydroxyethyl)terephthalate by various metallic catalysts

Bis(hydroxyethyl)terephthalate (BHET) was polymerized to poly(ethylene terephthalate) (PET) in the presence of various metallic catalysts. The influence of the nature and concentration of these catalysts on the rate of polymerization has been investigated. The effect of the reaction temperature has also been studied. The order of decreasing catalytic influence of various metal ions, on the polymerization of BHET was found to be: Ti>Sn>Mn>Zn>Pb>No.     

Swollen-state polymerization of poly(ethylene terephthalate) in fibre form

The swollen-state polymerization of poly(ethylene terephthalate) in fibre form was performed in hydrogenated terphenyl as the swelling solvent. Ultra-high-molecular-weight poly(ethylene terephthalate) (CHMW-PET) fibre with an intrinsic viscosity of 3–4dl g⁻¹ (M_n = 2–3 × 10⁵) was obtained. The polymerization rate of as-spun PET fibres in the swollen state was greater than that of PET granules in the swollen state. It was clarified that the polymerization rate was related to the chain mobility of the starting materials. The chain mobility was influenced by various conditions, such as changing rigidity of the segments during copolymerization, the chain orientation of the starting fibre before swollen-state polymerization and the temperature of pretreatment with the solvent. Pretreatment with solvent before polymerization was effective in increasing the chain mobility. The relation between chain mobility and polymerization rate was examined by wide-angle X-ray diffraction, density, differential scanning calorimetry, solvent content and viscoelastic measurements. Undrawn UHMW-PET fibres could be drawn 10 times or more by the zone drawing technique in spite of their high crystallinity, and the drawn fibre showed high tensile strength (12 g d⁻¹) and high modulus (240 g d⁻¹).     

Surface graft copolymerization of acrylic acid onto corona-treated poly(ethylene terephthalate) fabric

Acrylic acid (AA) was grafted onto the surface of poly(ethylene terephthalate) (PET) fabric after having short-time corona-discharge treatment (CDT) in an atmosphere in the presence of the initiator. The effect of N,N-dimethylformamide (DMF) pretreatment time, CDT time, graft copolymerization time and temperature, concentration of AA, and the content of initiator on graft yield of PET fabric was discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1161–1164, 1999     

Mechanical properties of poly(ethylene terephthalate) modified with functionalized polymers

This study examined the effect of blending poly(ethylene terephthalate) (PET) with 5% of a functionalized polymer. The blends were characterized by particle size and size distribution, unnotched tensile behavior, toughness, and notch sensitivity. The improved properties of blends that incorporated a functionalized elastomer were consistent with in situ formation of a graft copolymer by reaction with PET end groups. Triblock copolymers were examined that had styrene end blocks and an ethylene/butylene midblock (SEBS) with grafted maleic anhydride. The present study extended previous investigations that focused on level of grafting to examine the effects of component molecular weight and PET hydroxyl‐to‐carboxyl end‐group ratio. Increasing the molecular weight of the SEBS and decreasing the hydroxyl‐to‐carboxyl ratio of the PET increased the effectiveness of the SEBS. In addition, a mix of an unfunctionalized SEBS with a functionalized SEBS was more effective than a single SEBS with the same total anhydride content. The same elastomers were the most effective for modifying a lower molecular weight PET (intrinsic viscosity 0.73) and a higher molecular weight PET (intrinsic viscosity 0.95). Some functionalized polypropylenes included in the study did not enhance the properties of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 203–219, 1999     

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.     

聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。     

HT／Surlyn／PEG复合成核剂对PET结晶性能的影响

研究了水滑石(HT)/离子键聚合物(Surlyn)/聚乙二醇(PEG)复合成核剂对聚对苯二甲酸乙二醇酯(PET)非等温结晶性能的影响。通过正交实验选择最佳复合成核剂配方。差示扫描量热分析表明,HT/Surlyn/PEG复合成核剂各组分与PET的质量比为0．5/3/3/100时,PET的结晶温度提高,半结晶时间明显减少,说明PET的成核能力提高,结晶能力增强,结晶速率加快；同时,结晶放热焓和熔融吸热焓增加,说明PET的结晶度得到提高。     

Enthalpy relaxation in poly(ethylene terephthalate) and related polyesters

Enthalpic relaxation data are presented on poly(ethylene terephthalate), poly(ethylene naphthalate) and their copolymers. Analysis of these data allows the determination of the amount of energy absorbed at the glass transition, Q_t, and the location of the enthalpic recovery peak, T_max, as a function of the time of ageing of the samples. Ageing measurements were carried out for periods of up to 2016 h and at temperatures between 40 °C and 110 °C, depending upon the chemical composition of the system being investigated. The enthalpic relaxation rates are influenced by the chemical structure and reflect the effects of local order pinning the chains and influencing the rate of enthalpic recovery. © 2000 Society of Chemical Industry