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.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

有机羧酸钠盐对PET结晶和熔融行为的影响

采用差示扫描量热仪研究了5种具有不同取代基的苯甲酸钠盐作为结晶成核剂对聚对苯二甲酸乙二醇酯（HET）结晶和熔融行为的影响，并同滑石粉进行了对比。结果表明，成核剂的加入能明显改变PET的结晶和熔融行为。苯甲酸钠、对苯二甲酸甲酯单羧酸钠和对羟基苯甲酸钠提高既汀的熔融结晶温度（Tc）分别达22．93、21．7和19．37℃，但使PET降解严重；对苯酚钠甲酸钠能够提高Tc达17．75℃且对PET相对分子质量影响很小；对苯二甲酸二钠成核作用最差。低于滑石粉。此外，成核剂的成核能力越强，PET双熔融峰中的低温峰顶温度就越高。     

Degradation of polyethylene terephthalate films in the presence of lubricants for HFC 134a: a critical issue for hermetic motor insulation systems

Earlier studies conducted in the use of sealed tubes with polyalkylene glycol lubricants and polyethylene terephthalete (PET) films revealed that the PET films exhibited embrittlement and (visual) degradation. This led to an investigation of PET embrittlement mechanisms with the new lubricants used with HFC 134a. The lubricants studied were three polypropylene glycols (the monol, the diol and the completely end-capped glycols), pentaerythritol ester and a blend of monol and ester. The effects of moisture content, temperature and lubricant structure were studied. All lubricants in this study were of viscosity grade ISO-32 (150 SUS). The results were compared to PET film embrittlement in the presence of CFC 12 and mineral oil. This study reconfirmed the earlier findings that the PET films must be dried to lower than 0.1 wt.% moisture content for use in hermetic systems. This paper discusses the effect of the moisture content of the lubricant and the effect of the lubricant structure on PET films. The dependence of the various mechanisms on temperature is shown. Esters and end-capped polyalkylene glycols are recommended for use with HFC 134a.     

Effect of fluoropolymer antidripping agent on the microstructure and properties of polyesters

Poly(ethylene terephthalate) (PET) is of excellent mechanical properties and melt processability and is widely used as raw material for textile fibers. However, the flame retardant properties of PET were rather poor, and both reactive and additive phosphorus- and halogen-containing compounds have been employed to enhance the reaction-to-fire properties while the meltdripping behaviour during burning hasn’t been handled properly with the flame retardants. In this work, fluoropolymer was blended with both pure PET (pPET) and reactive phosphorus-containing flame retarded copolyester (fPET), and the flame retardance and char formation and mechanical properties of the resulted pPET and fPET blends were investigated. The tensile strengths of modified pPET samples were worsen whereas those of modified fPET samples were improved at low concentrations. The initial thermal degradation in nitrogen was accelerated remarkably for the two polyesters with fluoropolymer. The oxygen indices of the all modified samples were reduced while char formation and meltdripping suppression were encouraged. The apparent melt viscosity and elasticity for the two polyesters were gained much with antidripping agent. Therefore, fluoropolymer improved char formation of the two polyesters based on the gaseous phase mechanism while the partial suppression of meltdripping behavior and the decrease of mechanical properties mainly originated from the increase of melt viscosity via fibrillation for pPET.     

瓶级聚酯切片中乙醛含量的控制

对瓶级聚对苯二甲酸乙二酯(PET)原料中的乙醛含量、第三组份(间苯二甲酸)含量、原料比表面积以及工艺参数控制等对产品中乙醛含量的影响进行了讨论，得出了合适的工艺操作条件，并注意到预结晶单元和冷却单元的工艺参数控制对产品乙醛含量的影响最显著，从而为生产乙醛含量小于1．0μg/g的瓶级高粘度PET切片提供了参考。     

Thermal properties and crystalline structure of liquid crystalline poly(ethylene terephthalate‐co‐2(3)‐chloro‐1,4‐phenylene terephthalate)

Thermal properties and crystalline structure of liquid crystalline (LC) poly(ethylene terephthalate‐co‐2(3)‐chloro‐1,4‐phenylene terephthalate) [copoly(ET/CPT)] were investigated using differential scanning calorimetry (DSC), thermogravimetry (TGA), limiting oxygen index (LOI) measurement, electron dispersive X‐ray analysis (EDX), X‐ray diffractometry, and infrared spectrometry (IR). The thermal transition temperatures of copoly(ET/CPT) were changed with the composition. Copoly(ET/CPT) showed two thermal decomposition steps and the residues at 700°C and LOI values of copoly(ET/CPT) were almost proportional to its chlorine content. The activation energy of thermal decomposition of LC units was very low compared to that of poly(ethylene terephthalate)(PET) units. Crystal structure of copoly(ET/CPT) (20/80) was of triclinic system with the lattice constants of a = 9.98 A?, b = 8.78 A?, c = 12.93 A?, α = 97.4°, β = 96.1°, and γ = 90.8°, which is very close to that of poly(chloro‐p‐phenylene terephthlate) (PCPT) with the lattice constants of a = 9.51 A?, b = 8.61 A?, c = 12.73 A?, α = 96.8°, β = 95.4°, and γ = 90.8°. When copoly(ET/CPT)(50/50) was annealed at 220°C in vacuum, crystallization induced sequential reordering (CISR) was not observed but the heat of fusion was slightly increased due to the increase of the trans isomer content in PET units. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1286–1294, 2002; DOI 10.1002/app.10451     

Mechanical and thermal properties of poly(ethylene terephthalate) fibers crosslinked with disulfonyl azides

A novel method for the crosslinking of poly(ethylene terephthalate) fibers is described using 1,6‐hexanedisulfonyl azide, 1,3‐benzenedisulfonyl azide, and 2,6‐naphthalenedisulfonyl azide. The azides are diffused into poly(ethylene terephthalate) fibers (Dacron) from perchloroethylene solution, and the fibers are heat treated to bring about decomposition of the sulfonyl azide and give rise to crosslinking. A study is made of the mechanical and thermal properties of the resultant fibers, which are changed considerably in comparison to the untreated fiber. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1517–1527, 2002     

双噁唑啉化合物对PBT的增粘作用

以２．２＇－双（２－唑啉）和双（２－唑啉基）苯作扩链剂，用焙融挤出的方法，对聚对苯二甲酸丁二酯（ＰＢＴ）进行扩链，考察扩链剂的用量、反应时间和反应温度对ＰＢＴ的特性粘度及端羧基含量（ＣＶ）的影响。结果表明，当用２，２＇－双（２－唑啉）作扩链剂时，ＰＢＴ的特性粘度［η］从０．７９９提高到０．９２６ｄＬ／ｇ，ＣＶ降至５ｅｑ／１０￣６ｇ以下；当用双（２－　唑啉基）苯作扩链剂，［η］从０．７６３增至０．９２５ｄＬ／ｇ，ＣＶ降至１０ｅｑ／１０￣６ｇ以下，达到了较满意的扩链效果。