CHDM改性PBT共聚酯的非等温结晶动力学研究

采用直接酯化熔融缩聚工艺路线,以1,4-环己烷二甲醇(CHDM)为第三单体,制备了CHDM改性聚对苯二甲酸丁二醇酯(PBT)共聚酯(PBTG),利用差示扫描量热仪测定了PBT及PBTG在不同降温速率下的降温曲线,并采用Jeziorny方法分析了PBTG的非等温结晶动力学。结果表明:随着降温速率的增加,PBT及PBTG的结晶温度降低,结晶曲线变宽;在相同降温速率下,相比PBT,加入第三单体CHDM后的PBTG的非等温结晶动力学速率常数降低,证明PBTG的非等温结晶能力降低,结晶速率变慢; CHDM的加入不利于PBT结晶。     

PBT/PET共混切片结晶性质的研究

本研究采用JJY-Ⅰ型光学检偏振仪测试不同配比PBT/PET共混切片的等温结晶性质,用电子计算机处理数据,获得了PBT/PET共混切片的等温结晶动力学参数。并采用准等温处理方法,将等温结晶动力学参数用于非等温过程中,得到不同配比PBT/PET共混切片一系列结晶动力学特性参数。从其中的动力学结晶能力G,可判断在同一稳态纺丝条件下,不同配比PBT/PET卷绕丝的相对结晶度大小;采用PEDSC-Ⅱ型测试了不同共混配比的PBT/PET切片的非等温结晶性质,其结果和用JJY-Ⅰ型测试结果一致;本研究还探讨了添加剂(成核剂)对PBT/PET共混切片结晶性质的影响。     

PBT/PET共聚酯的结晶和熔融

研究了 PBT/PET 共聚酯的球晶形态、等温结晶动力学和热历史对其 DSC 曲线的影响。结果表明:在120℃下,随着共聚酯中 PBT 含量的增加,共聚酯的球晶形态有很大差异,结晶动力学参数 n,k,t_(1/2)~(-1)增大。经不同的温度热处理,共聚酯在 DSC 曲线上出现两个熔融峰。低温峰对应于不完善的结晶,高温峰属于在 DSC 的升温过程中形成的较完善的结晶。     

聚酯/热致液晶聚合物体系的非等温结晶动力学研究

热致性液晶共聚酯PET／60PHB组分对PET及PBT在两种共混体系中的非等温结晶行为的影响用DSC方法进行了研究，并用Ozawa方法处理了动力学数据。随共混体系中LCP含量的增加，PET的Avrami指数值n趋于降低而PBT的n值趋于增加，表明在非等混结晶条件下．对不同组成的共混物体系有着不同的成核和晶体生长的机理．     

PBT蓄能发光复合材料非等温结晶动力学研究

采用差示扫描量热(DSC)法研究非等温条件下环形对苯二甲酸丁二醇酯(CBT)反应性挤出加工所制聚对苯二甲酸丁二醇酯(PBT)蓄能发光复合材料的结晶行为,分别采用Ozawa,Jeziorny及Mo方程拟合分析复合材料的非等温结晶动力学。结果表明:采用Ozawa及Jeziorny方程所获拟合曲线均不成线性;Mo方程可很好地描述PBT蓄能发光复合材料的非等温结晶过程,拟合所得PBT复合材料的单位时间里体系到达结晶度时的降温速率(F(T))值均较纯PBT的低,且粉体质量分数为15%时,其F(T)值最小,表明加入发光粉体可加速体系的结晶过程,然而在高降温速率下,较高浓度的发光粉体反而会降低体系的结晶速率。     

PET—PBT嵌段共聚酯的结构性能研究

本文报告了用PSC法和X衍射法等对PET—PBT嵌段共聚酯的结构性能,特别如热性能和结晶性能等的研究结果.实验结果表明,不同PBT组份含量的共聚酯熔点变化呈V字形曲线,在摩尔比为50/50时熔点最低.结晶动力学研究表明,当共聚酯中PBT含量为10%时,结晶速率比常规PET有明显增高.X衍射分析还表明,拉伸对共聚酯结晶的发展有明显的诱导效应,尤其是C轴方向的晶粒尺寸增长.     

PBT/PET阻燃材料的非等温结晶动力学

制备了不同DecaBDE含量的PBT/PET合金,DSC和Jeziorny法研究降温速率分别为5、10、15、20、25℃/min时,PBT/PET/十溴联苯醚(DecaBDE)体系的非等温结晶动力学。结果表明:PBT/PET/DecaBDE体系随降温速率的增大,结晶速率加快,结晶放热焓下降;随着DecaBDE含量的增加,体系的初始结晶温度和结晶速率增加,DecaBDE能起异相成核作用并有利于其晶体生长;Jeziorny法比较适合处理PBT/PET/DecaBDE体系在较高降温速率下的非等温结晶过程。     

玻纤增强PC/PBT合金的结晶行为

研究了在玻纤增强的聚碳酸酯(PC)/聚对苯二甲酸丁二酯(PBT)合金中PBT的结晶行为。发现PBT的结晶过程是由两种相反的影响共同决定的,一方面玻纤能够诱导PBT成核,加快PBT的结晶速率;另一方面,PC会抑制PBT结晶,降低PBT的结晶速率。同时发现在不同组成比下,PC/PBT合金会形成不同的相形貌,也会影响玻纤对PBT结晶的成核作用和PC对PBT结晶的抑制作用,进而使PBT呈现加速结晶、分级结晶或者受限结晶行为。基于以上结果,提出了玻纤增强PC/PBT合金中PBT的结晶机理。同时考察了PC/PBT合金的结晶行为和热性能之间的关系。     

PBT非等温结晶动力学

用差示扫描量热法研究聚对苯二甲酸丁二酯（PBT）的非等温结晶动力学，并分别用Ozawa,Jeziorny和考虑综合因素法来处理PBT的非等温结晶数据。结果表明，PBT非等温结晶过程与Ozawa动力学方程相吻合，但不符合用Jeziorny方法处理的Avrami动力学方程；综合考虑温度和结晶程度对聚合物结晶速度的影响。PBT非等温结晶过程符合结晶动力学方程。     

PBT聚酯非等温结晶动力学

用差示扫描量热分析(DSC)法研究聚对苯二甲酸丁二酯(PBT)的非等温结晶动力学,并分别用Ozawa、Jeziorny和综合因素法等三种方法来处理PBT的非等温结晶数据。结果表明,PBT非等温结晶过程与Ozawa动力学方程相吻合,而不符合用Jeziorny方法处理的Avrami动力学方程;综合考虑温度和结晶程度对聚合物结晶速度的影响,PBT非等温结晶过程符合结晶动力学方程:dG(t)/dt=e~(-E/R(T-T_R)+F(T_m-T+α))(1-G(t))~nG(t)~m。     

Kinetics of isothermal and non‐isothermal crystallization of poly(butylene terephthalate)/ liquid crystalline polymer blends

The melting behavior and isothermal and non‐isothermal crystallization kinetics of poly(butylene terephthalate) (PBT)/thermotropic liquid crystalline polymer (LCP), Vectra A950 (VA) blends were studied by using differential scanning calorimetry. Isothermal crystallization experiments were performed at crystallization temperatures (T_c), of 190, 195, 200 and 205°C from the melt (300°C) and analyzed based on the Avrami equation. The values of the Avrami exponent indicate that the PBT crystallization process in PBT/VA blends is governed by three‐dimensional morphology growth preceded by heterogeneous nucleation. The overall crystallization rate of PBT in the melt blends is enhanced by the presence of VA. However, the degree of PBT crystallinily remains almost the same. The analysis of the melting behavior of these blends indicates that the stability and the reorganization process of PBT crystals in blends are dependent on the blend compositions and the thermal history. The fold surface interfacial energy of PBT in blends is more modified than in pure PBT. Analysis of the crystallization data shows that crystallization occurs in Regime II across the temperature range 190°C‐205°C. A kinetic treatment based on the combination of Avrami and Ozawa equations, known as Liu's approach, describes the non‐isothermal crystallization. It is observed that at a given cooling rate the VA blending increases the overall crystallization rate of PBT.     

Crystallization kinetics of glass fiber reinforced PBT composites

The effect of glass fibers on the crystallization of poly(butylene terephthalate) (PBT) was investigated by crystallization kinetics analysis under isothermal and nonisothermal conditions. From the crosspolar optical micrographs of melt‐ and solvent‐crystallized PBT composites, the glass fibers were found to increase the number density and decrease the size of crystallites. The glass fibers provided heterogeneous nucleation sites, and thus enhanced the overall rate of PBT crystallization in isothermal experiments. However, the Avrami exponent and the regime transitions were not significantly affected by the presence of glass fibers. For the nonisothermal kinetics of PBT composites, the model prediction was excellent in most ranges of crystallization, but it deviated above 70% of crystallization especially at fast cooling rates (>40°C/min). This discrepancy of the model seemed to result from the growth regime transitions, which were clearly observed especially at high undercoolings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 576–585, 2000     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Isothermal crystallization kinetics and melting behaviors of poly(butylene terephthalate) and poly(butylene terephthalate‐co‐fumarate) copolymer

The isothermal crystallization kinetics and melting behaviors after isothermal crystallization of poly(butylene terephthalate) (PBT) and poly(butylene terephthalate‐co‐fumarate) (PBTF) containing 95/5, 90/10, and 80/20 molar ratios of terephthalic acid/fumaric acid were investigated by differential scanning calorimetry. The equilibrium melting temperatures of these polymers were estimated by Hoffman–Weeks equation. So far as the crystallization kinetics was concerned, the Avrami equation was applied and the values of the exponent n for all these polymers are in the range of 2.50–2.96, indicating that the addition of fumarate does not affect the geometric dimension of PBT crystal growth. Crystallization activation energy (ΔE) and nucleation constant (K_g) of PBTF copolymers are higher than that of PBT homopolymer, suggesting that the introduction of fumarate hinders the crystallization of PBT in PBTF. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effects of size and shape of dispersed poly(butylene terephthalate) on isothermal crystallization kinetics and morphology of poly(lactic acid) blends

The isothermal crystallization kinetics and morphology of the poly(lactic acid) (PLA) blends containing three different sizes of both spherical and fibrous poly(butylene terephthalate) (PBT) domains have been comparatively investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The dynamic DSC measurement reveals that PBT domains significantly increase the degree of crystallinity of the PLA. Furthermore, the Avrami model is employed to evaluate the crystallization kinetics under isothermal conditions and it is found that PBT acts as nucleating agent, leading to a high overall crystallization rate constant k and shortened crystallization half time t_1/2. Furthermore, the crystallization rate of PLA is promoted with the incorporation of PBT with a large specific surface area. The average Avrami index n of all samples lies within the range of 3.3 ? 4.0, suggesting that morphologies of PBT do not affect the nucleation mechanism; however, the depression of equilibrium melting temperature in the blends ascribes the reductions of perfectness and size of the PLA crystallites. Besides, the nucleation of PLA crystallites around PBT fibers is probably faster than those around PBT spheres because the PBT chains oriented at the fiber surface as a result of flow‐induced crystallization during melt stretching may serve as the primary nuclei for PLA chains to drastically crystallize at the fiber surface. POLYM. ENG. SCI., 56:258–268, 2016. © 2015 Society of Plastics Engineers     

Crystallization kinetics of poly(butylene terephthalate) and its talc composites

Crystallization kinetics of poly (butylene terephthalate) (non‐talc‐PBT) and its 0.1 wt % talc composites (talc‐PBT) was determined for a wide range of cooling rates and isothermal temperatures. The critical cooling rate to suppress crystallization is 2000 K s^?1 for non‐talc‐PBT and 7000 K s^?1 for talc‐PBT. The cooling rate dependence of the total enthalpy change and heating rate dependence of enthalpy of cold crystallization are quantitatively discussed on the basis of the Ozawa's method. For isothermal crystallization, the annealing‐temperature (T _iso) dependence of crystallization half‐time (t _1/2) shows a bimodal curve with two minima. Talc shortens the t _1/2 at T _iso above 340 K and acts as a heterogeneous nucleation agent. Tammann's approach revealed that the t _1/2 is shortened by pre‐nucleation for non‐talc‐PBT but not for talc‐PBT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44739.     

Two-stage crystallization kinetics modeling of a miscible blend system containing crystallizable poly(butylene terephthalate)

A modified two-stage kinetic model is proposed to describe the crystallization/solidification from the melt state of a miscible binary blend system comprising amorphous poly(ether imide) (PEI) and crystallizable poly(butylene terephthalate) (PBT). Differential scanning calorimetry (DSC) was employed to monitor the isothermal melt-crystallization of the PBT/PEI blends. A nonlinear regression method was adopted for estimating the kinetic parameters in accordance with the modified two-stage series-parallel model in comparison with the Avrami model. The results suggested that the crystallization of the PEI/PBT blends could be more precisely described by using the modified model, which properly takes into account the changing mechanisms from early to later stage of crystallization. For practical applications, an optimal temperature window for solidifying PEI/PBT miscible blends may be determined by utilizing this model.     

聚对苯二甲酸丙二醇酯的结晶性能研究

采用热台偏光显微镜和DSC差示扫描量热仪对PET、PTT和PBT的结晶性能进行了研究。实验得到的结果是:PBT具有极强的结晶能力。在相同的△T下,PTT的结晶诱导期和球晶出现的时间比PET短,球晶的生长速率也比PET快;同时,在相同的△T下,PTT的总结晶速率大于PET。PET和PTT在较高的温度下等温结晶时倾向于异相成核,而随着等温结晶温度的降低,开始倾向于均相成核。     

Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry