聚丙烯在溶液中的等温结晶行为

采用差示扫描量热仪（DSC）分析聚丙烯（PP）在2种不同溶剂中的等温结晶过程,并使用Avrami方程研究等温结晶动力学。 结果表明,晶体生长速率随着结晶温度的升高而降低。 同时,根据Lauritzen⁃Hoffman 二次成核理论,PP在溶液中的成核常数K_g和折叠表面自由能σ_e低于PP原料,反映了其在溶液中的结晶速率较高。     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

A comparative study of polypropylene nucleated by individual and compounding nucleating agents. I. Melting and isothermal crystallization

In this study, melting and isothermal crystallization behaviors of polypropylene (PP) nucleated with different nucleating agents (NAs) have been comparatively studied. α‐phase NA 1,3 : 2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase NA aryl amides compound (TMB‐5), and their compounds were introduced into PP matrix, respectively. The crystallization and melting characteristics as well as the crystallization structures and morphologies of nucleated PP were studied by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). As indicated by previous work that a few amounts of α‐phase NA (DMDBS) or β‐phase NA (TMB‐5) has apparent nucleation effect for PP crystallization. However, the crystallization of PP nucleated with compounding NAs is dependent on the content of each NA. In the sample of PP with 0.1 wt % DMDBS and 0.1 wt % TMB‐5, the nucleation efficiency of TMB‐5 is much higher than that of DMDBS and PP crystallization is mainly nucleated by TMB‐5, and in this condition, β‐phase PP is the main crystallization structure. For the sample of PP with 0.2 wt % DMDBS and 0.2 wt % TMB‐5, 0.2 wt % DMDBS has higher nucleation efficiency than 0.2 wt % TMB5, and α‐phase is the main crystalline structure in this sample. The isothermal crystallization kinetics and crystallization structure have been analyzed in detail in this work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystalline memory effects in isothermal crystallization of syndiotactic polypropylene

Isothermal crystallization behavior after partial or complete melting of syndiotactic polypropylene was investigated by differential scanning calorimetry (DSC). On partial melting, the total concentration of predetermined nuclei was found to decrease with increasing fusion temperature and increasing time period that the sample spent at a specific fusion temperature. A significant effect of the rate of heating to the fusion temperature was also observed. On complete melting, the total concentration of predetermined nuclei was found to approach a constant value, which is the concentration of infusible heterogeneous nuclei (e.g., impurities, catalyst residues) present originally in the sample. At a specific fusion temperature, the concentration of predetermined athermal nuclei was found to decrease exponentially with the time period spent in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 337–346, 2000     

聚丙烯/海泡石复合材料的等温结晶行为

采用熔融共混的方法制备聚丙烯（PP）/海泡石复合材料,通过示差扫描量热仪和偏光显微镜研究有机化改性海泡石填充PP复合材料在不同温度下的等温结晶行为,考察海泡石对PP结晶行为的影响,采用Avrami方程处理等温结晶过程,并计算结晶动力学参数。结果表明,海泡石的加入使复合材料的结晶时间缩短,结晶度增大;随着结晶温度的升高,各体系的结晶速率下降,结晶速率常数n、K降低,并且随着结晶温度（Tc）的升高,半结晶时间（t1/2）增大;在同一结晶温度（Tc）下,海泡石的加入提高了基体的结晶速率,加快了PP的异相成核过程,使得PP球晶尺寸减小。     

高流动抗冲PP的结晶特性及结晶动力学

采用X射线衍射仪、差示扫描量热仪和偏光显微镜研究了5种高流动抗冲聚丙烯(PP)树脂的结晶特性和结晶动力学。结果发现：国产试样的结晶度与晶粒尺寸明显不同于进口试样;在等温结晶条件下。总结晶速率常数和总结晶速率随结晶温度的增加而下降,而结晶半值期增加;在所研究的温度范围内。所有试样的Avrami指数基本为2～3的非整数;在133℃以下,5^#试样的球晶生长速率明显高于其他试样,但在相同结晶温度时,国产试样的总结晶速率大于进口试样。5种试样在抗冲击性能上的差异归因于它们在结晶特性和结晶动力学方面的不同。     

Isothermal crystallization behavior and melting characteristics of injection sample of nucleated polypropylene

The isothermal crystallization behavior and melting characteristics of pure polypropylene (PP) and PPs nucleated with a phosphate nucleating agent (A) and a sorbitol derivative (D) have been studied by differential scanning calorimetry (DSC). Compared with pure PP, nucleated PPs show a shorter half‐times of crystallization. Dependence of crystallization rate of nucleated PP on the crystallization temperature is stronger than that of pure PP at the higher crystallization temperature, whereas the opposite results are obtained at the lower crystallization temperature. Addition of nucleating agent shifts the temperature at the deviation from the baseline of DSC melting curve, T, and the temperature at the completion of melting, T, to higher temperatures, indicating that nucleated PPs exhibit a higher perfection of PP crystals. A shoulder peak in the high temperature range of melting peak of nucleated PP and a wider low temperature region in the melting peak of pure PP are observed. Obviously, PP and nucleated PPs form different distribution of crystal perfection in the isothermal crystallization process. According to the half‐time of crystallization, nucleating agent A is more effective than D. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2547–2553, 2000     

Cavitation during isothermal crystallization of isotactic polypropylene

Cavitation during isothermal crystallization of thin films of isotactic polypropylene was investigated systematically by light microscopy. Cavitation results from the negative pressure buildup due to density change during crystallization in the pockets of melts occluded by impinging spherulites. The morphology of such areas was also studied by SEM. The value of the negative pressure at the moment of cavitation was calculated from the drop of the spherulite growth rate. It was shown that the process of cavitation and the value of the negative pressure causing cavitation depend on the crystallization temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2439–2448, 2001     

聚丙烯/聚磷酸铵复合材料的等温结晶行为

采用差示扫描量热法研究了聚丙烯(PP)聚/磷酸铵(APP)复合材料的等温结晶过程。引入APP后,PP/APP复合材料的平衡熔点升高,结晶速率大幅度提高。采用Avrami方程研究了该体系的结晶动力学,发现PP/APP复合材料呈现明显的异相成核特征,随w(APP)的增加,Avrami结晶速率常数增大,半结晶时间降低。     

PET/分子筛原位聚合复合材料的等温结晶性能

采用原位聚合的方法制备了聚对苯二甲酸乙二酯(PET),分子筛复合材料,并通过差示扫描量热仪研究了不同分子筛含量复合材料的等温结晶性能。结果表明：分子筛的加入有明显的异相成核效果,加快了结晶速率,增加了结晶度,减小了晶粒尺寸分布。在210℃的结晶温度下,当分子筛质量分数为4％时,半结晶时间为156s,结晶热焓为37．84J/g,结晶峰半峰宽为1．88s。     

Thermal properties and isothermal crystallization of syndiotactic polypropylenes: Differential scanning calorimetry and overall crystallization kinetics

Isothermal crystallization and subsequent melting behavior of five samples of syndiotactic polypropylene are presented. Crystallization studies were carried out in the temperature range of 60°C to 97.5°C using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited double melting endotherms. The high melting peak was concluded to be the result of the melting of crystals formed by recrystallization during the reheating process. Overall crystallization kinetics was studied based on the traditional Avrami analysis. Analysis of crystallization times based on the modified growth rate theory suggested that, within the crystallization temperature range studied, the syndiotactic polypropylenes crystallize in regime III. Kinetic crystallizability parameters also were evaluated, and were found to be in the range of 0.41°C s⁻¹ to 2.14°C s⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 44–59, 2000     

聚丙烯固相接枝双单体共聚物的等温结晶行为

用差示扫描量热法结合Avrami方程研究了聚丙烯(PP)与马来酸酐、甲基丙烯酸甲酯双单体固相接枝物的等温结晶行为;用Arrhenius公式分析了接枝支链对PP结晶活化能的影响。研究表明：接枝支链引起PP的结晶成核和结晶生长方式发生变化,既起到异相成核作用,又阻碍了分子链的运动,降低了晶体生长速率。     

Effect of nucleating agent addition on crystallization of isotactic polypropylene

The isothermal and nonisothermal crystallization kinetics of nonnucleated and nucleated isotactic polypropylene (iPP) were investigated by DSC and a polarized light microscope with a hot stage. Dibenzylidene sorbitol (DBS) was used as a nucleating agent. It was found that the crystallization rate increased with the addition of DBS. The influence of DBS on fold surface energy, σ_e, was examined by the Hoffman and Lauritzen nucleation theory. It showed that σ_e decreased with the addition of DBS, suggesting that DBS is an effective nucleating agent for iPP. Ozawa's theory was used to study the nonisothermal crystallization. It was found that the crystallization temperature for the nucleated iPP was higher than that for nonnucleated iPP. The addition of DBS reduced the Ozawa exponent, suggesting a change in spherulite morphology. The cooling crystallization function has a negative exponent on the crystallization temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2089–2095, 1998     

Isothermal melt crystallization and melting behaviour of syndiotactic polypropylene

The lamellar morphological information and subsequent melting behaviour of syndiotactic polypropylene (s‐PP) samples isothermally crystallized at crystallization temperatures ranging from 30 to 95 °C have been investigated using a combination of wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC) techniques. Three known methods for determining the equilibrium melting temperature T_m°, namely the Gibbs–Thomson extrapolation, the linear Hoffman–Weeks extrapolation and the non‐linear Hoffman–Weeks extrapolation, have been employed to evaluate this important thermodynamic parameter, and the results obtained are compared. Finally, an estimate of the equilibrium melting temperature for a perfect s‐PP sample (T_m°)_100% is given. © 2000 Society of Chemical Industry     

Melting,nonisothermal crystallization behavior and morphology of polypropylene/random ethylene—propylene copolymer blends

The melting, nonisothermal crystallization behavior and morphology of blends of polypropylene (PP) with random ethylene–propylene copolymer (PP‐R) were studied by differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and X‐ray diffraction. The results showed that PP and PP‐R were very miscible and cocrystallizable. Modified Avrami analysis was used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was heterogeneous, the growth of the spherulites was tridimensional, and the crystallization mechanism of PP was not affected by PP‐R. The crystallization activation energy was estimated using the Kissinger method. An interesting result was obtained with the modified Avrami analysis and the Kissinger method, whose conclusions were in good agreement. The addition of a minor PP‐R phase favored an increase in the overall crystallization rate of PP. Maximum enhancing effect wass found to occur with a PP‐R content of 20 wt %. The relationship between the composition and the morphology of the blends is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 670–678, 2006     

Effect of isotacticity distribution on crystallization kinetics of polypropylene

The crystallization kinetics of isotactic polypropylene (iPP) depends not only on the undercooling but also on its microstructure characteristics. In this paper the effect of isotacticity distribution on the isothermal kinetics of iPPs in the crystallization regime III was examined by differential scanning calorimetry. The microstructure features of two commercial film grade iPPs were characterized with temperature rising elution fractionation and size exclusion chromatography. The results indicated that, although the overall isotacticities and molecular weights of two iPPs were similar, their isothermal crystallization kinetics displayed marked differences due to the disparity in isotacticity distributions. With increasing molecular weight of components containing crystallizable units, the isothermal crystallization rate exhibited a higher temperature dependence. When the isotactic defects in polypropylene chains increase with the molecular weight of components, both the fold surface free energy σ_e and the work of chain folding q decreases, in spite of the higher molecular weight. © 2002 Society of Chemical Industry     

Isothermal crystallization and spherulite nucleation in blends of polypropylene with metallocene‐prepared polyethylene

The isothermal crystallization behavior and morphology of a polypropylene (PP)‐based copolymer, a metallocene‐prepared linear low‐density polyethylene (M‐LLDPE) and their three 10/90, 30/70 and 50/50 M‐LLDPE/PP blends have been investigated. The PP and M‐LLDPE contained 5 ethylene and 3.3 mol% hexene‐1 as a comonomer, respectively. Isothermal crystallization studies revealed a different temperature‐dependence on crystallization for M‐LLDPE, PP and their blends and the crystallization half‐life for the M‐LLDPE was higher than either PP or the blends at a certain temperature. The PP‐rich blends also showed a quite similar crystallization rate to that of PP. Investigations on the variation of spherulite growth rate of PP in the blends at different temperatures revealed no significant change and was quite independent of the amount of M‐LLDPE being employed. The morphology studies revealed that the nucleation densities of the PP spherulites decreased by introducing M‐LLDPE into PP and the M‐LLDPE remained as discrete droplets dispersed throughout the PP spherulites. The results obtained were consistent with no miscibility between the two components. Copyright © 2005 Society of Chemical Industry     

Effect of silicon dioxide on crystallization and melting behavior of polypropylene

The crystallization and melting behavior of isotactic polypropylene (iPP) and polypropylene copolymer (co‐PP) containing silicon dioxide (SiO₂) were investigated by differential scanning calorimeter (DSC). SiO₂ had a heterogenous nucleating effect on iPP, leading to a moderate increase in the crystallization temperature and a decrease in the half crystallization time. However, SiO₂ decreased the crystallization temperature and prolonged the half crystallization time of co‐PP. A modified Avrami theory was successfully used to well describe the early stages of nonisothermal crystallization of iPP, co‐PP, and their composites. SiO₂ exhibited high nucleation activity for iPP, but showed little nucleation activity for co‐PP and even restrained nucleation. The iPP/SiO₂ composite had higher activation energy of crystal growth than iPP, indicating the difficulty of crystal growth of the composite. The co‐PP/SiO₂ composite had lower activation energy than co‐PP, indicating the ease of crystal growth of the composite. Crystallization rates of iPP, co‐PP, and their composites depended on the nucleation. Because of its high rate of nucleation, the iPP/SiO₂ composite had higher crystallization rate than iPP. Because of its low rate of nucleation, the co‐PP/SiO₂ composite had lower crystallization rate than co‐PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1889–1898, 2006     

β晶型成核剂对PP结晶行为的影响

制备了β晶型聚丙烯(β-PP),利用广角X射线衍射仪与偏光显微镜表征了球晶形态,研究了其非等温结晶行为,并用Jeziorny法、莫志深法和Kissinger法对所得数据进行处理。结果表明,添加β晶型成核剂后,PP由α晶型向β晶型转变,起始结晶温度明显提高,总结晶时间缩短,结晶活化能降低。β-PP的Avrami指数在1．69～1．89,小于PP,表明β晶型成核剂的加入改变了PP的成核机理及生长方式。     

Thermal and crystallization behavior of silane‐crosslinked polypropylene

Silane‐crosslinked polypropylene (PP) has been prepared first by the grafting of silane onto the backbone of PP in a melt process and then by crosslinking in warm water. The effects of type and concentration of silane and peroxide on the silane grafting on PP were investigated. The thermal behavior of the silane‐crosslinked PP was studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) methods. TG results show that PP prepared via silane crosslinking increases its thermal stability greatly. It has been found from DSC measurements that the crystallization temperatures, ie the onset temperature and peak temperature of the exotherm of the silane‐crosslinked PP, increase compared with those of the pure PP. The silane crosslinking hardly changes the crystallinity degree of PP. The crystallization behavior of the silane‐crosslinked PP was also studied by wide‐angle X‐ray diffraction analysis. Copyright © 2004 Society of Chemical Industry