含氟基团对聚酰胺酰亚胺非等温结晶动力学的影响

通过3,3′,4,4′-二苯醚四甲酸二酐(ODPA)和六氟二酐(6FDA)分别与11-氨基十一烷酸反应,合成了两种酰亚胺二酸单体,再用合成的酰亚胺二酸单体按照不同配比和对苯二胺反应合成了6FDA物质的量分数(在两种酰亚胺二酸单体中)分别为10%和25%的含氟共聚酰胺酰亚胺(PAI–F10和PAI–F25),同时按照相同工艺合成了不含6FDA的共聚酰胺酰亚胺(PAI–F0)。利用差示扫描量热仪测试了这3种聚合物的非等温结晶过程及其熔融行为,发现PAI–F10的结晶能力最强,其次为PAI–F0,PAI–F25的结晶现象不明显。采用Jeziorny法和Mo法分析了PAI–F0和PAI–F10的非等温结晶动力学,发现在较低降温速率下,PAI–F10生成晶体的能力更强,结晶度更高。进一步利用Kissinger方程求得PAI–F0和PAI–F10结晶活化能,发现PAI–F10具有更低的结晶活化能。以上研究结果表明含氟基团在低含量时可以促进聚酰胺酰亚胺的结晶能力,而在高含量时却抑制了聚酰胺酰亚胺的结晶。     

改性PET共聚酯的非等温结晶行为

采用差示扫描量热法(DSC)研究了2-甲基-1,3-丙二醇(MPO)改性共聚酯的非等温结晶行为。研究结果表明:MPO的加入使聚对苯二甲酸乙二醇酯(PET)结晶温度降低,半结晶时间(t_(1/2))延长;采用Jeziorny法分析了此体系的非等温结晶行为,发现结晶速率常数(Z_c)随MPO的加入而减小,表明MPO的加入降低了PET的结晶能力,此改性共聚酯将在瓶材和板材方面有更为广阔的应用前景。     

低TiO_2含量的PET非等温结晶性能的研究

采用差示扫描量热法研究了低二氧化钛(TiO_2)含量对聚对苯二甲酸乙二醇酯(PET)的非等温冷结晶和熔融结晶性能的影响。结果表明:PET中加入TiO_2质量分数为0~0.3%时,随着TiO_2含量的增大,PET的结晶温度下降,熔融结晶温度升高,晶粒分布变窄,结晶能力增强;在冷结晶过程中,加入TiO_2的质量分数小于0.3%时,其对PET结晶起一定抑制作用,当TiO_2质量分数为0.3%时,Jeziorny结晶速率常数与纯PET的相当,半结晶时间比纯PET的小;在熔融结晶过程中,加入TiO_2,PET的Avrami指数值增大,半结晶时间有所减小,但对PET的熔融结晶速率影响不大。     

超支化聚酯对PET非等温结晶行为的影响

利用差示扫描量热法(DSC)研究了2种不同端基的超支化聚酯(HBP)对聚对苯二甲酸乙二醇酯(PET)非等温结晶行为的影响,用莫志深法对非等温结晶动力学进行了分析,通过偏光显微镜(POM)观察了各体系的结晶形态。结果表明:PET和PET/HBP的非等温结晶过程可用莫志深动力学方程来描述;HBP的加入并没有改变PET的结晶成核机理和生长方式;端羟基超支化聚酯(HBP-OH)的加入使得PET的结晶速率变慢,对晶体生长起到了抑制作用;端十六烷基超支化聚酯(HBP-C16)在PET中起到了很好的结晶促进剂作用,能够促进PET结晶。     

半芳香族耐高温PA10T/1010的非等温结晶动力学研究

利用对苯二甲酸、癸二胺、癸二酸合成了聚对苯二甲酰癸二胺(PA10T)和聚酰胺(PA)1010的共聚物PA10T/1010,通过差示扫描量热法研究了PA10T/1010的非等温结晶动力学,结果表明随着降温速率的增加,结晶温度和熔点不断降低,同时结晶温度的范围变宽,结晶所需时间减少。用Jeziorny法描述了PA10T/1010的非等温结晶过程,发现其结晶过程分为两段,晶体生长方式在前期为二维盘状生长,后期为多维生长。通过Mo法描述了PA10T/1010的非等温结晶动力学,发现降温速率越大,在单位时间内PA10T/1010所能达到的相对结晶度越高。最后通过Kissinger方法计算得到PA10T/1010非等温结晶活化能为–171.47 k J/mol。     

染色改性共聚酯的热性能研究

在聚对苯二甲酸乙二醇酯(PET)分子链上分别引入聚醚、间苯二甲酸乙二醇酯-5-磺酸钠(SIPE)、脂肪链酯类,得到染色改性共聚酯,考察了改性组分对改性共聚酯热性能及热稳定性的影响。结果表明:改性共聚酯的玻璃化转变温度(T_g)均低于常规PET,醚改性共聚酯结晶性能稍好于常规PET,加入SIPE、醚型/酯型单体制备的共聚酯(ECDP)结晶性能弱于常规PET,其中酯型ECDP结晶能力最弱;在空气氛围下,改性共聚酯的非等温降解可分为三个阶段,第一阶段的降解活化能(△E)均小于常规PET,第二、第三阶段的△E大于常规PET;醚改性共聚酯的等温降解过程接近二级反应,ECDP的等温降解过程为一级反应。     

PET/PBT共混物非等温结晶行为的研究

采用差示扫描量热法(DSC)研究了聚对苯二甲酸乙二醇酯/聚对苯二甲酸丁二醇酯(PET/PBT)共混物的非等温结晶行为;研究了冷却速率对PET/PBT滑/石粉(Talc)成/核剂(P250)共混物结晶行为的影响。对其数据分别采用Jeziorny法、Ozawa法和Mo法进行处理。结果表明:PET/PBT共混物在加入滑石粉后相对结晶度(Xc)有所下降,但是结晶速率提高;PET/PBT/Talc体系单独引入成核剂体系效果更优;PET/PBT/Talc/P250体系随降温速率的增大,结晶度下降,结晶速率加快;Jeziorny法和Mo法处理非等温结晶过程比较理想,Ozawa法则具有一定的局限性。     

成核剂对PET/PEN共混体系非等温结晶的影响

采用差示扫描量热法(DSC)研究了三种成核剂苯甲酸钠(SB)、1,3∶2,4-二亚苄基-D-山梨醇(DBS)、碳酸钙(CaCO3)对聚对苯二甲酸乙二醇酯(PET)/聚2,6-萘二甲酸乙二醇酯(PEN)共混体系的非等温结晶动力学的影响。结果表明,在PET/PEN/成核剂共混体系的非等温熔融结晶过程中,随着冷却速率的升高,结晶起始温度、终止温度、结晶峰温度都向低温方向移动,成核剂的加入使得不同速率下PET/PEN的结晶温度明显提高,结晶更为容易,SB、CaCO3、DBS均起到了较好的成核作用。由于次级结晶的存在,采用Ozawa法不能很好地描述PET/PEN/成核剂共混体系的非等温熔融结晶过程;莫志深法能较好地描述体系的非等温熔融结晶过程。     

PETG/PET纤维制备及性能

通过将聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)与聚对苯二甲酸乙二醇酯(PET)粒料共混纺丝,制备不同质量比的PETG/PET复合纤维。运用DSC研究复合体系的结晶行为。在等速升温的过程中,DSC曲线只出现一个玻璃化转变温度Tg,表明体系是相容的。随着PET含量的增加,冷结晶温度Tc降低,熔点Tm升高。在等温降速的过程中,随着PET含量的增加,熔融结晶温度Tmc变大,峰越尖,说明PET的加入促进了复合体系结晶。在力学强度测试中,随着PET的增加,强度也随之增加。结果表明,PET的加入对PETG的结晶能力产生了很大影响,使复合体系具有良好的可纺性及力学性能。     

齐聚物对PET结晶性能的影响

运用差示扫描量热法研究了不同齐聚物含量的聚对苯二甲酸乙二酯(PET)的非等温结晶过程。结果表明:随齐聚物含量的增加,PET的熔融结晶温度向低温偏移,过冷度增大,结晶热焓增加,结晶度先增大后减小;在相同的结晶温度下,随着齐聚物含量的增加,PET的结晶温度区域逐渐变宽,半结晶周期增大,结晶速率降低。     

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。     

Isothermal crystallization kinetics of commercially important polyalkylene terephthalates

The isothermal crystallization kinetics of virgin, melt‐mixed, and nucleated specimens of polyethylene terephthalate (PET), polypropylene terephthalate (PPT), and polybutylene terephthalate (PBT) were measured. The purpose of the study was to determine the difference in crystallization rate of PPT, which is to be commercially available in the near future, to the extensively studied, commercially important polyalkylene terephthalates PET and PBT. At equivalent supercooling, the crystallization rate of PPT was between that of PET and PBT, with PBT being the fastest crystallizing polymer. Melt‐mixing virgin materials resulted in a substantial increase in the crystallization rate for all three polyalkylene terephthalates. The addition of talc or sodium stearate as a nucleating agent resulted in a further increase in crystallization rate for all three polyesters. Although the addition of talc or sodium stearate to PPT and PET greatly enhanced crystallization rate, these nucleating agent–containing materials still did not crystallize as fast as PBT melt‐mixed in the absence of any intentionally added nucleating agents. Analysis of the crystallization kinetic data using the Avrami equation showed that melt‐mixing and the addition of sodium stearate resulted in an increase in the average Avrami exponent. This result suggested a change in the mechanism of nucleation toward more sporadic nucleation. For the sodium stearate–nucleated materials, the Avrami exponent was found to increase with increasing crystallization temperature, but a precise explanation of this behavior could not be provided without a knowledge of crystallite morphology. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1296–1307, 2000     

Optical monitoring of polyesters injection molding

An optical fiber sensor similar to the one developed by Thomas and Bur 1 was constructed for the monitoring of the crystallization of three polyesters during the injection molding process. The polyesters studied were: polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polyethylene terephthalate (PET). With this optical system it was possible to obtain, in real time, some essential parameters of the polyester crystallization kinetics at different processing conditions. Thus, a study of the influence of injection molding variables on the nonisothermal crystallization kinetics of these polyesters was done. The processing variables were: mold wall and injection temperatures, T_w and T_i, respectively; flow rate, Q; and holding pressure, P_h. The experiments were done following a first order central composite design statistical analysis. The morphology of the samples was analyzed by polarized light optical microscopy, PLOM. The signal of the laser beam during the filling and the crystallization stages of the injection molding of these materials was found to be reproducible. The measurements showed that this system was sensitive to variations of the crystallization of different types of polymers under different processing conditions. The system was not able, however, to monitor the crystallization process when the crystallinity degree developed by the sample was very low, as in the PET resin. It was also observed that T_w and T_i were the most influential variables on the crystallization kinetics of PBT and PTT. Due to its slower crystallization kinetics, PTT was found to be more sensitive to changes in these parameters than the PBT. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 563–579, 2006     

成核剂对PET非等温结晶动力学的影响

利用差示扫描量热仪(DSC)研究了滑石粉、苯甲酸钠和离子聚合物Surlyn对聚对苯二甲酸乙二醇酯(PET)非等温结晶行为的影响,并用Ozawa模型计算了非等温结晶动力学参数。结果表明:三种成核剂均是PET的良成核剂,其中苯甲酸钠的成核效果最为显著。与纯PET相比,三种成核剂的加入均使PET的结晶峰温度Tmc向高温偏移,过冷度(Tm-Tmc)明显降低,结晶速率常数K明显增大。纯PET和PET/成核剂共混体系的Ozawa指数n值介于1-4之间,均不为整数,且PET/成核剂共混体系的Ozawa指数n值小于纯PET的n值。     

Nonisothermal crystallization behavior of poly (butylene terephthalate)–poly (ethylene terephthalate‐co‐isophthalate‐co‐sebacate) segmented copolyesters

In this paper, two different analytical methods were applied to investigate nonisothermal crystallization behavior of copolyesters prepared by melting transesterification processing from bulk polyesters involving poly (butylene terephthalate) (PBT) and ternary amorphous random copolyester poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PETIS). The results show that the half‐time of crystallization of copolyesters depended on the reaction time and decreased with the content of ternary polyesters in the amorphous segment. The modified Avrami model describes the nonisothermal crystallization kinetics very well. The values of the Avrami exponent range from 2.2503 to 3.7632, and the crystallization kinetics constant ranges from 0.0690 to 0.9358, presenting a mechanism of three‐dimensional spherulitic growth with heterogeneous nucleation. Ozawa analysis, however, failed to describe the nonisothermal crystallization behavior of copolyesters, especially at higher cooling rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1232–1238, 2003     

Blends of thermoplastic polyesters with amorphous polyamide. I. Thermal and crystallization behavior

The thermal and crystallization behavior of blends of three thermoplastic polyesters with different degrees of crystallizability, with an amorphous aromatic polyamide is reported. The thermoplastic polyesters used in the investigation were poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET) and a co-polyester of 1,4 cyclohexane-dimethanol, ethylene glydol and terephthalic acid (PETG). The blends exhibited a single glass transition temperature indicating mlseibility in the amorphous phase. The results of thermal analysis indicated that the crystallization of all the three polyesters is facilitated in the molten phase as a result of blending. The blending significantly Increased the degree of crystallinity of PET, but there was no change in the crystallinity of PBT. It is thus observed that the extent of change in both the crystallization rate and the degree of crystallinity of polyesters depend on the inherent crystallizability of the individual polyester.     

端苯基超支化聚酯对PET结晶行为和构象的影响

采用差示扫描量热法(DSC)和衰减全反射傅里叶变换红外光谱(ATR-FTIR)研究了不同代数和含量的端苯基超支化聚酯(HBP)对聚对苯二甲酸乙二醇酯(PET)结晶行为和构象的影响,计算了晶带与内标峰的吸光度比值以及左右式构象的相对含量.其中975 cm?1和1340 cm?1处的吸收峰归属于反式构象,1370 cm?1处归属于左右式构象,793 cm?1和873 cm?1处的吸收峰为内标峰.结果表明,6%的第三代超支化聚酯对PET的结晶促进能力最强.随着超支化聚酯含量或代数的增加,各吸光度比值基本上都呈现出先增大后减小的趋势,左右式构象的含量则表现出先减小后增大的趋势.端苯基超支化聚酯既可以充当成核剂,又可以充当结晶促进剂,因而可以促进PET结晶.     

工程塑料用PET的结晶性能研究

选用有机化蒙脱土、苯甲酸钠、聚乙二醇等物质为改性添加剂,采用正交试验L9(34)设计方法,制备了一系列在缩聚过程中添加各因素不同水平数的改性聚对苯二甲酸乙二醇酯(PET)。探讨了各因素对PET冷结晶温度(Tcc)、热结晶温度(Tmc)和结晶温度范围(△Tc=Tmc-Tcc)的影响趋势及其原因。实验结果表明,苯甲酸钠、聚乙二醇是PET很好的结晶改性剂,有机化蒙脱土对结晶改性作用次之。筛选出的优方案组方合成的PET试样,其结晶性能较常规PET大为改善。     

Effects of absorbed water on physical properties of polyesters

In previous articles, we reported the change in physical properties of hydrophobic polymers caused by absorption of a very small amount of water. This article describes the changes in physical properties of three polyesters owing to absorption of water. The tested polymers were poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), and polyethylene 2,6-naphthalate (PEN). PBT has more flexible main chains than that of PET, and PEN has more rigid main chains. The dielectric measurements revealed that water absorption results in shortening the relaxation time for PET, while the relaxation time for moist PBT becomes longer. The larger amount of absorbed water yields the higher density of PET and the lower density of PBT. The water absorption of the polyesters also yields increments in dielectric constants and relaxation strength. Distribution of relaxation time of the polyesters is narrowed by absorption of water.