涤纶HOY生产工艺探讨

对ＨＯＹ生产的关键技术做了简要论述。生产ＨＯＹ的原料质量要求较高,干切片含水率应控制在２０μｇ／ｇ以下,ＨＯＹ的纺丝温度,侧吹风温度及集束点位置等工艺参数的设定也很重要     

湿度对单轴取向PET纤维结晶过程的影响

采用DSC研究了不同拉伸比的单轴取向PET纤维在不同湿度下的冷结晶过程。发现湿度可以诱导纤维双重结晶峰的出现。从DSC图可以看出,随着湿度的提高,结晶峰向低温移动,且分化成两个较小的结晶峰,结晶可在玻璃化转变温度之下发生。DSC数据处理结果表明,所得Avrami指数呈规律变化,由于湿度的影响,单轴取向PET纤维在低温时的结晶机理发生变化。     

Spinning speed–throughput rate relationships for polyester,nylon, and polypropylene fibers

The relationship between spinning speed and throughput rate has been investigated for fibers having the same fiber denier in the drawn state when produced by melt spinning of poly(ethylene terephthalate), nylon 6, and polypropylene polymers over a range of take-up speed (750–3000 m min^-1) and throughput rate. To understand the structural origin of the relationship, a limited amount of characterization of structure and properties of the as-spun and drawn fibers was also done. A comparison of the results for the three polymers shows that while the increase in productivity with increase in spinning speed is relatively less for polyester and nylon 6, it is quite high for polypropylene. The birefringence data show that while molecular orientation increases rapidly with increasing wind-up speed in polyester and nylon 6, the rate of increase is relatively less in the case of polypropylene. The possible reasons for the observed differences in behavior are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1773–1788, 1997     

A comparative study of structure–property relationships in highly oriented thermoplastic and thermotropic polyesters with different chemical structures

Structure and properties of commercially available fully oriented thermoplastic and thermotropic polyester fibers have been investigated using optical birefringence, infrared spectroscopy, wide‐angle X‐ray diffraction and tensile testing methods. The effect of the replacement of p‐phenylene ring in poly(ethylene terephthalate) (PET) with stiffer and bulkier naphthalene ring in Poly(ethylene 2,6‐naphthalate) (PEN) structure to result in an enhanced birefringence and tensile modulus values is shown. There exists a similar case with the replacement of linear flexible ethylene units in PET and PEN fibers with fully aromatic rigid rings in thermotropic polyesters. Infrared spectroscopy is used in the determination of crystallinity values through the estimation of trans conformer contents in the crystalline phase. The analysis of results obtained from infrared spectroscopy data of highly oriented PET and PEN fibers suggests that trans conformers in the crystalline phase are more highly oriented than gauche conformers in the amorphous phase. Analysis of X‐ray diffraction traces and infrared spectra shows the presence of polymorphic structure consisting of α‐ and β‐phase structures in the fully oriented PEN fiber. The results suggest that the trans conformers in the β‐phase is more highly oriented than the α‐phase. X‐ray analysis of Vectran® MK fiber suggests a lateral organization arising from high temperature modification of poly(p‐oxybenzoate) structure, whereas the structure of Vectran® HS fiber contains regions adopting lateral chain packing similar to the room temperature modification of poly(p‐oxybenzoate). Both fibers are shown by X‐ray diffraction and infrared analyses to consist of predominantly oriented noncrystalline (63–64%) structure together with smaller proportion of oriented crystalline (22–24%) and unoriented noncrystalline (12–15%) structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 142–160, 2006     

Influence of branching on the properties of poly(ethylene terephthalate) fibers

A series of branched poly(ethylene terephthalate) samples was prepared by employing 0.07–0.42 mol % trimethylolpropane (TMP) for melt polycondensation. These polymers were characterized with respect to molar mass, intrinsic viscosity, and melt viscosity. Spinning into fibers took place at spinning speeds ranging from 2500 to 4500 m/min. The molecular orientation of the fibers as measured by birefringence and polarized fluorescence decreases with growing amounts of TMP, as does crystallinity. Thus with slightly branched polymers, higher spinning speeds than with a linear polymer can be used to achieve a certain property profile. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 728–734, 1999     

Characterisation of shrinkage in oriented PET films and containers by thermomechanical analysis (TMA)

In this paper, we report from an extensive series of tests in which the thermal shrinkage behaviour of poly(ethylene terephthalate) (PET) homopolymer and copolymer films and containers has been studied by thermomechanical analysis (TMA). Several independent variables have been investigated, and the accuracy of dynamic TMA scans of temperature-dependent shrinkage has been verified by parallel measurements made isothermally. Typical shrinkage levels of biaxially oriented films, of draw ratios between 2.7 and 4.1, are of the order of 5% at 100°C. The magnitude of shrinkage increases with draw ratio, and any evidence to suggest that PET copolymer is marginally more prone to shrinkage is thought to arise from differences in strain-induced crystallinity induced by elongational deformations during processing. Correlations between measurements made on films and commercial containers are good enough to suggest that the simulation technique used is sufficiently valid for further experimentation on processing behaviour.     

PET/PTT合金结晶形态的研究

采用XP-201热台偏光显微镜研究了对苯二甲酸乙二醇酯（PET）/对苯二甲酸丙二醇酯（PTT）合金等温结晶时的结晶形态及影响因素。研究结果表明：随着等温结晶温度的升高,PET/PTT(40/60)合金的结晶诱导期变长;在观察的时间范围内各样品的球晶尺寸随着时间的延长而增大;随着PTT含量的增加,样品球晶的线生长速率增大,球晶尺寸增大;对比不同温度下等温结晶的球晶形态,PET/PTT(100/0)样品在190℃结晶时球晶尺寸最大, PET/PTT(40/60)样品和PET/PTT(100/0)样品在180℃结晶时球晶尺寸最大; PET/PTT(0/100)样品等温结晶时呈现出了复杂的条带球晶。     

Studies on high‐speed melt spinning of noncircular cross‐ section fibers. I. Structural analysis of as‐spun fibers

Flat fibers and hollow fibers were prepared through the high‐speed melt spinning of poly(ethylene terephthalate) (PET), and the structures of these fibers were compared with those of circular fibers. The cross‐sectional shape of each fiber changed to a dull shape in comparison with that of the respective spinning nozzle. The change in the cross‐sectional shape was slightly suppressed with an increase in the take‐up velocity. There was a significant development of structural variation in the cross section of flat fibers in that the molecular orientation and crystallization were enhanced at the edge. Despite the difference in the cross‐sectional shape, the structural development of flat, hollow, and circular fibers with increasing take‐up velocity showed almost similar behavior. Considering that the tensile stress at the solidification point of the spin line is known to govern the structure development of high‐speed spun PET fibers, it was speculated that the effects of the enhancement of cooling and air friction on the tensile stress at the solidification point cancel each other. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1575–1581, 2001     

PET/PTT合金非等温结晶行为的研究

采用差示扫描量热仪对熔融共混制备的聚对苯二甲酸乙二醇酯（PET）/聚对苯二甲酸丙二醇酯（PTT）合金的非等温结晶行为进行研究。结果表明,在相同的降温速率时, 随着PTT含量的增加,PET/PTT合金结晶峰温度向低温方向移动,而且当合金中PET与PTT含量接近时,合金样品出现了双重结晶峰;在降温结晶的过程中,随着降温速率的增大,各合金样品结晶峰温度均降低,其结晶峰均宽化;采用Jeziorny法对上述非等温结晶过程进行了分析,分析结果表明,随着降温速率的增大,各合金样品非等温结晶速率常数增加,其Avrami指数在1~5之间,并且逐渐减小。     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

PTT／PET共混体系结晶行为和形态研究

利用差示扫描量热仪、正交偏光显微镜研究了聚对苯二甲酸丙二醇酯(PTT)、聚对苯二甲酸乙二醇酯(PET)及PTT/PET共混体系(质量比为25∶75)的结晶行为、形态和等温结晶动力学。结果表明,PTT/PET共混物中,少量的PTT部分地起到了成核作用,但在一定程度上阻碍了PET链段规则地进入晶格,影响了结晶速率。偏光显微镜观察到PET、PTT和PTT/PET共混物在120℃下1、20min的溶液滴膜有较清晰的球晶。     

Preparation and characterization of PET/silica nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were fabricated by direct polymerizing PET monomer dispersed with organic modified silica nanoparticles. The characteristics and properties of these nanocomposites were investigated by the transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis, respectively. The results show that (1) the nanoparticles have been well dispersed in the polymer matrix; (2) the addition of nanoparticles can speed up the crystallization and melting point; and (3) the addition has no significant effect on the synthesis process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1229–1232, 2004     

Structure and property relationship of thermotropic liquid crystal polymer and polyester composite fibers

Poly(ethylene 2,6‐naphthalate) (PEN) and poly(ethylene terephthalate) (PET) composite fibers reinforced with a thermotropic liquid crystal polymer (TLCP) were prepared by the melt blending and spinning process to achieve high performance fibers with improved processability. Polymer composite fibers consisting of cheap polyester and small quantity of expensive TLCP are of interest from an economic point of view and from an industrial perspective. The increase in the birefringence and density of the TLCP/PEN/PET composite fibers with the spinning speed was attributable to the enhancement of the molecular orientation and effective packing between chains in the TLCP/PEN/PET composite fibers. Annealing process resulted in the formation of more ordered and perfect crystalline structure and higher crystallinity, improving the mechanical properties of the TLCP/PEN/PET composite fibers. The increase in the crystallite size and the degree of chain extension with increasing spinning speed resulted in the gradual increment of the long period for the TLCP/PEN/PET composite fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006.     

PET/PLA共混物相容性和结晶性能的研究

研究了相容剂钛酸四丁酯[Ti(OBu)4]含量、聚乳酸(PLA)含量对聚对苯二甲酸乙二醇酯(PET)/PLA共混物相容性的影响,探讨了共混物的熔融和结晶行为,并对其结晶形貌进行了观察。结果表明,Ti(OBu)4含量为PLA的4%(质量分数,下同)时,PET/PLA共混物的相容性良好,但当PLA含量超过30%时,共混物出现相分离;PLA的加入使PET的结晶峰变窄,结晶速率增加,且结晶峰温度向高温方向移动;PLA的加入使PET的晶粒尺寸大幅减小,晶粒数目大幅增加,结晶更加完善。     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Morphology and melting behaviour of poly(ethylene terephthalate) crystallized from the glassy state

The influence of annealing conditions on the morphology and melting behaviour of poly(ethylene terephthalate) (PET) was studied. PET annealed under isothermal conditions often shows double melting endotherms depending on the annealing temperature (T_a) and the heating rate of the calorimeter. It was found that the morphological structure and the lower melting peak depend strongly on the annealing temperature, T_a. The increase of the lower melting peak temperature with T_a is due to an increase of the lamellar thickness within the spherulitic structure and to a higher crystallite perfection.     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Uniaxial Orientation and Crystallization Behavior of Amorphous Poly(ethylene terephthalate) Fibers

The effects of drawing conditions on the orientation and crystallinity of poly(ethylene terephthalate) (PET) fibers were investigated by using optical birefringence, sonic velocity, and wide-angle X-ray diffraction measurements, respectively. The preferred condition for preparation of uniaxially oriented amorphous PET fibers was suggested. The crystallization behavior of oriented PET fibers under relaxed and fixed length conditions was investigated by using differential scanning calorimetry (DSC). The multi-overlapping peaks were observed in the non-isothermal DSC curves of oriented PET fibers under relaxed condition. The kinetics of non-isothermal crystallization of oriented PET fibers under relaxed condition was analyzed by using an equation which takes the multi-crystallization processes into account. The kinetic parameters of every process were obtained and the crystallization mechanism was discussed. The crystallization behavior under fixed length condition differs from that under relaxed condition.     

Effect of low‐temperature annealing on dimensional stability of poly(ethylene 2,6‐naphthalene dicarboxylate) fibers melt‐spun at high speed

To investigate structural factors, necessary to obtain a valuable industrial fiber possessing excellent thermomechanical properties, poly(ethylene 2,6‐naphthalene dicarboxylate) (PEN) fibers were produced by high‐speed melt‐spinning to a take‐up speed of 8 km/min, followed by low‐temperature annealing between the glass‐transition temperature (T_g) and exothermic cold crystallization temperature (T_{c cold}), where little transition of crystalline phase, as well as little thermal degradation, takes place. Their thermomechanical behavior, as well as structural variations, were investigated through differential scanning calorimetry, Rheovibron, thermomechanical analysis (TMA), and tensile testing. Two types of the α‐ and α′‐dispersions were observed at near T_g and at a temperature 50–60°C higher than T_g, respectively. The dispersions were affected by rearranged structures, which are generated by developing an inhomogeneous taut structure with rigidity of aromatic segment and aliphatic segment. The α‐dispersion seemed to reflect an inhomogeneous taut structure by the less nearly arranged segments. Consequently, at intermediate take‐up speeds between 2 and 6 km/min the inhomogeneous taut structure may be partially formed, but the homogeneously ordered structure may be enlarged as the take‐up speed and annealing temperature increased. Thermal shrinkage increased above the α‐dispersion temperature, which suggested that the onset point of dimensional change in PEN fibers was attributed to α‐dispersion. In the case of annealed fibers, the start of length change coincided with the respective annealing temperatures, which indicated that dimensional stability could be gained from restraining the inhomogeneous taut structure in the amorphous region without the transition of crystalline phase by annealing between T_g and T_{c cold}. Therefore, to obtain dimensional stability in PEN fibers, it is supposed that the inhomogeneous taut structure exhibited by the α‐dispersion should be controlled. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 212–218, 2005     

Rigid amorphous phase and low temperature melting endotherm of poly(ethylene terephthalate) studied by modulated differential scanning calorimetry

The rigid amorphous phase, the low temperature melting endotherm, and their development with thermal treatment in poly(ethylene terephthalate) (PET) were investigated by means of modulated differential scanning calorimetry. The differential of the reversing heat capacity and nonreversing heat flow signals were used to analyze the behavior of the glass transition and the low temperature melting endotherm. With increasing annealing time, the increment of the heat capacity at the glass‐transition temperature decreased and the increment of heat capacity at the annealing temperature increased. It was suggested that the origin of the low temperature melting endotherm mainly resulted from the transition of the rigid amorphous fraction for the PET used. The glasslike transition of the rigid amorphous fraction occurred between the glass transition and melting. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2779–2785, 2001