Characterization of polypropylene�Cpolyethylene blends by temperature rising elution and crystallization analysis fractionation

The introduction of single-site catalysts in the polyolefins industry opens new routes to design resins with improved performance through multicatalyst-multireactor processes. Physical combination of various polyolefin types in a secondary extrusion process is also a common practice to achieve new products with improved properties. The new resins have complex structures, especially in terms of composition distribution, and their characterization is not always an easy task. Techniques like temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) are currently used to characterize the composition distribution of these resins. It has been shown that certain combinations of polyolefins may result in equivocal results if only TREF or CRYSTAF is used separately for their characterization.     

Fusion of homopolymers and ordered copolymers containing ethylene sebacate structural units

The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.     

Effects of stereo-defect distribution and molecular mass in the non-isothermal crystallization behavior of β-nucleated isotactic polypropylene

In this study, based on the synthesis of two Ziegler–Natta iPP with nearly same average isotacticity but different uniformities of stereo-defect distribution, we further prepared two series of β-iPP with different molecular masses by addition of different concentration of peroxide. We investigated the combination effects of stereo-defect distribution and molecular mass on the non-isothermal crystallization behavior and polymorphic composition behavior of β-iPP by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and scanning electron microscope (SEM). The results of non-isothermal crystallization kinetics revealed that the iPP molecular mass has only slight influence on the crystallization temperature of β-iPP, while the uniformity of stereo-defect distribution not only evidently influences the crystallization temperature, but also affects the dependency of crystallization temperature on cooling rate. β-iPP with less uniformity of stereo-defect distribution leads to higher dependency of crystallization temperature on the cooling rate. The calculation of crystallization activation energy ΔE showed that the lower the molecular mass, the lower the ΔE, indicating that it is easier for the occurrence of crystallization. Meanwhile, iPP with more uniform stereo-defect distribution has lower ΔE. Moreover, both stereo-defect distribution and molecular mass are important factors in determining the polymorphic composition. A more uniform stereo-defect distribution is more favorable for the β-phase crystallization; the lower the molecular mass, the harder for β-phase crystallization to take place. However, compared with iPP molecular mass, the uniformity of stereo-defect distribution is the first-order factor in determining the β-phase crystallization of iPP. Moreover, the thermal stability and the dependency of β-phase proportion on the cooling rate are also found to be highly dependent on the iPP molecular mass.     

氯离子柱撑复合氢氧化物纳米微晶的制备及属性

用共沉淀法制备前驱体后,在水热、微波和沸热等不同晶化方式下合成了一系列层状氯离子柱撑镁铝复合氢氧化物(LDH-Cl),在EDS,XRD,IR,TG-DTA,TEM和N₂吸附-解吸测试表征的基础上,讨论了LDH-Cl的组成与结构的关系及制备条件对组成、结构和性质的影响.研究结果表明:LDH-Cl具有超分子结构和水滑石型层状结构的特征;微晶生长习性在不同晶化过程中的差异决定了粒子发育程度的不同、组成与结构相关性的不同;微晶粒子在不同合成条件和晶化方式下表现了不同的结晶度水平从而引起红外吸收、热稳定性及比表面积等基本属性的变化.     

Crystallization Elution Fractionation and Thermal Gradient Interaction Chromatography. Techniques Comparison

Summary: The chemical composition distribution has been shown to be the most critical and discriminating parameter in understanding the performance of industrial polyolefins with non homogeneous comonomer incorporation. The chemical composition distribution is being analyzed by well known techniques such as temperature rising elution fractionation, TREF, crystallization analysis fractionation, CRYSTAF and crystallization elution fractionation, CEF. These techniques separate according to crystallizability and provide a powerful and predictable separation of components based on the presence of branches, irregularities or tacticity differences, independently of the molar mass. TREF, CRYSTAF and CEF can not be used, however, for the separation of more amorphous resins, and may not always provide the best solution for complex multi-component resins due to the existence of some co-crystallization. The application of high temperature interactive HPLC to polyolefins opened a new route to characterize these types of polymers. The use of solvent gradient HPLC for separation of polyethylene and polypropylene and the developments in HPLC on carbon based columns extended further the application of high temperature HPLC in polyolefins. A new approach has been developed recently using the carbon based column but replacing solvent gradient by a thermal gradient which facilitates the analysis of polyethylene copolymers and provides a powerful tool for the analysis of elastomers. Thermal gradient interaction chromatography (TGIC) is being compared with TREF and CEF with the analysis of model samples. The advantages/disadvantages of each technique are being investigated and discussed. The combination of TGIC and TREF/CEF provides an extended range of separation of polyolefins.     

Copolymerization of ethylene and 1-hexene with supported metallocene catalysts: Effect of support treatment

The effect of different catalyst support treatments in the 1-hexene/ethylene copolymerization with supported metallocene catalysts was investigated through the analysis of molecular weight and chemical composition distributions by means of high temperature gel permeation chromatography (GPC) and crystallization analysis fractionation (CRYSTAF). The molecular weight distributions of all copolymers are narrow, indicating a uniform catalyst site. However, with respect to chemical composition distribution, some supported catalysts show broad and sometimes bimodal distributions, which indicates the presence of two or more active site types.     

Melt crystallization of CuFe2S3 in the Cu–Fe–S system

The possibility of melt crystallization of the compound with CuFe₂S₃ composition was established by carrying out quasiequilibrium directional crystallization. The initial liquid had the following composition: Fe 33.3, Cu 16.7, and S 50.0 at.%. The produced sample consisted of three zones with different chemical compositions. The volume fraction of the first zone was 6 %, the second zone was 77 % and the third zone was 17 %. The composition of the first zone corresponded to pyrrhotite solid solution (poss). The second zone had the constant composition CuFe₂S₃. The third zone had variable composition. In the article this zone is not described. We constructed the curves describing the variations in the composition of solid ingot and melt during poss and CuFe₂S₃ crystallization, calculated the distribution coefficients of components, and determined the equation of phase reaction while transferring from the first to the second zone. A polythermal cross-section of phase diagram of the Cu–Fe–S system was built using the directional crystallization and thermal analysis of specially synthesized samples along the crystallization path. It is shown that stoichiometric CuFe₂S₃ compound crystallized from melt and the cross-section of phase diagram along the crystallization path is quasibinary. Thus, liquidus surface of the Fe–Cu–S system contains the region of primary crystallization of CuFe₂S₃, which is located between the crystallization fields of poss and intermediate solid solution.     

Crystaf: Crystallization analysis fractionation. A new approach to the composition analysis of semicrystalline polymers

Crystallization Analysis Fractionation is a new technique for the analysis of composition distribution in semicrystalline polymers; more specifically for the analysis of branching distribution in Polyethylene and tacticity in Polypropylene type resins. CRYSTAF as well as TREF (Temperature Rising Elution Fractionation) are separation techniques which fractionate species of differing crystallizability by slow cooling of a polymer solution. TREF however, demands in addition to the crystallization step a second temperature cycle, elution step, to obtain the polymer composition. CRYSTAF, on the other hand, extracts the information in the crystallization cycle by monitoring the solution concentration depression as temperature goes down; thus reducing significantly the analysis time and simplifying the hardware needs. CRYSTAF principles are discussed and various applications are described.     

IMPACT PROPERTIES OF METALLOCENE - CATALYZED ETHYLENE-α-OLEFIN COPOLYMERS

The impact properties of two selected metallocene-catalyzed ethylene-butene copolymers and one conventionalcopolymer were evaluated using Izod impact test. It is found that the metallocene-catalyzed copolymer shows superior impactproperties. This result was explained on the basis of the more homogeneous inter-molecular composition distribution andnarrower molecular weight distribution, which leads to more homogeneous morphology with fewer defects. Stepwisecrystallization improves the impact properties, especially in the crack propagation process, to a large extent. This is due to thedecrease of entanglements by stepwise crystallization, which is advantageous for the chain slip and shear. The polymer withheterogeneous intra-molecular composition distribution exhibits a more evident improvement of impact properties understepwise crystallization.     

New concept of solute distribution around a diffusive crystal-solution interface of a binary Lennard-Jones mixture from the viewpoint of molecular dynamics

Directional crystallization from a binary mixture was performed by pseudo-NpT ensemble molecular dynamics. The initial crystal phase having a face-centered-cubic (fcc) structure grew toward the whole cell according to the temperature gradient in the universal cell. The growing crystal phase was not planar even though the solute molecules grew in two-dimensional coordinates because the solvent molecules disturbed the crystallization of the solute molecules at the diffusive crystal-solution interface. This represented the essential phenomenon of solute distribution during crystallization. Consequently, the growing crystal phase still contained solvent molecules having a liquid structure. The time change of the solute composition in the early phase of crystal growth showed an increase in solute composition as the time step proceeded. The resulting solute composition in this early phase was considered at different temperature gradients in the universal cell and it increased as the temperature of the initial crystal-solution interface increased. A new distribution coefficient model was proposed as a function of the difference between the local solute composition and bulk solute composition in the solution around the crystal-solution interface. The impurity-solvent distribution coefficient could be represented by the new model for faster growth of the lower temperature's initial interface. As regards a better distribution coefficient, there was found to be a very dilute solution phase over the crystal phase. The new variable "distribution rate" instead of the ambiguous variable "growth rate" was considered as a function of temperature gradient in the universal cell.     

Effect of Chain Microstructure and Cooling Rate on Crystaf Calibration Curves: An Experimental Study

Summary: Crystallization analysis fractionation (Crystaf) is a polymer characterization technique based on differences in chain crystallizabilities in a dilute solution during non-isothermal crystallization. Crystaf profiles, a weight distribution function of chains crystallized at each temperature, can be used to infer the chemical composition distribution (CCD) of copolymers when a Crystaf calibration curve, a relationship between peak crystallization temperature and average comonomer content, is known. In this investigation, the effect of the number average molecular weight, comonomer type, and cooling rate on Crystaf calibration curves were experimentally investigated. It was found that the cooling rate and comonomer type may strongly affect Crystaf calibration curves, while the influence of molecular weight is relatively subtle.     

Crystallization and equilibrium melting behavior of PBT/PETG blends

The results of studies of equilibrium melting point and crystallization behavior of PBT/PETG blends are reported for the first time. A single composition‐dependent glass‐transition temperature is observed in the DSC studies. The isothermal crystallization studies of the blends indicate retardation in crystallization rate as evidenced by the increase in crystallization half time. The retardation in crystallization rate has been attributed to the miscibility in the molten state and the hindrance to the diffusion of crystallizable units. This assumption is further supported by the composition dependence of the crystallization half time. A composition‐dependent melting point depression has been observed which has been attributed to the possible thermodynamic and morphological effects. The interaction parameter calculated by analyzing equilibrium melting point depression shows composition‐dependent negative values confirming the miscibility of the systems. These results are in good agreement with our earlier results on mechanical and dynamic mechanical properties of PBT/PETG blends. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2439–2444, 1999     

Distribution of Impurities During Low-Temperature Directed Crystallization of Water Solutions

Trends in the distribution of impurities at low-temperature directed crystallization of water solutions of various concentrations are described and the mechanism of their incorporation in the solid phase is explained. The data on the distribution coefficients of the impurities between the solid and liquid phases are presented. It is shown that the behavior of the impurities in the process of directed crystallization is the same and does not depend on the nature of the macrocomponent. The unique case of CsI is explained due to the negative values of hydration of iodide and cesium ions. It is recommended to use the observed trends for the purification of water or analytical pre-concentration of impurities.The coefficients of enrichment of the impurities after low-temperature directed crystallization of aqueous solutions with different composition and total concentration of the dissolved salts are estimated and their dependencies on the composition and concentration of the aqueous solution are shown.     

两嵌段共聚物PB-PDMS中PDMS的结晶行为与共聚物形态结构的关系

聚二甲基硅氧烷(PDMS)的结晶熔融温度(T_m)约为-43℃,远高于其玻璃化转变温度(T_g)(-124℃),为扩大其低温使用范围,需要破坏其链结构规整性以抑制结晶发生。但是我们发现在前人工作中,含PDMS段的嵌段共聚物,即使不破坏PDMS段的链结构规整性,其动态力学谱上有时也观测不到PDMS的结晶峰。遗憾的是这些作者末曾对这一不寻常现象给予足够的重视。无疑,搞清共聚物中PDMS不寻常结晶行为同共聚物形态结构的关系,对提高含有PDMS段的嵌段型热塑性弹性体的低温使用范围将有指导意义。本文报导PB-PDMS中的结晶行为与共聚物形态结构的关系。     

苯乙烯-丙烯嵌段共聚物等温结晶动力学的研究

用DSC法研究苯乙烯-丙烯嵌段共聚物(iPS-b-iPP)的等温结晶动力学。结果表明,在所选择的结晶温度(127～132℃)范围内,共聚物很好地符合Avrami动力学方程;共聚物结晶温度、结晶速率、结晶成核和生长方式都与共聚物结构和组成比有关,随着嵌段共聚物中iPS段含量的增加,结晶速率和Avranu指数(n)明显降低。     

Crystallization behavior of some unimodal and bimodal linear low‐density polyethylenes at moderate and high supercooling

Effect of molar mass distribution (MMD) and composition distribution (CD) on crystallization behavior of linear low‐density polyethylene materials at moderate and high supercooling was studied using differential scanning calorimetry, hot‐stage polarized light microscopy, small‐angle light scattering, and chip nanocalorimetry methods. A set of uni‐ and bimodal materials having small variation in average molar mass, density, and melt flow rate, but large differences in MMD and CD, was investigated. The results indicate a clear effect of structural heterogeneity on morphology and crystallization behavior of the materials. Broader MMD and CD increased in average radius of superstructures, melting, crystallization temperatures, and isothermal crystallization rate at different supercoolings. Origin of such behavior is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1577–1588, 2008     

Separation of ethylene‐propylene copolymers and ethylene‐propylene‐diene terpolymers using high‐temperature interactive liquid chromatography

Ethylene‐propylene‐diene terpolymers (EPDM) are generally amorphous and, therefore, do not crystallize from solution. Consequently, fractionation techniques based on crystallization, such as crystallization analysis fractionation or temperature rising elution fractionation, cannot be used to analyze their chemical composition distribution. Moreover, no suitable chromatographic system was known, which would enable to separate them according to their chemical composition. In this study, two different sorbent/solvent systems are tested with regard to the capability to separate EPDM‐terpolymers and ethylene‐propylene (EP)‐copolymers according to chemical composition. While porous graphite/1‐decanol system is selective towards ethylene and ethylidene‐2‐norbornene, carbon coated zirconia/2‐ethyl‐1‐hexanol is preferentially selective towards ethylene. Consequently, the earlier system enables to separate both EP copolymers and EPDM according to the chemical composition and the latter mainly according to the ethylene content. The results prove that the chromatographic separation in both sorbent/solvent systems is not influenced by molar mass of a sample or by its long chain branching. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

聚(丁二酸丁二酯-co-丁二酸丙二酯)的等温结晶行为研究

以1,4-丁二酸、1,4-丁二醇和1,3-丙二醇为原料通过直接熔融缩聚法合成了聚丁二酸丁二酯(PBS),聚丁二酸丙二酯(PPS)和聚(丁二酸丁二酯-co-丁二酸丙二酯)(PBSPS)等脂肪族聚酯.利用1H-NMR,WAXD,DSC和POM等研究了聚酯的结晶结构和结晶动力学过程等结晶行为.PBSPS的结晶晶型与PBS一致,说明只有丁二酸丁二酯(BS)单元结晶而丁二酸丙二酯(PS)单元处于无定形区.聚酯等温结晶后,在升温熔融过程中出现了多重熔融峰.分析表明多重熔融峰主要来自于聚酯升温过程中的熔融-重结晶行为.利用Avrami方程分析了聚酯的等温结晶动力学,Avrami指数n为2.2~2.8,说明聚酯等温结晶时主要以异相成核的三维生长方式进行;随着PS单元的增多,聚酯的表观结晶活化能升高,也就是说BS单元的结晶变得困难.POM观察到聚酯等温结晶时都出现了环带球晶现象,球晶形态会随着结晶温度和化学结构差异而改变.     

苯乙烯-丙烯等规立构嵌段共聚物(iPS-b-iPP)的非等温结晶动力学的研究

用DSC法研究了苯乙烯-丙烯等规立构嵌段共聚物的非等温结晶动力学。结果表明:冷却速率在5～20℃/min范围内,共聚物的非等温结晶动力学参数能很好地符合Avrami动力学方程,非等温结晶速率常数与冷却速率有关,动力学结晶能力则同时受到冷却速率和共聚物组成比的影响。文中还讨论了在非等温结晶条件下共聚物的结晶成核和生长方式与共聚物组成和结构的关系。联合Avrami方程和Ozawa方程推导的非等温结晶动力学方程较好地描述了iPS-b-iPP嵌段共聚物的非等温结晶动力学过程。