热致液晶性PHB／PET共聚酯的热性能

以对羟基苯甲酸(PHB)和聚对苯二甲酸乙二酯(PET)为原料,经熔融缩聚制备了一系列不同配比的液晶性PHB/PET共聚酯;并研究了这些共聚酯的热转变行为和热稳定性。结果丧明:20PHB/PET共聚酯的冷结晶温度比PET高,而结晶温度比PET低,表明PHB/PET在未形成液晶相的情况下,少量PHB的刚性链段阻碍了PET链节的运动,使其比纯PET更难结晶;在空气介质中,共聚酯的第一热分解温度均高于380℃。PHB含量少于80mol%时,第一热分解温度变化不大,多于80mol%时则迅速上升;第二热分解温度均高于490℃,且随PHB含量增加而呈直线上升。     

PET固相缩聚工艺技术分析

综述了聚酯(PET)固相缩聚过程特点,重点对比分析了Bepex、Buhler、Sinco及Dupont的NG3连续固相缩聚工艺、关键设备构型及主要操作参数。PET固相缩聚过程中结晶增长与缩聚反应共存并互相耦合,因而结晶工序是固相缩聚工艺的重要组成部分,也是各工艺专利商的专利技术之所在。有效的结晶增长、结晶形态与缩聚反应的解耦合是强化固相缩聚技术的科学基础。     

全芳液晶聚酯固相缩聚及其性能的研究

研究了用固相缩聚方法提高全芳液晶聚酯的分子量。以２，６－萘二甲酸，对／间羟基苯甲酸、双酚类单体为原料，经熔融酯交换合成低聚物，再以固相反应制备共聚酯。通过对共聚酯熔融指数的变化，探讨固相缩聚中反应时间和反应温度的效应，共聚酯分子结构和聚集态结构与固相缩聚反应速率的关系；并通过Ｘ－射线衍射分析，考察固相缩聚对聚酯结晶性的影响。得出全芳聚酯固缩聚过程是一个由化学反应为主要控制，继而转化到物理扩散为主要     

固相缩聚PET的分子量分布

在研究聚酯（PET）固相缩聚反应动力学的基础上,进一步利用多组分模型,模拟分析了固相缩聚PET的分子量分布,模拟结果与凝胶渗透色谱测试结果相吻合。     

PET/PEG共聚酯连续熔融终缩聚过程两相稳态模型分析

针对高性能共聚酯PET/PEG缩聚过程,建立了圆盘反应器中连续熔融聚合两相稳态模型,模拟分析了缩聚反应温度、压力、停留时间以及传质系数对气相组成、共聚酯数均分子量、端羧基浓度以及副产物二甘醇和水浓度的影响。结果表明：挥发组分主要在反应器的前半部分产生,在z > 0.4后气相挥发总量已经很小;乙二醇占气相组成的比例极高,约为90%,而二甘醇的含量极低,只为0.5%左右;随反应器温度、真空度、停留时间、传质系数的增加,共聚酯产物的分子量增大,当传质系数大于0.1 s^-1后,反应器出口的共聚酯分子量几乎不再变化,此时已不受传质控制,最终产物的分子量约26000。     

聚酯固相缩聚等温结晶特性的研究

聚酯(PET)固相缩聚(SSP)中切片的结晶性能及其演变影响固相缩聚反应,采用差示扫描量热仪(DSC)和热台偏光显微镜研究了固相缩聚反应前后PET切片的等温结晶特性。结果表明:PET切片在DSC中的等温结晶符合Avrami 方程,等温结晶温度升高,结晶速率常数K值减小,即结晶速率降低;热台偏光显微镜中不同等温结晶温度下形成了不同的球晶形态:黑十字消光图以及环形消光图;随着PET特性粘数(平均分子质量)增大,结晶速率常数K值减小,球晶生长速率减小,Avrami指数n值增大,形成更加复杂的消光图。对于固相缩聚前PET基础切片,球晶最大结晶速率在190℃左右。     

固相缩聚生产高粘度聚酯

叙述了高粘度聚酯的发展概况以及制造工艺,并重点阐述了影响固相缩聚生产高粘度聚酯反应的主要因素。指出聚酯固相缩聚应选择合理的原料路线,严格精选切片颗粒大小及预聚体切片结晶度(预聚体极限密度控制为1.38g/cm~3);根据最终产品需要选取不同的催化体系并通过调整 PTA/EG 配比控制预聚体中醚键含量;反应温度及反应时间是固相缩聚反应的主导影响因素,但控制反应中副产物的去除是破坏反应平衡、提高固相缩聚表观反应速率的重要手段。     

粉末PET固相缩聚的研究

系统地研究了粉末聚酯(PET)固相缩聚,得到了有效的干燥结晶条件:140℃干燥120 min,180℃再结晶45 min,切片含水率低于30μg／g;研究了反应温度,粉末粒径和N2流量对PET固相缩聚的影响,分析粉末固相缩聚存在N2流量阈值的机理。结果表明:反应温度越高,颗粒越小,固相缩聚反应速度越快;粉末 PET预聚体在一定温度下固相缩聚,存在N2流量阈值。在此流量下,达到该温度下的该粒径粉末的最大界面扩散速率和固相缩聚的最大反应速度。相同反应温度下,粉末粒径越小,阈值N2流量越大。     

专利摘登

聚酯热稳定性和光稳定性的改进方法;具有良好耐热性的双轴取向PET薄膜;高收缩率薄膜用聚酯材料的制备;在多段流动床反应器中进行连续固相缩聚的设备和方法;制造具有良好结晶和表面性能含有二聚脂肪酸的PET共聚物……[编者按]     

专利摘登

<正>特性黏度超高的聚酯的生产方法本发明提供了生产特性黏度超高的聚酯的方法,此法生产出来的聚酯,其特性黏度至少在0.9dL/g。它包括固相缩聚,固相缩聚所用的原料聚酯的特性黏度必须大于0.65 dL/g而小于0.9 dL/g。这种原料聚酯为PET,可以含有1种或1种以上的共聚物单体,数量可达到30%的摩尔分数,其中聚     

Studies on fiber formation of thermotropic copolyesters

Thermotropic copolyesters PET/60 PHB and PET/80 PHB fibers are melt spun at different extrusion temperatures and at different draw-down ratios. The flow behavior of PET/60 PHB is studied at different temperatures and shear rates. The melt of (PET/60 PHB) at temperatures above 265°C exhibit low viscosity and low activation energy of flow. The modulus and strength for both PET/60 PHB and PET/80 PHB fibers increase with the increase in extrusion temperature and draw-down ratio in the ranges studied. High birefringence, indicating the presence of mesophase is observed between 265 and 300°C on a hot stage polarizing microscope. X-ray diffraction patterns show that the molecular orientation increased with increasing draw-down ratio. Scanning electron microscopy of these fibers shows a well-developed highly oriented fibrillar structure. Superior mechanical performance of fibers spun at around 275°C are attributed to the presence of nematic mesophase in the polymer melt. © 1993 John Wiley & Sons, Inc.     

Melt spinning and annealing of poly(ethylene terephthalate)/p‐hydroxybenzoate liquid crystalline polymer

Poly(ethylene terephthalate)/p‐hydroxybenzoate (PET/PHB) copolymer materials have relatively low melt viscosity because of the 60 mol % PHB material having a value that is lower by approximately two orders of magnitude than the value for PET homopolymer. The structure development during melt spinning and thermal treatment (annealing) of liquid crystalline copolyesters, with a rigid backbone structure, were analyzed through the density, birefringence, X‐ray diffraction, DSC, dynamic viscoelasticity, and tensile testing. As the take‐up velocity increased, the birefringence of PET/PHB as‐spun fiber increased, which indicated that it directly influenced the initial modulus and specific stress. The lateral packing of PHB molecular chain in a copolymer was shown to be loosened in the course of thermal treatment. The thermal treatment slightly increased the crystal orientation factor, whereas total molecular orientation was decreased by annealing. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1265–1278, 2004     

Solidification behavior and recovery kinetics of liquid crystalline polymers

The supercooling behavior of three thermotropic liquid crystalline polymers (TLCP's), 60 mole% p-hydroxybenzoic acid and 40 mole% poly(ethyleneterephthalate), 60/40 PHB/PET, 80 mole% p-hydroxybenzoic acid and 20 mole% poly(ethyleneterephthalate), 80/20 PHB/PET and a copolyester of 73 mole% p-hydroxybenzoic acid and 27 mole% of 2-hydroxy-6-naphthoic acid, Vectra A900, was studied by means of both rheological and thermal methods. 60/40 PHB/PET and Vectra A900 exhibited a degree of supercooling as high as 80°C while there was only 20°C of supercooling for 80/20 PHB/PET. The degree of supercooling for the blends of 60/40 PHB/PET and 80/20 PHB/PET also decreased with the increase in 80/20 PHB/PET content. The increase in G′ as the temperature decreased was more gradual for 60/40 PHB/PET and Vectra A900 than that for 80/20 PHB/PET, which was beneficial from a processing point of view. The solidification of the LCP melt was attributed to both the crystallization and the freezing of the mesophase. The degree of crystallinity for all three TLCP's was very small, less than 5%, as measured by the DSC. It was found that both 60/40 PHB/PET and Vectra A900 showed an induction period of a few minutes during solidification while 80/20 PHB/PET solidified continuously at the test temperature. Therefore, 60/40 PHB/PET and Vectra A900 seem to be more suitable for use in processes such as blow molding and film blowing than 80/20 PHB/PET.     

固相缩聚PET相对分子质量及其分布研究

建立了 PET固相缩聚反应的数学模型 ,对相对分子质量及粒子内部相对分子质量的梯度分布的模拟与实验结果相符。实验假定粒子内任一微小体积元内聚合物的相对分子质量服从 F lory分布 ,计算产物相对分子质量多分散系数 MWD ,发现粒子内相对分子质量的梯度分布对产物相对分子质量分布的加宽无明显的贡献。认为相对分子质量分布的加宽是由于晶区被排除在反应体系以外造成的 ,且反应条件越苛刻 ,相对分子质量分布越宽。     

Microstructure and properties of poly(ethylene terephthalate)/organoclay nanocomposites prepared by water‐assisted extrusion: Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites containing different concentrations of the organoclay were prepared using two different twin‐screw extrusion processes: conventional melt mixing and water‐assisted melt mixing. The reduction of the molecular weight of the PET matrix, caused by hydrolysis during the water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses showed intercalated/exfoliated morphology in all PET/C30B nanocomposites, with a higher degree of intercalation and delamination for the water‐assisted process. Rheological, thermal, mechanical, and gas barrier properties of the PET nanocomposites were also studied. Enhanced mechanical and barrier properties were obtained in PET‐C30B nanocomposites compared to the neat PET. The nanocomposites exhibited higher tensile modulus and lower oxygen permeability after SSP. The elongation at break was significantly higher for SSP nanocomposites than for nanocomposites processed by conventional melt mixing. POLYM. ENG. SCI., 54:1879–1892, 2014. © 2013 Society of Plastics Engineers     

Sandwich injection molding of thermotropic copolyesters and filled polyester

Mold filling studies have shown that thermotropic liquid crystalline copolyesters of p-hydroxybenzoicacid (PHB) and polyethyleneterephthalate (PET) fill by an advancing front mechanism similar to flexible chain polymers. The structure and orientation developed during filling as determined on solid specimens by an etching method, X-ray diffraction, and shrinkage study on thin microtomed samples appear to be most pronounced at the surface. Based on this information copolymers of 60 and 80 mole percent PHB/PET were co-injection molded with filled PET under various processing conditions. Because of the low viscosity of the copolyesters, they readily coated filled PET under most processing conditions to give a sheath/core structure. The bending modulus of co-injection molded bars with as little as 35 percent PHB/PET was as high as the sample consisting of 100 percent liquid crystalline copolyester. Electron micrographs of fracture surfaces revealed excellent adhesion between the two polymers.     

Solid‐state polymerization of poly(ethylene terephthalate): Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites of different organoclay concentrations were prepared using a water‐assisted extrusion process. The reduction of the molecular weight (M_w) of the PET matrix, caused by hydrolysis during water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). Viscometry, titration, rheological, and dynamic scanning calorimetry measurements were used to analyze the samples from SSP. The weight‐average molecular weight (M_w) of PET increased significantly through SSP. PET nanocomposites exhibited solid‐like rheological behavior, and the complex viscosity at high frequencies was scaled with the M_w of PET. The Maron–Pierce model was used to evaluate the M_w of PET in the nanocomposites before and after SSP. It was found that the extent and the rate of the SSP reaction in nanocomposites were lower than those for the neat PETs, due to the barrier effect of clay platelets. Consequently, the SSP rate of PET increased with decreasing particle size for the neat PET and PET nanocomposites. The effect of the M_w of PET on the crystallization temperature, crystallinity, and the half‐time, t_½, of nonisothermal crystallization was also investigated. With increasing M_w of PET, t_½ increased, whereas T_c and X_c decreased. POLYM. ENG. SCI., 54:2925–2937, 2014. © 2014 Society of Plastics Engineers     

Dispersion of nanoclays with poly(ethylene terephthalate) by melt blending and solid state polymerization

Melt intercalation of clay with poly(ethylene terephthalate; PET) was investigated in terms of PET chain mobilities, natures of clay modifiers, their affinities with PET, and nanocomposite solid state polymerization (SSP). Twin screw extrusion was used to melt blend PET resins with intrinsic viscosities of 0.48, 0.63, and 0.74 dL/g with organically modified Cloisite 10A, 15A, and 30B montmorillonite clays. Clay addition caused significant molecular weight reductions in the extruded PET nanocomposites. Rates of SSP decreased and crystallization rates increased in the presence of clay particles. Cloisite 15A blends showed no basal spacing changes, whereas the basal spacings of Cloisite 10A and Cloisite 30B nanocomposites increased after melt extrusion, indicating the presence of intercalated nanostructures. After SSP these nanocomposites also exhibited new lower angle X‐ray diffraction peaks, indicating further expansion of their basal spacings. Greatest changes were seen for nanocomposites prepared from the lowest molecular weight PET and Cloisite 30B, indicating its greater affinity with PET and that shorter more mobile PET chains were better able to enter its galleries and increase basal spacing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PABA与PET共聚合反应的研究Ⅲ．共聚动力学及相关问题讨论

研究了ＰＡＢＡ与ＰＥＴ共聚合反应动力学，表明随反应温度升高，反应速度增加，可近似看成一级反应。考察了乙二醇对聚对羟基苯甲酸酯的醇解作用，表明基本上不发生醇解反应。根据ＰＡＢＡ自聚反应、ＰＥＴ酸解反应等研究结果，结合本文的工作，讨论了提高ＰＥＴ／ＰＨＢ共聚酯分子量和改进序列分布的问题。     

CDP固相缩聚的研究

对N_2保护下CDP的固相缩聚进行了基础研究,得出了CDP固相缩聚的一般规律,并对实验结果进行了讨论,与常规PET固相缩聚的一些规律进行了比较,同时还比较了不同反应氛围下CDP的分子量变化情况.