PET/PEN/DBS共混体系结构与形貌的研究

共混是改善聚合物性能的一种简单而又行之有效的方法,PET和PEN均为结晶性聚酯,由于PEN合成原料的影响,致使PEN的价格较高,但性能比PET优良,通过二者的共混,既可以提高PET的性能,又可以降低PEN成本,有关PET／PEN共混体系的研究已引起人们的关注,而对于共混体系结晶形态和结晶条件的研究较少,由于成核剂能够提高结晶速率,减小球晶尺寸,因此本文对PET／PEN／DBS共混体系中,组分组成的影响及不同结晶条件下共混物的结晶形貌进行研究。     

PET分子量对PET/PC共混体系高压结晶行为的影响

以往高压合成的聚合物伸直链晶体尺寸较小且合成时间过长,不能满足单晶应用的要求。加入10wt%PC于不同分子量的PET中,采用自制高压装置,制备共混体系,用WAXD,SEM,DSC等表征手段,研究了PET/PC共混体系在高压下的结晶行为。研究结果表明:通过PET/PC体系在高压下化学反应诱导的自组装,不同分子量PET的PET/PC共混体系均在较短的时间内生成了尺寸较大的聚酯伸直链晶体,对应于三斜晶系,其中PET/PC体系最适于大尺寸伸直链晶体的合成,仅需6hr时间即生成PE需200hr方可合成的40μm厚度的伸直链晶体。同时提出了PET1/PC体系中伸直链晶体高温下缺陷自我修复模型。     

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。     

PTT/PET共混体系晶体形态与结晶性能的研究

用差示扫描量热仪(DSC)、广角X射线衍射(WAXD)和正交偏光显微镜研究了聚对苯二甲酸丙二酯(PTT)和聚对苯二甲酸乙二酯(PET)共混体系的晶体形态与结晶性能.结果表明,共混体系结晶性能与PTT的含量有关.PET的加入,使共混体系的球晶尺寸减小.球晶完善性降低.当PTT含量为40wt%～60wt%时,共混物分别出现了双重熔融峰和双重结晶峰.双重熔融峰是加热过程中熔融重结晶造成的,双重结晶峰说明不完善的晶体产生的次级结晶.     

PC/PET/EPDM共混体系的结晶与熔融行为

本文用解偏振光法与DSC法分别测定并研究了PC/PET/EPDM共混体系的结晶速度、结晶度、Avrami指数(n)和熔融温度及其影响因素,共混物中PET的结晶速度、结晶度均随PC含量增加而下降;EPDM用量不超过10%时,可提高PET的结晶速度,但不影响结晶度和成核与增长方式,n值不变。当EPDM为5%时,结晶速度呈现极大值。经退火处理的共混物呈现熔融双峰,PC量增加,高温熔融峰略移向高温方向;热处理温度升高或时间延长,则低温熔融峰移向高温方向。     

纤维素芳族酯热致液晶对PET结晶成核作用的研究

用自制的热致液晶性纤维素芳族酯(CAE)作聚对苯二甲酸乙二醇酯(PET)的成核剂,研究了PET/CAE体系(CAE含量≤1%)在110～200℃温度范围内的等温结晶动力学特性.结果表明,CAE能显著加快PET结晶速率(Z),Z随结晶温度和CAE含量变化均有极大值Z_max(T_C)和Z_max(W_CAE),Z_max(T_C)对应的温度T_max随CAE含量增加而降低,CAE促进PET结晶的作用机理与普通成核剂不同.     

氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物及其马来酸酐接枝共聚物增韧聚对苯二甲酸乙醇酯共混材料的辐射效应

采用双螺杆熔融共混的方法制备了含三羟甲基丙烷三丙烯酸酯(TMPTA)的聚对苯二甲酸乙二酯/氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物（PET/SEBS）和聚对苯二甲酸乙二酯/马来酸酐接枝氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物（PET/SEBS-g-MAH）共混材料,并在Co-60源中对其进行辐照。 通过对共混材料的力学性能、相态结构测和凝胶含量分析,对比研究了辐射对以上2种共混材料结构及性能的影响。 扫描电子显镜观察和凝胶含量分析结果表明,在适量TMPTA存在时,辐射有效地改善了PET/SEBS体系的相容性。 冲击强度的变化证实了这种增容效应,当SEBS的质量分数为20%、TMPTA质量分数为1%,经50 kGy辐照后,冲击强度达到17.3 kJ/m2。 当在SEBS分子链上引入马来酸酐官能团,辐照后,体系的相态结构变化并不明显,冲击强度最大值仅为11.5 kJ/m2,明显低于不含马来酸酐官能团的体系。     

PET/PEN/DBS共混物非等温结晶动力学研究

采用DSC方法, 用修正的Avrami, Ozawa, Ziabicki宏观动力学模型描述PET/PEN/DBS[PET: 聚对苯二甲酸乙二醇酯; PEN: 聚2,6-萘二甲酸乙二醇酯; DBS: 1,3∶2,4-二(亚苄基)-D山梨醇]共混物的非等温熔融结晶过程, 研究结果表明, 修正的Avrami模型能很好地描述此共混物非等温结晶过程. 冷却速率在5-20 ℃/min范围内, Ozawa方程能很好地描述初期结晶过程, 但结晶后期由于忽略次级结晶而不适宜. 由Ziabicki结晶动力学参数可知, 该共混物的结晶随着成核剂DBS含量的增加而降低, 结晶速率随着成核剂DBS含量的增加而提高. 在非等温结晶条件下, 共混物结晶同时受到冷却速率和共混物组成的影响, 与共混物非等温结晶过程的有效能垒分析结果基本一致.     

PET/LCP反应性共混物的非等温结晶动力学

采用DSC方法研究了聚对苯二甲酸乙二酯 (PET)和热致性液晶共聚酯 6 0PHB PET (LCP)体系在少量扩链剂双 (2 唑啉 ) (BOZ)存在下形成的反应性共混物的非等温结晶动力学 .结果表明反应性共混物的Avrami指数均在 3 0～ 4 5之间 ,BOZ的加入使反应共混物中PET组分的结晶速率降低 ;表明BOZ对酯交换的促进作用 ,使所生成的共聚酯中PET嵌段的数均序列长度变短 ,而使结晶在某种程度上较为困难 ,但对体系的成核和结晶生长机理无明显影响 .结果还表明 ,随冷却速率的增大结晶峰向低温方向移动     

PET/PC共混体系结晶行为研究进展

聚对苯二甲酸乙二醇酯(PET)／聚碳酸酯(PC)合金材料是综合性能优异的工程塑料,对其结晶行为的研究,可为设计,调节及控制材料的性能提供理论基础。评述了近年来PET／PC共混体系结晶行为研究的最新工作和理论进展,包括PET／PC共混体系酯交换、相容性及结晶性的关系,退火对PET／PC共混体系结晶行为的影响,第三组分对PET／PC共混体系结晶行为的影响,PET／PC共混体系结晶动力学以及PET／PC共混体系高压结晶行为的研究。并对今后的深入研究作了展望。     

Lamellar‐level morphology induced by combined crystallization and liquid–liquid demixing in a poly(ethylene terephthalate)/poly(ethylene‐2,6‐naphthalate) blend

The lamellar‐level morphology of an extruded poly(ethylene terephthalate) (PET)/poly(ethylene‐2,6‐naphthalate) (PEN) blend was investigated with small‐angle X‐ray scattering (SAXS). Measurements were made as a function of the annealing time in the melt and the crystallization temperature. The characteristic morphological parameters at the lamellar level were determined by correlation function analysis of the SAXS data. At a low crystallization temperature of 120 °C, the increased amorphous layer thickness was identified in the blend, indicating that some PEN was incorporated into the interlamellar regions of PET during crystallization. The blend also showed a larger lamellar thickness than pure PET. A reason for the increase in the lamellar thickness might be that the formation of thinner lamellar stacks by secondary crystallization was significantly restricted because of the increased glass‐transition temperature. At high crystallization temperatures above 200 °C, the diffusion rates of noncrystallizable components were faster than the growth rates of crystals, with most of the noncrystallizable components escaping from the lamellar stacks. As a result, the blend showed an interfibrillar or interspherulitic morphology. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 317–324, 2002     

Transesterification kinetics of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate) blends with the addition of 2,2′‐bis(1,3‐oxazoline)

The kinetics of the transesterification reaction between poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) with and without the addition of a chain extender were studied with ¹H NMR. Different kinetic approaches were considered, and a second‐order, reversible reaction was accepted for the PET/PEN reactive blend system. The addition of 2,2′‐bis(1,3‐oxazoline) (BOZ) promoted the transesterification reaction between PET and PEN in the molten state. The activation energy of the transesterification reaction for the PET/PEN reactive blend with BOZ (94.0 kJ/mol) was lower than that without BOZ (168.9KJ/mol). The rate constant k took an almost constant value for blend samples with different compositions mixed at 275 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2607–2614, 2001     

PET/PEN共混物的相容性与酯交换反应

通过用1H-NMR对聚对苯二甲酸乙二酯(PET)与聚2,6-萘甲酸乙二酯(PEN)、PET/PEN共聚物的共混物酯交换反应的研究,测得了反应速率常数、反应活化能和诱导期.根据酯交换反应程度和不同反应温度下的诱导期探讨了酯交换反应与相容性的关系,认为PET与PEN的相容导致或增强了酯交换反应,即相容性是酯交换的必要条件;同时酯交换的发生又促进了PET与PEN的相容.酯交换和相容是聚酯共混物熔融时相互关联的两个过程.     

Studies of miscibility,transesterification and crystallization in blends of poly(ethylene terephthalate) and Poly(ethylene-2,6-naphthalene dicarboxylate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene-2,6-naphthalene dicarboxylate) (PEN) were obtained by coprecipitation from solution followed by melt-pressing for different timest _mand quenching in iced water. When the melt-pressing time was 0.2 and 0.5 min, two glass transition temperaturesT _gwere observed by means of dynamic mechanical analysis (DMA), indicating that there are two phases present, a PEN-rich phase and a PET-rich phase. The differential scanning calorimetry (DSC) curves show two crystallization peaks and two melting peaks which, according to wide-angle x-ray scattering (WAXS) measurements, can be attributed to PET and PEN, respectively. In the case oft _m=2 min or longer, a single value ofT _gand thus a single phase is found to exist. Fort _m=10 min and 45 min no crystallization and melting at all is observed during heating with 10°C/min, indicating that a copolyester of PET and PEN has been formed by transesterfication during melt-pressing.Time-resolved WAXS measurements during isothermal crystallization show that, in the blend, the half-time of crystallization of PET is different from that of PEN, and not the same as that which is found in the pure polymer.Dedicated with best wishes to Prof. Dr. E.W. Fischer on the occasion of his 65th birthday     

Intimate blend of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate) via formation with and coalescence from their common inclusion compound with γ‐cyclodextrin

The experimental procedures to place poly(ethylene 2,6‐naphthalate) (PEN) guest molecules within γ‐cyclodextrin (γ‐CD) host molecules are described along with the subsequent verification of inclusion‐compound (IC) formation. In addition, the simultaneous complexing of PEN and poly(ethylene terephthalate) (PET) with γ‐CD to form their common IC is documented. Coalescence from their common γ‐CD IC generates an intimate blend of the PET and PEN polymers contained therein. Thermal analysis via differential scanning calorimetry reveals thermal behavior indicative of an intimate blend of PET and PEN. ¹H NMR analysis confirms that the intimate blending of PET and PEN achieved by coalescence from their common γ‐CD IC is not due to transesterification into a PET/PEN copolymer during thermal analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 139–148, 2003     

Non-isothermal crystallization kinetics of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends

The glass-transition temperature and non-isothermal crystallization of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) (PTT/PEN) blends were investigated by using differential scanning calorimeter (DSC). The results suggested that the binary blends showed different crystallization and melting behaviors due to their different component of PTT and PEN. All of the samples exhibited a single glass-transition temperature, indicating that the component PTT and PEN were miscible in amorphous phase. The value of T_g predicted well by Gordon-Taylor equation decreased gradually with increasing of PTT content. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization. The kinetic parameters suggested that the PTT content improved the crystallization of PEN in the binary blend. The crystallization growth dimension, crystallization rate and the degree of crystallinity of the blends were increased with the increasing content of PTT. The effective activation energy calculated by the advanced iso-conversional method developed by Vyazovkin also concluded that the value of E_a depended not only on the system but also on temperature, that is, the binary blend with more PTT component had higher crystallization ability and the crystallization ability is increased with increasing temperature. The kinetic parameters U^* and K_g were also determined, respectively, by the Hoffman-Lauritzen theory.     

三元共聚液晶聚酯酰亚胺/PET共混体系结构与性能研究

通过熔融共混的方式,将实验室自行设计合成的三元共聚热致液晶聚酯酰亚胺(PPDI)与聚对苯二甲酸乙二酯(PET)进行共混,制备一系列不同液晶聚合物含量的共混体系.采用示差扫描量热仪(DSC)、广角X-射线衍射仪(WAXD)和动态力学性能分析仪(DMA)对共混体系的结构与性能进行表征.结果表明,共混体系中两组份之间具有良好...     

Dielectric and conductivity processes in poly(ethylene terephthalate) and poly(ethylene naphthalate) homopolymers and copolymers

Electrical relaxation and conductivity processes in amorphous and semicrystalline poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) homopolymers and certain PET/PEN copolymers have been studied by means of dielectric spectroscopy. Homopolymers and copolymers able to crystallize were subjected to successive thermal runs to investigate the influence of the thermal history upon the morphology and the electrical behavior of the polymeric systems. The morphology of the untreated as well as the heat‐treated specimens was determined by means of Differential Scanning Calorimetry (DSC). All samples exhibit β‐relaxation process, due to local motions of the C?O polar side groups, and α‐relaxation process associated to the glass/rubber transition. In the PEN spectrum an additional, subglass, mode was recorded, most probably attributed to cooperative motions of the naphthalene groups. Finally, the dynamic nature of the crystallization process is expressed via the over glass transition mode and the temperature dependence of dc conductivity recorded in amorphous PET, PEN, and PET/PEN (85/15) (wt/wt) samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3078–3092, 2006     

Relaxation behavior of poly(ethylene terephthalate)/poly(ethylene naphthalene 2,6‐dicarboxylate) blends prepared by cryogenic blending

A method including cryogenic grinding, melt pressing from the molten state, and quenching was used to prepare blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) in which the two phases were highly dispersed. The effect of melt‐pressing times on the thermal properties and relaxation behavior of PET/PEN films were characterized with differential scanning calorimetry and dielectric spectroscopy. For short melt‐pressing times, two glass‐transition, two crystallization, and two melting peaks were observed, indicating the presence of PET‐rich and PEN‐rich phases in these blends. Longer melt‐pressing times revealed a single glass transition and a single α‐relaxation process, showing that PET–PEN block copolymers were likely to be formed during the melt pressing. The experimental findings were examined in terms of the transesterification reactions between the blend components, as revealed by ¹H NMR measurements. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2570–2578, 2002