PET/离聚物共混体系的相容性及形态结构

本文对聚对苯二甲酸乙二酯(PET)与四种不同结构离聚物(Ionomer)的共混体系的相容性及形态结构用差示扫描量热(DSC)和扫描电镜(SEM)等方法进行了详细的研究。结果表明,在通常条件下,PET与Surlyn Na型(S-Na)以及Aclyn钠型与Zn型(A-Na与A-Zn)离聚物为不相容的两相体系,但离聚物的加入,由于离子-偶极间的作用使共混物中PET组分的了Tg略有增高;当离聚物含量高于9％时,共混体系的相容性有所改善;适当的热处理条件下,PET与离聚物间可发生一定的化学反应而使共混体系的相客性得以明显改善。结果还表明,离聚物骨架链的结构以及离子的种类均对共混体系的相容性及形态结构有一定的影响。     

水解稳定性聚对苯二甲酸乙二酯(PET)的研制

本文讨论了聚对苯二甲酸乙二酯(聚酯)在湿热条件下的水解和阻止水解的机理和方法。将合成的水解稳定剂添加到聚酯切片中进行纺丝和水解试验。结果表明,在60～130℃饱和蒸汽长达96h 处理后,水解稳定性聚酯纤维的强度保持率较普通聚酯的高30%以上;水解速率仅为普通聚酯的1/2～1/3(分别为1.7×10~(-6)～4×10~(-4)和3.9×10~(-6)～7.9×10~(-4));水解活化能比普通聚酯的高2.72kJ/mol 左右;纤维热失重(TGA)结果表明,水解稳定性聚酯的分解峰温度比普通聚酯的高10℃左右。     

Rotor-synchronized two-dimensional 13C CP/MAS NMR studies of the orientational order of polymers 2. Melt-extruded poly(ethylene terephthalate) fibers

Determination of the orientational order of morphological components in polyethylene terephthalate (PET) is sought through quantitative application of two-dimensional rotor synchronized magic angle spinning (ROSMAS) ¹³C NMR technique. Previous study in our laboratories had established a procedure for resolution of the carbonyl carbon (CA) and glycol ethylene carbon (GE) resonances into those corresponding to four morphological components.¹ Due to paucity of sidebands in the GE resonances, the focus has been on the CA resonances in this attempt to obtain orientation distributions. A set of PET fibers possessing a broad range of crystalline and orientational order has been used to infer the meaning of NMR-based orientation measurements vis-a-vis other techniques. A surprising finding of this study is the observation that the orientational orders of the broad component in the ¹³C CP/MAS spectrum and the narrow component are very similar in these fibers. ©1995 John Wiley & Sons, Inc.     

Optical characteristics of uniaxial polyester films with the optical axis perpendicular to the surface

The functions of the main indices of refraction n(ν) and absorption κ(ν) of uniaxial thin polyethylene terephthalate films have been calculated by the experimental spectra of frustrated total reflection of s-and p-polarized radiation in the 700–760-cm⁻¹ range. The κ_o(ν) maximum falls at the the 727-cm⁻¹ frequency and the maximum of κ_e(ν) falls at the the 724-and 732-cm^{− 1} frequencies. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 756–759, November–December, 2005.     

New insight into melting and crystallization behavior in semicrystalline poly(ethylene terephthalate)

After isothermal crystallization, poly(ethylene terephthalate) (PET) showed double endothermic behavior in the differential scanning calorimetry (DSC) heating scan. During the heating scans of semicrystalline PET, a metastable melt which comes from melting thinner lamellar crystal populations formed between the low and the upper endothermic temperatures. The metastable melt can recrystallize immediately just above the low melting temperature and form thicker lamellae than the original ones. The thickness and perfection depends on the crystallization time and crystallization temperature. The crystallization kinetics of this metastable melt can be determined by means of DSC. The kinetics analysis showed that the isothermal crystallization of the metastable PET melt proceeds with an Avrami exponent of n = 1.0 ∼ 1.2, probably reflecting one‐dimensional or irregular line growth of the crystal occurring between the existing main lamellae with heterogeneous nucleation. This is in agreement with the hypothesis that the melting peaks are associated with two distinct crystal populations with different thicknesses. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 53–60, 2000     

Crystallization kinetics of poly(trimethylene terephthalate)

The isothermal crystallization kinetics of poly(trimethylene terephthalate) (PTT) have been investigated using differential scanning calorimetry (DSC) and polarized light microscopy (PLM). Enthalpy data of exotherm from isothermal crystallization were analyzed using the Avrami theory. The average value of the Avrami exponent, n, is about 2.8. From the melt, PTT crystallizes according to a spherulite morphology. The spherulite growth rate and the overall crystallization rate depend on crystallization temperature. The increase in the spherulitic radius was examined by polarized light microscopy. Using values of transport parameters common to many polymers (U* = 1500 cal/mol, T_∞= T_g − 30 °C) together with experimentally determined values of T (248 °C) and T_g (44 °C), the nucleation parameter, k_g, for PTT was determined. On the basis of secondary nucleation analyses, a transition between regimes III and II was found in the vicinity of 194 °C (ΔT ≅ 54 K). The ratio of k_g of these two regimes is 2.1, which is very close to 2.0 as predicted by the Lauritzen–Hoffman theory. The lateral surface‐free energy, σ = 10.89 erg/cm² and the fold surface‐free energy, σ_e = 56.64 erg/cm² were determined. The latter leads to a work of chain‐folding, q = 4.80 kcal/mol folds, which is comparable to PET and PBT previously reported. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 934–941, 2000     

Synthesis and Molecular Structure of Binuclear Tin(IV) Complex Bridged by Terephthalate Anion

ＩｎｔｒｏｄｕｃｔｉｏｎＢｅｃａｕｓｅｔｈｅｐｏｌｙｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓ ,ｃｏｎｓｉｓｔｉｎｇｏｆａｒｏｍａｔｉｃｍｕｌｔｉ ｃａｒｂｏｘｙｌｉｃａｃｉｄａｎｄｔｒａｎｓｉｔｉｏｎｍｅｔａｌ,ｈａｖｅａｖａｒｉｅｔｙｏｆｐｏｓｓｉｂｌｅａｐｐｌｉｃａｔｉｏｎｓｒａｎｇｉｎｇｆｒｏｍｆｉｎｅｒｅｔａｒ ｄａｎｔｓｔｏｃａｔａｌｙｓｔｓ ,ａｎｄｐｏｔｅｎｔｉａｌｌｙｖａｌｕａｂｌｅｐｒｏｐｅｒｔｉｅｓｒｅｍｉｎｉｓｃｅｎｔｏｆｚｅｏｌｉｔｅｓ ,ｔｈｅｓｔｕｄｙｏｎｔｈｅｍｈａｓｂｅｅｎａｎ…     

Copolyesterification between poly(butylene terephthalate), terephthalic acid and hydroquinone diacetate: a kinetic analysis

The kinetics of liquid crystalline copolyester synthesis via melt transesterification between poly(butylene terephthalate) (PBT), terephthalic acid (TA) and hydroquinone diacetate (HQDA) is examined. Two different copolyester compositions PBT30/(HQDA+TA) 70 and PBT 50/(HQDA+TA) 50 mol% ratio were synthesized. The ratio of HQDA to TA was kept constant for all the reactions.The copolyesters were synthesized via melt polycondensation route at 265°C, 275°C and 285°C using two different transesterification catalysts, zinc acetate and dibutyl tin oxide. A key postulation assumed in this work is that the reaction originates between TA and HQDA to form a dimer which slices PBT chain. The copolyesterification rate constant for a system containing butylene glycol a more nonpolar moiety compared to ethylene glycol in poly(ethylene terephthalate) has been determined. The activation energy values for the different copolymer systems has also been determined. The rate constants for the uncatalyzed and catalyzed copolyesterification reaction and the activation energy values for the reaction have been determined.     

PET,PBT结晶过程Avrami方程的探讨

用解偏振光法研究了PET,PBT以及PET-PBT,PBT-PBI共聚物在不同条件下的等温结晶过程.结果表明,Avrami指数n值和结晶速度常数随条件不同呈明显规律变化,且n值在绝大多数情况下不成整数.由此提出了这样的假设:n值是一个与晶核中结晶生长点数目相关的参数.