Studies of the comonomer distributions in low density polyethylenes using temperature rising elution fractionation and stepwise crystallization by DSC

The comonomer distributions of commercial linear low density polyethylenes (LLDPE) and linear very low density polyethylenes (VLDPE) produced with traditional high activity Ziegler–Natta (Z–N) catalysts were characterized by temperature rising elution fractionation (TREF). In order to develop faster characterization methods the polymers were also characterized using a segregation fractionation technique (SFT) based on a stepwise crystallization by differential scanning calorimetry (DSC). Comparative studies of SFT and TREF demonstrated that SFT provides an alternative tool for the relative qualitative analysis of the chemical composition distribution (CCD) and the technique is useful to characterize the heterogeneity in comonomer unit distribution. Lamellar thickness distributions can be calculated from the DSC endo-therms by applying the Thomson–Gibbs equation. The SFT technique was also applied to commercial single-site (metaliocene) LLDPE and VLDPE polymers. In spite of their more homogeneous structure compared with the Z–N copolymers, which contain many active sites, these single site copolymers also gave thermograms resolved into several peaks.     

乙烯三元共聚合研究现状及展望

从三元共聚合制备高性能聚乙烯(PE)和热塑性弹性体两个领域综述了乙烯三元共聚合机理的研究现状。高性能PE的研究主要集中在聚合过程中的“共单体效应”和“促进效应”;而三元乙丙橡胶的研究重点在对催化剂的研究和二烯烃的选择上。介绍了乙烯三元共聚合的工业化应用情况,总结了目前乙烯三元共聚合研究中存在的问题,并提出今后的研究方向。     

振荡操作制备双峰聚乙烯的模拟

以流化床乙烯气相聚合工艺为例,提出了通过控制聚合反应条件的振荡操作,在单一反应器内实现制备双峰分子量分布聚乙烯的新工艺.通过模拟计算,分别考察了氢气、乙烯、共聚单体进料速率和反应温度的振荡操作对聚乙烯分子量分布的影响.计算结果表明,采取振荡操作后,聚乙烯树脂的分子量分布呈明显的双峰分布,表明在一个反应器里通过控制反应条件的振荡来制备双峰聚乙烯是可行的,而控制氢气进料速率的振荡操作是制备双峰聚乙烯最为有效的方法.     

阳离子型共聚单体DMC在MMA/BA/DMC无皂乳液聚合中的影响

研究了阳离子型共聚单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)的用量对甲基丙烯酸甲酯(MMA)/丙烯酸丁酯(BA)/DMC无皂乳液聚合速率、聚合物在THF中的溶解性、乳液稳定性及pH值的影响。实验结果证明,此体系中所生成的乳胶粒子均匀,表面清洁,并且DMC含量在1.5wt%~3.5wt%时(建立在BA和MMA总质量基础上),乳液具有较高的稳定性。     

Isothermal crystallization of metallocene‐based propylene/α‐olefin copolymers

Isothermal crystallization and subsequent melting behavior of two propylene/hexene‐1 copolymers and two propylene/octene‐1 copolymers prepared with metallocene catalyst were investigated. It is found that γ‐modification is predominant in all copolymers. The Avrami exponent shows a weak dependency on comonomer content and comonomer type. At higher crystallization temperatures (T_c) the crystallization rate constant changes more rapidly with T_c and the crystallization half‐time substantially increases. Double melting peaks were also observed at high T_c, which is attributed to the inhomogeneous distribution of comonomer units along the polymer chains and the existence of crystals with different lamellar thicknesses. The equilibrium melting temperatures (T) of the copolymers were obtained by Hoffman–Weeks extrapolation. It was found that the T decreases with increasing comonomer content, but are independent of comonomer type, implying that comonomer units are excluded from the crystal lattice. Dilation of the crystal lattice was also observed, which depends on crystallization, comonomer content, and comonomer type. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 240–247, 2005     

耐热聚乙烯管材专用树脂的结构与性能

研究了3种耐热聚乙烯管材专用树脂的结构与性能。它们的共同特征为熔体流动速率低于0.7 g/10 min,密度为0.930~0.944 g/cm3,相对分子质量为(1.5~2.5)×105,可以为窄相对分子质量分布,也可以为中等相对分子质量分布。1-己烯共聚产品与1-辛烯共聚产品性质较为接近,都是窄相对分子质量分布,而1-丁烯共聚产品具有相对分子质量高(2.0×105以上),相对分子质量分布中等(10左右),熔体流动速率低(低于0.3 g/10min)、密度高(大于0.940 g/cm3)、拉伸屈服强度高、弯曲模量高、熔融峰温高、结晶峰温高的特点。相同条件下,1-丁烯共聚产品具有较高的黏度和模量。     

Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl2‐TiCl4‐based Ziegler‐Natta catalysts

The characteristic features of LLDPE polymerization with ZN catalyst are the time drift effect during polymerization and the bending effect when trying to decrease density of the copolymer by adding more comonomer to the polymerization. The time drift in LLDPE polymerization is revealed by a constant decrease of comonomer incorporation during polymerization time. The bending is revealed by difficulties in lowering the density of LLDPE material below the density of 920 kg/m³. With increasing comonomer content during polymerization, the density does not decrease, but the soluble fraction increases. To try to observe if these phenomena are connected, two types of catalysts, SiO₂ supported and precipitated MgCl₂ ZN catalysts, were studied. A short time (10 min) and an extended time (60 min) copolymerization test series where the polymerizations were performed in the presence of a gradually increasing comonomer amount. Both catalysts show a strong bending when density is presented as a function of 1‐hexene both in 10‐ and 60‐min polymerization, indicating no connection between time drift and bending. The density, melting point, and crystallinity results all indicate that both catalysts are making similar copolymer material with identical chemical composition distribution. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Clarifying the effects of comonomer distribution between short and long chains on physical and mechanical properties of ethylenic copolymers

In this paper, two Zigler-Natta catalysts (ZNCs) were used to synthesize a commercially available linear low-density polyethylene (LLDPE), widely used in the packaging industry, on an industrial scale. The catalysts differ only in their ability to distribute comonomers between short and long chains. Both catalysts were fully characterized in the first section, and two similar ethylene/1-butene copolymers were made using them. Afterward, the produced copolymers were fully characterized using different techniques; namely, differential scanning calorimetry (DSC), successive self-nucleation and annealing (SSA), oxygen induction time (OIT), melt flow index (MFI), rheometric mechanical spectroscopy (RMS), and a wide range of mechanical experiments. It was revealed that while the presence of comonomers in short chains can reduce their resistance against oxidation (by more than 30%) and can cause a dramatic change in friction coefficients (by more than 20%), some of the other main mechanical properties of the made copolymers were independent of comonomer distribution between long and short chains. In addition, it was shown that ethylenic copolymers' strain hardening modulus (SHM) takes advantage of the homogenous distribution.     

界面剂与共聚单体对固相接枝聚丙烯表面性质的影响

采用固相接枝方法,研究了以二甲苯为界面剂,以苯乙烯(St)、丙烯酸丁酯(BA)为接枝共聚单体对马来酸酐接枝聚丙烯(PP-g-MAH)表面性能的影响。研究结果表明,随着二甲苯用量的增加,PP- g-MAH的表面能和极性力分量呈先升后降的趋势,当w(二甲苯)=15%时,表面能(37.52 mN/m)和极性力分量(2.47 mN/m)均达到最大值;共聚单体St、BA的加入可以显著提高PP-g-MAH的表面能和极性力分量,共聚单体St的作用更为有效,其接枝物的极性力分量分别是PP-g-(MAH-co-BA)的2倍,PP- g-MAH的4.8倍。     

Synthesis and electrochemical polymerization of N‐ethylcarbazole‐bis‐3,4‐etyhlenedioxythiophene‐N‐ethylcarbazole comonomer

A new comonomer ECz‐BEDOT‐ECz (EBEE) [ECz: N‐ethylcarbazole‐BEDOT:2,2′‐bis(3,4‐ethyhlenedioxy) thiophene] has been synthesized, characterized, and electropolymerized on Pt and carbon fiber microelectrodes (CFME). The ECz side group of the comonomer plays an important role in determining its physical properties PEBEE and it resembles the behavior of corresponding homopolymer (PECz). PBEDOT was increased by the incorporation of ECz monomer into structure. The environmental stability of PBEDOT was increased by incorporating the ECz unit into the structure. The new comonomer seems prefer to be electrodeposited onto CFME as opposed to Pt. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 795–801, 2007