聚对苯二甲酸二甲酯/聚2,5-呋喃二甲酸二甲酯嵌段聚酯的合成与表征

以生物基单体2,5-呋喃二甲酸、乙二醇为原料合成聚2,5-呋喃二甲酸乙二醇酯(PEF)。采用熔融酯交换法以PEF聚酯部分取代聚对苯二甲酸乙二醇酯(PET),制备了系列PET-b-PEF嵌段共聚酯。通过核磁共振仪(NMR)、差示扫描量热仪(DSC)、热失重仪(TGA)、X射线衍射仪(XRD)等技术手段表征了共聚酯的结构和性能。结果表明,该系列共聚酯的玻璃化转变温度(Tg)在75.8~80.3℃之间,且随着PEF链段质量分数的增加,PET-b-PEF嵌段共聚酯的Tg先降低后升高,结晶度和熔融温度逐渐降低。当PEF链段含量高于15%时,共聚酯没有结晶峰。该系列共聚酯具有良好的热稳定性,起始分解温度在392.2~407.9℃之间,与所制备的PET起始分解温度403.3℃接近。且当共聚酯中PEF链段含量低于15%时,起始分解温度均在407℃左右,优于PET的热稳定性。     

链段相容性对聚酯-聚醚多嵌段共聚物组成均一性的影响

<正> 由结晶型芳族聚酯为硬链段,无定型脂肪族聚醚为软链段的聚酯-聚醚多嵌段共聚物,是一类性能优良的热塑弹性体,本文研究链段相容性对这类聚合物组成均一性的影响,因此,合成了一系列不同链段结构的聚酯-聚醚多嵌段共聚物。 如硬链为聚对苯二甲酸乙二醇酯(PET)和丁二醇酯(PBT);软链段有聚乙二醇醚(PET)、聚丁二醇醚(PTMG)、聚二醇醚(PPG)和四氢呋喃同环氧丙烷的共聚醚二醇     

聚丙烯与聚酯-聚醚多嵌段共聚物共混的研究

聚丙烯和聚酯-聚醚多嵌段共聚物的熔融共混物是微多相分散体系,其力学性能和软链段的结构有关。DSC和偏光显微镜图分别表明共混物中聚丙烯结晶度以及球晶尺寸随聚酯-聚醚的混入量而变小。聚丙烯和少量聚酯-聚醚多嵌段共聚物共混,可改进聚丙烯的流变性,吸湿性和染色性。     

微相分离及链结构对聚酯-聚醚嵌段共聚物分子运动的影响

本文首先研究了成型方法和热处理对聚对苯二甲酸乙二酯与聚氧四亚甲基嵌段共聚物动态力学温度谱的影响,结合应力-应变曲线讨论了微相分离与力学性能的关系。其次,比较了三种不同链结构的聚酯-聚醚嵌段共聚物在不同温控程序下的动态力学温度谱,讨论了链结构对软链段结晶的影响。最后观察了聚氨酯-聚醚嵌段共聚物双重玻璃化转变现象并作了解释。     

聚酯-聚醚多嵌段共聚物的共聚改性

高硬段含量和高软段分子量的聚酯-聚醚多嵌段共聚物有明显的组成不均一性,可分离出大量高熔点的氯仿不溶组份.通过和5mol%间苯二甲酸二甲酯(DMI)共聚,可改进其表观组成均一性,得到不含氯仿不溶物和力学性能优良的硬段含量为40wt%、软段分子量为4000的聚对苯二甲酸乙二酯-聚乙醇醚多嵌段共聚物(PET-PEG).另一合成途径是以间苯二甲酸(IPA)酸解 PET,再和端羟基聚乙二醇醚共缩聚,也可制得相应的改性 PET-PEG.降低聚醚分子量可以有效地改进其组成均一性.     

含异山梨醇的全生物基PBS嵌段共聚酯的制备及性能

采用熔融扩链法制备了高分子量的全生物基聚丁二酸丁二醇酯(PBS)-聚丁二酸异山梨醇酯嵌段共聚酯.GPC测试结果表明,该嵌段共聚酯在较高的异山梨醇(Is)含量时仍具有较高的分子量,其M_n介于3.5×10~4~7.0×10~4之间.采用TGA和DSC对嵌段共聚酯的热稳定性和结晶性能进行了研究,结果表明嵌段共聚酯保持了PBS优异的热稳定性和结晶性能,即使异山梨醇含量达60 mol%,其熔点较PBS仅下降2 K.采用DMA分析了嵌段共聚酯的玻璃化转变温度T_g,发现随着异山梨醇含量的增加,其T_g随之升高,当Is含量为60mol%时,嵌段共聚酯的T_g高达68℃,并且共聚酯的2个链段具有很好的相容性.力学性能测试结果表明,异山梨醇的引入可使PBS的力学性能得到明显地提高和调控,随着异山梨醇含量的增加,嵌段共聚酯的拉伸强度先增加后降低,断裂伸长率约是PBS的2倍,其中,当异山梨醇含量达60 mol%时,嵌段共聚酯的屈服强度由PBS的35.0 MPa增至43.0 MPa.     

多嵌段聚醚-酯共混物的微相结构与血液相容性研究

本工作合成了两种性质不同的聚醚-酯多嵌段共聚物,一种是以聚对苯二甲酸乙二酯为硬链段,聚乙二醇(PEGT)为软链段的亲水性多嵌段共聚物,另一种是以聚对苯二甲酸乙二酯为硬链段,聚四亚甲基醚二醇(PTMGT)为软链段的疏水性多嵌段共聚物。将两种共聚物以一定的比例共混,制备多嵌段聚醚-酯共混物。 改变共混物的组成,研究其微相结构与血液相容性的关系。采用动态力学谱(VES)、示差扫描量热(DSC)、透射电镜(TEM)和扫描电镜(SEM)等测定共混物的微观结构,采用微球柱法评价共混物的血液相容性。实验结果表明:材料的微观非均相结构及亲水平衡是决定血液相容性的重要因素。     

嵌段聚醚聚氨酯-酯热塑性弹性体的合成和性质

 本文用对苯二甲酸双羟基乙二醇酯及其二聚体作扩链剂,合成了一系列聚醚聚氨酯-酯嵌段共聚物(PEUE),并用热分析法、动态力学分析、应力-应变等方法对所合成的聚氨酯材料进行了形态结构和性能关系的研究,结果表明:这类聚氨酯弹性体由于硬段具有较好的结晶性,致使材料的力学性能得到提高;另外,由于硬段酯基与软段聚醚的相互作用,材料的相容性有所改进.     

聚对苯二甲酸乙二醇酯/聚乙二醇醚插层嵌段共聚物的结晶性能

合成了不同用量、不同分子量的聚乙二醇醚(PEG)或聚丁二醇醚(PTMC)与聚对苯二甲酸乙二醇酯(PET)/蒙脱土(MMT)的嵌段共聚物。研究了MMT在共聚物中的分散状态及PEG或PTMG对PET/MMT插层聚合物结晶性能的影响。结果表明,MMT在共聚物中以纳米尺寸分散;加入PEG或PTMG增强了聚酯链段的柔顺性,使共聚物熔体降温过程的结晶温度提高,冷结晶温度降低,即插层嵌段共聚物的结晶速率提高;在合成的共聚物中,分子量为2000,用量为DMT的6%的PEG对插层共聚物结晶速率的促进作用最大     

PET类共聚酯的玻璃化转变

用DSC,IR和DLI(解偏振光法)等方法研究了聚(对苯二甲酸/间苯二甲酸)乙二醇酯[P(ET/EI)]和聚对苯二甲酸(乙二醇/丁二醇)酯[P(ET/BT)]系列共聚酯的玻璃化转变.结果表明,共聚酯的玻璃化转变是玻璃态有序结构解序后的一种转变.随ET链段含量的减少,两系列共聚酯的玻璃化转变在DSC中均表现出由拐折渐变为峰形,这是由于需要维持构象转变的ET链段在数量上的减少所致.玻璃态共聚酯的有序结构与分子链末端的游离羟基有关,游离羟基与羰基形成氢键是PET及可结晶共聚酯在结晶时必须经历的一个过程,而不能结晶的共聚酯(IPA30)则因该氢键的形成导致其玻璃化转变的消失.     

On the Structure of Poly-(Ethylene Oxide) When Immersed in Water

It can be shown that poly-(ethylene oxide) in its monomeric form, at molecular weights greater than about 1,000, cannot be soluble in water. Nonetheless, in actual practice poly-(ethylene oxide) is widely used for its hydrophilicity and for its unlimited aqueous solubility. The explanation for this apparent contradiction lies in the fact that poly-(ethylene oxide) molecules form a nonionic surfactant of a novel category, with its hydrophilic and hydrophobic chains attached to each other over their entire length so that its hydrophilic ethylene oxide side is exposed to the water interface while the hydrophobic poly-(ethylene) side remains hidden thanks to the formation of micelles.     

Shape Memory Properties in Poly(ethylene oxide)–Poly(ethylene terephthalate) Copolymers

Memory effects of several copolymers of poly(ethylene oxide) (PEO) and poly(ethylene terephthalate) (PET) were illustrated with photos, determined with shrinkage experiments and characterized by the recovery of samples to their original figures. Copolymers of appropriate composition could undertake an approximately full recovery which is tightly related to the annealing temperature at which shrinkage of samples occurs to some extent. Melting and recrystallization of PEO segments may be responsible for the memory effect. The memory properties of samples almost kept unchanged after many fatigue cycles (e.g. 15–20 cycles), which could make these copolymers useful in practical applications as novel shape memory materials. © 1997 John Wiley & Sons, Ltd.     

结晶性芳香聚酯高压结晶行为研究进展

运用高压极限手段研究聚合物的结构、形态和性能是20世纪60年代以来兴起的一项聚合物前沿课题。本文主要结合作者自己的研究工作，重点叙述聚对苯二甲酸乙二醇酯(PET)的高压结晶行为研究，包括温度、压力、时间及分子量对PET高压结晶行为的影响，高压结晶PET的形态。以及对PET伸直链晶体结晶机理的探讨，同时简要介绍了对其它结晶性芳香聚酯诸如聚对苯二甲酸丁二醇酯(PBT)及聚对萘二甲酸乙二醇酯(PEN)的高压结晶行为研究，反映了该领域的研究概况和最新进展。并对今后的研究提出了展望。     

An evoluted bio-based 2,5-furandicarboxylate copolyester fiber from poly(ethylene terephthalate)

A series of bio-based poly(ethylene terephthalate-co-ethylene 2,5-furandicarboxylate) (PEFT) fibers was prepared via the industrially feasible melt-spinning and hot-drawing process. The effect of 2,5-furandicarboxylic acid (FDCA) content on the fibers properties was studied using differential scanning calorimetry, wide-angle X-ray diffraction, sound velocity, tensile, and boiling water shrinkage tests. It was found that the PEFT fibers showed comparable or superior tenacity to the PET fibers under the same conditions, especially the PEFT-4 fibers exhibited the highest tenacity (2.3, 2.9 cN/dtex for the drawn PET and PEFT-4 fibers prepared at the same take-up speed of 2500 m/min and a fixed draw ratio of 1.6). Moreover, the boiling water shrinkage of the PEFT fibers was quite close to that of the PET fibers under the same conditions, showing that the PEFT fibers were comparable to the PET fibers in heat resistance. The results indicated that the bio-based PEFT fibers would be a feasible alternative for the PET fibers, in terms of sustainability, processability, and mechanical properties. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 320–329     

Liquid adsorption chromatography of polyethers: experiments and simulation

The adsorption behavior of poly(ethylene glycol) (PEG) in reversed-phase chromatography is studied both experimentally and theoretically and a computer simulation of chromatograms is performed on the basis of these studies. The experimental conditions were: different reversed-phase adsorbents and a solvent methanol–water system as the mobile phase. At varying mobile phase compositions highly resolved chromatograms of PEG samples were obtained, in which all peaks could be identified, and the dependencies of the distribution coefficient on the degree of polymerization for PEG molecules were evaluated by processing these chromatograms. The data were interpreted by using a theory of homopolymers based on a continuum Gaussian chain model of flexible macromolecules and a slit-like model of pores of stationary phase. The theory proved to describe well the experimental data in the whole range of studied molecular masses, and the thermodynamic parameters characterizing interactions of ethylene oxide repeating units in PEG molecules with the adsorbent pore walls have been determined from the comparison of the theory with the experimental data. The dispersion of chromatographic peaks corresponding to individual oligomer molecules is also estimated. In the system studied the peak width occurred to be proportional to the distribution coefficient of corresponding macromolecule. The theory is used to develop a computer-assisted procedure for simulation of chromatograms for samples of linear homopolymers. Using the obtained data on the thermodynamic parameters and the estimates of peak dispersion, chromatograms are simulated for PEG samples at two different chromatographic conditions. These simulated chromatograms were in good quantitative agreement with the real chromatograms.     

Thermal degradation chemistry of poly(ethylene naphthalate) – A study by thermal volatilisation analysis

Although the fundamental degradation chemistry of poly(ethylene naphthalate), PEN, is thought to be similar to that of poly(ethylene terephthalate), PET, there is very little evidence in the literature to support this. This paper presents data on the thermal degradation of PEN, in comparison to PET, with particular reference to evolved gas analysis undertaken by thermal volatilisation analysis (TVA). Our thermal degradation studies highlight strong similarities in the degradation behaviour of PET and PEN, despite some evidence of increased thermal stability of PEN in comparison to PET. Identical primary and secondary thermal degradation mechanisms are proposed for PET and PEN, with radical degradation processes thought to dominate at high temperature.     

Miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends by transesterification

The effects of transesterification on the miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) were studied. Blends were obtained by solution precipitation at room temperature to avoid transesterification during blend preparation. The physical blends and transesterified products were analyzed by wide-angle x-ray scattering, differential scanning calorimetry, and nuclear magnetic resonance spectroscopy. It was found that the physical blends are immiscible and when the extent of transesterification reaches 50% of the completely randomized state, independent of blend composition, the blends are not crystallizable and show a single glass transition temperature between those of starting polymers. The interchange reactions were significantly influenced by annealing temperature and time but negligibly by blend composition. © 1996 John Wiley & Sons, Inc.     

Determination of poly(ethylene glycol)s by both normal-phase and reversed-phase modes of high-performance liquid chromatography

A normal-phase HPLC system using an amino column has been developed to characterise oligomers of poly(ethylene glycol)s (PEGs) of average M_r 400 to 2000 with derivatisation by dinitrobenzoate. Normal-phase HPLC with gradient elution using ternary solvents of hexane, dichloromethane and methanol has produced a baseline resolution for oligomers of PEG 400, 600 and 1000, while PEG 1000 and 2000 were analysed by using binary solvents of acetonitrile and water. Mixtures of PEGs have been determined by these HPLC systems. PEG 400 in a textile finish has also been determined with satisfactory recovery. It has been found that the hydroxyl group of solvents in normal-phase HPLC plays an important role in resolution and retention of PEG oligomers. Derivatisation efficiency for PEGs by dinitrobenzoyl chloride and quantitative determination of derivatised PEGs by HPLC have been studied. A reversed-phase (RP) mode of HPLC was examined for determination of PEG 400 oligomers. The normal-phase system provided greater resolution for oligomers of PEGs.     

The Synthesis of Poly(ethylene oxide)-Block-Polybutylacrylate

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