氟气处理孔洞聚丙烯膜显著改善的电荷存储特性

通过衰减全反射(attenuated total reflection,ATR)红外光谱分析与开路热刺激放电(thermally stimulated discharge,TSD)电流、原位实时电荷TSD和电荷等温衰减的测量,研究了氟气对孔洞聚丙烯(PP)膜的氟化改性及氟化改性对其驻极性能的影响.研究结果表明：尽管在负压状态且较低的氟气分压及较低的反应温度(约60℃)和较短的反应时间(约15min)下,氟气能有效地氟化孔洞PP膜,更易于氟化预氧化的孔洞PP膜,氟化改性的孔洞PP膜,尤其是预氧化后的氟化改性 关键词： 孔洞聚丙烯膜 氟气 氟化改性 电荷稳定性     

Theoretical investigation on the model active site for isotactic polypropylene in heterogeneous Ziegler-Natta catalyst: A density functional study

The stereoselectivity of the model active site formed by the adsorption of Ti₂Cl₇ on the (1 0 0) surface of MgCl₂ was investigated by density functional calculations. The analysis of energetics for successive propylene insertions into the model active site reveals that the insertion of propylene into the model active site is energetically more favorable when a growing chain and one chlorine atom (that makes the active site chiral) are on the opposite side rather than on the same side. From this result, it is realized that the model active site is highly stereoselective. It is also observed that the Cl atoms near the growing chain significantly affect the activation energy barrier through the interaction with the growing chain.     

聚环氧丙烷／聚苯乙烯接枝与嵌段共聚物的合成和阻尼性能

合成接枝和嵌段共聚物是研究阻尼材料的重要途径。可以在较广的范围内,调整共聚物的结构,使之具有良好的阻尼性能。我们选择聚环氧丙烷与顺丁烯二酸酐反应,制成端乙烯基大分子单体和遥爪低聚物,与苯乙烯共聚,制成接枝和交联嵌段共聚物。探讨了不同结构因素对阻尼性能的影响规律,研究结果有益于阻尼材料的分子设计。     

Long chain branching on linear polypropylene by solid state reactions

A method was developed for the long chain branching (LCB) of isotactic polypropylene (iPP) via modification in the solid state. PP long chains have been linked as branches to the original linear iPP chains using solid state reactions in the presence of a free radical initiator and a multifunctional monomer (co-agent). The modified samples of branched iPP were characterised by gel permeation chromatography (GPC) and rheological measurements. Several methods were applied in order to estimate indirectly the extent of branching. A ranking was made of the co-agents according to their ability in inducing LCB as opposed to cross-linking and degradation of iPP. The furfuryl sulphide (FS) showed the highest efficiency for the branching reaction, while the divinylbenzene (DVB) is not suitable for branching.     

等规聚丙烯β晶形态研究

本文用正交偏光显微镜和扫描电镜观察了加成核剂βIPP的晶体形态,发现偏光下βIPP为彩色树枝状,是由弧形晶片生长成的球晶,并提出了β晶是由一个中心向相反方向枝化生长的晶体模型。     

Thermally Induced Structural and Dynamic‐Mechanical Transition of Form II of Syndiotactic Polypropylene

Abstract

The elusive helical form II of syndiotactic polypropylene (sPP), not yet fully clarified, was recognized in a fiber drawn at 90°C and its thermally induced transitions were followed by x‐ray diffraction and dynamic‐mechanical analysis as a function of temperature. It was found that this form is stable up to 100°C; afterwards a melting and recrystallization phenomenon occurs leading to the ordered form I. In correspondence to this structural change, the dynamic‐mechanical analysis shows a strong dissipation peak that can be unambiguously associated to the transition and, therefore, can be considered distinctive evidence of the presence of form II.     

Rheological and electrical analysis in carbon nanofiber reinforced polypropylene composites

Two different types of carbon nanofibers (CNF) were incorporated in the same polypropylene (PP) matrix by twin‐screw extrusion. The electrical characterization of both CNFs/PP composites as a function of volume fraction show different electrical performance: conducting and nonconducting. The objective of this work is to study the rheological behavior of both composites with the aim of relating it to the electrical behavior. The results indicate that the rheological behaviors are different, suggesting that rheology differentiates the microstructural variations responsible for the electrical performance. Furthermore, the main rheological parameters were correlated to the electrical conductivity. The results show that G′/G″ and G′ are the most sensitive parameters when compared with the onset of electrical percolation. Finally, in spite of the intrinsic measuring differences between electrical and rheological analysis, the two calculated thresholds are very similar: ～0.5 for the rheological and ～0.4 for the electrical. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Deformation of disentangled polypropylene crystalline grains into nanofibers

It was shown that a solid‐state deformation of polypropylene (PP) being in the form of partially disentangled powder is possible by blending with another molten polymer. During mixing of disentangled polypropylene powder with polystyrene at the temperature below melting of polypropylene crystals the shear forces deform powder grains into nanofibers. All disentangled powder particles larger than 0.7 µm underwent deformation into nanofibers having the mean thickness between 100 and 200 nm. Polypropylene nanofibers got entangled during blending and form a network within polystyrene matrix, reinforcing it. Network of entangled nanofibers can be further deformed with pronounced strain hardening and strength reaching 70 MPa at 135 °C. Blending resulted in generation of PP nanofibers and formation of PP nanofibers entangled network, thus formation of “all‐polymer nanocomposites” in one step compounding. The crucial feature for ultra‐deformation of PP grains by shearing during mixing is disentanglement of macromolecules. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1983–1994     

流场作用对聚丙烯结晶成核过程和晶体生长过程动力学的影响

通过改进基于构象张量构建的流动诱导结晶理论模型,考虑了流场对结晶生长的影响,对比研究了流场作用对聚丙烯(PP)结晶过程中成核与晶体生长两阶段速率的不同影响程度.理论研究表明,虽然相比成核过程,流场诱导作用对PP晶体生长速率的加速程度有限,但要更为精确地描述流动引起的整个结晶动力学过程,特别是在剪切速率较高且熔体结晶温度较低的情况下,考虑流场对结晶生长速率的影响是十分必要的.研究结果还显示,由于分子链的松弛作用,PP在较低温度下的晶体生长速率受剪切流场的影响要大于较高温度下的影响.本文理论预测结果与实验现象和实验数据的很好吻合亦说明模型改进的合理性和可行性.     

On clarification of haze in polypropylene

The mechanism of reducing light scattering in isotactic polypropylene (i‐PP), through the addition of so‐called clarifying agents, is studied with small‐angle light scattering (SALS) and scanning electron microscopy (SEM). The clarifying agents used in this study depict monotectic phase behavior with i‐PP, crystallizing in a relatively narrow concentration range in a nanofibrillar network, providing an ultrahigh nucleation density in the i‐PP melt. It is found that the clarifying effect, a dramatically increased transparency and reduced haze, that occurs within the aforementioned additive concentration range, coincides with a change in morphology from strongly scattering spherulites to shish‐kebab‐like crystalline structures, as evidenced by in situ SALS measurements and confirmed by SEM images. A simple scaling law, relating the diameter of the shish‐kebab structures to the fibril diameter and volume fraction of the clarifying agent is proposed, suggesting that the performance of a (fibril‐forming) clarifying agent will improve by reducing the fibril diameter and/or increasing the volume concentration of the clarifying agent. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 865–874