高橡胶含量透明MBS合成及其对PVC的改性

高橡胶含量透明ＭＢＳ合成及其对ＰＶＣ的改性高南，肖贵斌，胡伟军（上海大学化学系上海嘉定２０１８００）关键词　ＭＢＳ树脂，ＰＶＣ树脂，乳液聚合，塑料增韧，透射电镜ＭＢＳ（甲基丙烯酸甲酚－丁二烯－苯乙烯）树脂具有复杂的多相结构，可用作硬质聚氯乙烯（ＰＶＣ...     

IPN结构的SIS-PAn导电复合物

合成了互穿网络（ＩＰＮ）结构的ＳＩＳ（苯乙烯－异戊二烯－苯乙烯嵌段共聚物）－ＰＡｎ（聚苯胺）导电复合物。Ａｎ／ＳＩＳ的投料比为０．２ｇ／１．０ｇ时，制得复合物膜电导率即可达７Ｓ·ｍ－１。复合物的电导率随基体ＳＩＳ交联程度的增大而降低。研究了溶剂、反应时间和分散剂用量对复合物膜性能的影响。     

苯乙烯－丁二烯－苯乙烯／聚（苯乙烯－甲基丙烯酸盐）热塑性互穿聚合物网络的形态和玻璃化转变

使用化学共混法和机械共混法制备了三嵌段苯乙烯－丁二烯－苯乙烯共聚物（ＳＢＳ）／聚（苯乙烯－甲基丙烯酸盐）热塑性互穿聚合物网络（ＩＰＮ）．用透射电镜和动态力学方法研究了它们的形态和玻璃化转变行为．实验结果显示出，由母体形成ＩＰＮ提高了体系的相容性，且化学共混方法明显好于机械共混法．ＩＰＮ样品均呈微观相分离形态，具有两个分属于聚丁二烯相和聚（苯乙烯－甲基丙烯酸盐）相的玻璃化转变温度．通过Ｂｕｄｉａｎｓｋｙ方程和Ｋｅｒｎｅｒ方程对动态模量数据的分析表明，ＩＰＮ样品具有两相连续性，且随ＳＢＳ（聚合物Ⅰ）组分含量的增加，聚（苯乙烯－甲基丙烯酸）（聚合物Ⅱ）的连续程度降低     

苯乙烯－丁二烯－苯乙烯工嵌段共聚物／聚（苯乙烯－甲基丙烯酸盐）热塑性IPN中离子聚集结构的研究

苯乙烯－丁二烯－苯乙烯工嵌段共聚物／聚（苯乙烯－甲基丙烯酸盐）热塑性ＩＰＮ中离子聚集结构的研究韦雨春，袁惠根，潘祖仁（浙江大学化工系杭州３１００２７）关键词互穿聚合物网络，离子聚集，远红外光谱，Ｘ－光散射以苯乙烯－丁二烯－苯乙烯三嵌段共聚物（ＳＢＳ）...     

苯乙烯－乙烯共聚物的合成及其结构性能的研究

用负载型钛系催化剂ＭｇＣｌ_２／ＴｉＣｌ_４，ＮｄＣｌ_３／ＡｌＥｔ_３（ＳＮ－１催化剂）制备出组份比例变化的苯乙烯－乙烯共聚产物．共聚产物通过溶剂萃取分离、~１３Ｃ－ＮＭＲ、ＩＲ、动态粘弹谱进行表征，并初步进行了与聚苯乙烯（ａＰＳ）共混作用的研究．结果表明，ＳＮ－１催化剂能有效地催化苯乙烯与乙烯共聚合．共聚产物为含有均聚聚苯乙烯的共聚物复合物，其中的２５ｍｏｌ％的苯乙烯参加了共聚．共聚产物与ａＰＳ共混可明显提高ａＰＳ的冲击强度和断裂伸长率．     

丙烯酸丁酯－苯乙烯－丙烯腈共聚物的结构与力学性能

丙烯酸丁酯－苯乙烯－丙烯腈共聚物的结构与力学性能张会轩，韩业，张会良，冯之榴（吉林工学院化工系长春１３００１２）（中国科学院长春应用化学研究所长春）关键词ＡＳＡ，乳液聚合，粒子，力学性能丙烯酸丁酯－苯乙烯－丙烯腈共聚物（ＡＳＡ）是两相结构，聚丙烯酸丁...     

用SN型催化剂合成苯乙烯一丙烯嵌段共聚物的研究──Ⅰ．聚合条件对共聚合反应的影响

用稀土化合物改性的钛系载体催化剂（ＳＮ催化剂）进行苯乙烯和丙烯顺序嵌段共聚合（Ｓｅｑｕｅｎｔｉａｌｂｌｏｃｋｃｏｐｏｌｙｍｅｒｉｚａｔｉｏｎ）的研究．考察了苯乙烯预聚时间、单体比、外加给电子体（ＥＢ）、烷基铝浓度、催化剂浓度和聚合温度等条件对共聚合的影响．发现外加酯（ＥＢ）降低了共聚合反应催化活性，在ＥＢ／Ｔｉ摩尔比为５范围内，外酯有助于提高嵌段共聚物（ｉＰＳ—ｂ—ｉＰＰ）中ＰＳ段和ＰＰ段的等规度及增加苯乙烯链节含量．ＳＮ型催化剂对苯乙烯一丙烯嵌段共聚合有较高的催化活性，催化效率在１００ｇ聚合物／ｇ－Ｔｉ以上．共聚物通过溶剂革取分级除去均聚物后，所得嵌段共聚物中苯乙烯链节含量可在１５～８５ｍｏｌ％之间调节．其结构表征续见第ＩＩ报．     

聚环氧氯丙烷聚氨酯／聚（甲基丙烯酸甲酯－苯乙烯）IPN的研究

改变聚（甲基丙烯酸甲酯－苯乙烯）（Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中甲基丙烯酸甲酯的含量（Ｗ_（ＭＭＡ）），通过一步法合成出聚环氧氯丙烷聚氨酯（ＰＵ（ＰＥＣＨ）／Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）ＩＰＮ．ＤＳＣ、ＴＥＭ和动态粘弹谱研究结果表明：当Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中Ｗ_（ＭＭＡ）大于０．６时，ＩＰＮ仅有一个Ｔｇ；当Ｗ_（ＭＭＡ）小于０．４时，ＩＰＮ有２个Ｔ_ｇ，ＴＥＭ上出现相区，Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）溶度参数（δ）及δ的氢键作用分量（δｈ）与相态、力学性能有密切关系。     

1,4—双（取代苯乙炔基）苯及反,反—1,4—双（β—取代苯乙…

测定了１，４－双（取代苯乙炔基）苯（Ⅰ）和反，反－１，４－双（β－取代苯乙烯基）苯（Ⅱ）的紫外光谱、荧光光谱。用ＣＮＤＯ／Ｓ－ＣＩ和ＨＭＯ方法对苯乙炔、二苯乙炔和（Ⅰ）及苯乙烯、１，２－二苯乙烯和（Ⅱ）的激发能进行了计算和研究。讨论了化合物结构对光谱的影响。     

聚环氧丙烷聚氨酯／聚（甲基丙烯酸甲酯—苯惭烯）IPN的研究

改变聚（甲基丙烯酸甲酯－苯乙烯（Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中 甲基丙烯酸甲酯的含量（ＷＭＭＡ），通过一步法合成出聚环氧氯丙烷聚氨酯（ＰＵ（ＰＥＣＨ）／Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）ＩＰＮ．ＤＳＣ、ＴＥＭ和动态粘弹谱研究结果表明：当Ｐ（ＭＭＡ＿ｃｏ－Ｓｔ）中ＷＭＭＡ大于０．６时，ＩＢＮ仅有一个Ｔｇ；当ＷＭＭＡ小于０．４时，ＩＰＮ有２个Ｔｇ，ＴＥＭ上出现相区，Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）深度参数（δ）及δ的氢键作     

A novel staining technique for studying toughening mechanisms in saturated acrylic rubber-modified polymers

A novel technique which utilizes a two-stage staining approach, (i.e., styrene absorption followed by osmium tetraoxide staining) is introduced for staining saturated polyacrylate rubbers. This novel staining approach, which stains and hardens polyacrylate rubber, is found to be useful for room temperature microtomy of polyacrylate rubber-modified polymers. Therefore, both the morphology and the crack tip toughening mechanisms of polyacrylate rubber-modified systems can be studied. Details concerning staining time, staining media, and use of solvents are discussed.     

Experimental approach for microscale mechanical characterization of polymeric structured materials obtained by additive manufacturing

In this paper, an original experimental method is developed for local strain characterization at the surface of additively manufactured polymeric materials. The process used herein is material extrusion. This experimental method is based on the use of microscopic speckle pattern deposited at the surface of micro single edge notched specimen (μ_SENT) made of acrylonitrile butadiene styrene (ABS). Two configurations of filament orientation were used for the specimen manufacturing. Images of the μ_SENT specimen surface were recorded during in-situ tensile test. The quantitative analysis of images was made by digital image correlation (DIC). The evolutions of the local strain heterogeneities and the crack tip are evidenced on the kinematic fields. It is shown that the crack propagates in the low resistance path which is the interface area between filaments. It is also evidenced that the intersection of perpendicular filaments in two adjacent layers blocks crack growth. The local strain evolutions at the surface of the specimen are compared to the macroscopic response of the material. The method developed herein allows the determination of the materials mechanical properties. The identification of the crack tip location using digital image correlation (DIC) and J-integral calculation lead to plot the J-R curve. The J-R curves comparison of the two specimen configurations shows that the fracture toughness is directly related to the material structure.     

Improvement of the impact and crack resistance of epoxy thermosets and thermoset-based composites with the use of thermoplastics as modifiers

Main methods for the modification of epoxy composites that aim to increase their impact and crack resistances are considered with the main attention focused on modification with the use of thermally stable thermoplastics as additives. The influence of various factors (the modifier–matrix chemical bond and the morphology and molecular weight of the modifier) on the physicomechanical characteristics of the composites is discussed. New approaches to the toughening of polymeric composite materials based on epoxy thermosets that involve the use of modified binders or the introduction of a modifier between layers of the composite prepreg are advanced.     

Nanocavitation around a crack tip in a soft nanocomposite: A scanning microbeam small angle X‐ray scattering study

We explore nanocavitation around the crack tip region in a styrene‐butadiene random copolymer filled with typical carbon black (CB) particles used in the rubber industry for toughening the rubber. Using quasistatic loading conditions and a highly collimated X‐ray microbeam scanned around the crack tip, we demonstrate the existence of a damage zone consisting of nanovoids in a filled elastomer matrix. The existence of voids near the crack tip is demonstrated by a significant increase of the scattering invariant Q/Q₀ in front of both fatigued and fresh cracks. The size of the zone where cavities are present critically depends on the macroscopic strain ε_m, the loading history, and the maximum energy release rate G applied to accommodate the crack. Our findings show that nanovoiding occurs before fracture in typical CB‐filled elastomers and that realistic crack propagation models for such elastomers should take into account a certain level of compressibility near the crack tip. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 422–429     

核-壳粒子增韧聚合物的研究进展

核-壳粒子增韧结合了弹性体增韧和刚性粒子增强的优点，将其用于聚合物共混体系中有可能得到比基体树脂更高韧性更好刚性的复合材料。本文综述了相关核-壳粒子的分类、形态、形成机制，以及它们对聚合物基体的增韧机理，并详细阐述了反应性和非反应性聚合物共混体系中原位形成的核-壳粒子形态演化规律及其对共混物力学性能的影响。     

Crack propagation behavior in rubber materials

Within the linear viscoelastic theory, crack tip fields are calculated at various crack tip velocities. A transition from rubbery to glassy material behavior in the vicinity of the crack tip can be observed. Shear and bulk behavior is analyzed separately. Whereas the increase of tearing energy at higher crack tip velocities can be ascribed to the shear behavior, bulk behavior influences the fracture mechanism. The results support experimental investigations that the instability separating stable from unstable crack propagation is related to a change in the fracture mechanism. At low crack tip velocities, material separation is the result of formation, growth, and coalescence of cavities. At high crack tip velocities, cavitation is suppressed and fracture is driven by a rather brittle mechanism resulting in a decreased amount of energy to propagate the fracture process zone. Published in Russian in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 5, pp. 882–891. This article was submitted by the authors in English.     

Electron-beam-induced fracture of polymers

When a notched polymeric material is stressed, the notch opens into a wide crack tip, exposing a region of high stress concentration. The consequences of electron bombardment of the tip of such a stressed material under vacuum are explored here for the first time. Evidence is presented for electron-induced crack growth at stress far below that needed for crack growth due to stress alone. The electron current densities used in these experiments are sufficiently small that thermal heating of the zone near the crack tip is minimal. To provide information on the phenomena involved, we present simultaneous measurements of electron current, gas pressure, and sample load in response to periodic bombardment of the sample. Experiments involving the bombardment of un-notched polymers under stress are also described. Fractography of the unique structures obtained by fracture due to the combination of electron bombardment and stress are presented and interpreted in terms of a crosslinking mechanism.     

The effects of annealing on fatigue crack propagation in polyethylene

Fatigue crack propagation tests on annealed and quenched medium-density polyethylene showed the annealed specimens to have much lower resistance to crack initiation and subsequent propagation. Although the same fracture mechanism, in which the brittle crack gradually becomes more ductile, prevailed in both cases, the voided and fibrillated crack tip root craze in the annealed material was much weaker that the nonfibrillated quenched root craze. Microstructural analyses indicate that the annealed material had separate crystallite populations, whereas the quenched material had a more homogeneous morphology. The highest melting fraction of the annealed material was composed of lamellae that were about 270 Å thick, and the quenched lamellae were estimated to be 160 Å thick. The reduced fatigue crack propagation resistance of the annealed material was suggested to be a result of a lower concentration of tie molecules and its reduced damping capability, compared to the quenched material. © 1995 John Wiley & Sons, Inc.     

Mapping the damaged zone around the crack tip in high density polyethylene with synchrotron microfocus small angle X-ray scattering technique

<正>The structural changes around a crack tip in a high density polyethylene were investigated by means of scanning synchrotron microfocus small-angle X-ray scattering technique.The scattering data confirm the process of craze structure development near a crack tip based on the evolution of voids.In addition,it was found that the main stress in the plastic zone near a crack tip exhibited a gradient distribution with respect to its strength and direction.The whole damaged area showed a strain distribution indicating a flow behavior toward the crack tip.     

Experimental and theoretical investigation of stress corrosion crack (SCC) growth of polyethylene pipes

Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semicrystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. Stress corrosion cracking (SCC) results from strongly coupled thermo-mechano-chemical processes, and is sensitive to material composition and morphology. The individual crack propagation stage is critical in determining the lifetime of pipe. Based on author's previous works, crack layer (CL) theory model is adopted in this study to describe the individual stress corrosion (SC) crack propagation kinetics and the time interval from crack initiation to instability and break through. The effect of localized chemical degradation at the crack tip on SC crack growth kinetics is addressed. Typical SC crack growth is presented and discussed as a step-wise manner based on the proposed model. In addition, scanning electron microscopy (SEM) observation and Fourier transform Infrared spectroscopy (FTIR) analysis of failed samples obtained by accelerated SCC tests are applied to validate the proposed model. SEM is useful to identify the change of fracture mechanisms from chemically driven crack to mechanically driven crack by the formation of visible striations. FTIR analysis enables tracking of the accumulation of chemical degradation by detecting the amount of carbonyls on the crack surface. Carbonyl index is defined to compare the amount of chemical degradation quantitatively. The purpose of this paper is to continue to develop the technical theory and understanding behind SCC phenomena to facilitate all polymer pipe industries and in particular the polyethylene pipe industry to design better resins and piping systems.