聚烯烃嵌段共聚物技术的研究进展

综述了聚烯烃嵌段共聚物(OBC)的制备方法,包括链穿梭聚合法、活性聚合法、短周期停流聚合法和管式反应器技术。重点介绍了链穿梭聚合法的基本原理、催化体系及生产工艺,该方法在制备OBC产品方面具有很大的优势。介绍了OBC的表征方法、产品的性能及应用。对利用链穿梭聚合法制备OBC提出了展望。     

Electro-thermal and -mechanical model of thermal breakdown in multilayered dielectric elastomers

Multiple breakdown phenomena may take place when operating dielectric elastomers. Thermal breakdown, which occurs due to Joule heating, becomes of special importance when using multilayered stacks of dielectric elastomers, due to the large volume-to-surface-area-ratio. In this article, a 2D axisymmetric finite-element model of a multilayered stack of dielectric elastomers is set up in COMSOL Multiphysics®. Both the electro-thermal and electro-mechanical couplings are considered, allowing for determination of the onset of thermal breakdown. Simulation results show that an entrapped particle in the dielectric elastomer drastically reduces the possible number of layers in the stack. Furthermore, the possible number of layers is greatly affected by the ambient temperature and the applied voltage. The performance of three hyperelastic material models for modeling the elastomer deformation are compared, and it is established that the Gent model yields the most restrictive prediction of breakdown point, while the Ogden model yields the least restrictive estimation.     

Crystallization-Directed Anisotropic Electroactuation in Selectively Solvated Olefinic Thermoplastic Elastomers: A Thermal and (Electro)Mechanical Property Study

Dielectric elastomers (DEs), a class of soft electroactive polymers that change size upon exposure to an external electric field, constitute an increasingly important class of stimuli-responsive polymers due primarily to their large actuation strains, facile and low-cost fabrication, scalability, and mechanical robustness. Unless purposefully constrained, most DEs exhibit isotropic actuation wherein size changes are the same in all actuation directions. Previous studies of DEs containing oriented, stiff fibers have demonstrated, however, that anisotropic actuation along a designated direction is more electromechanically efficient since this design eliminates energy expended in nonessential directions. To identify an alternative, supramolecular-level route to anisotropic electroactuation, we investigate the thermal and mechanical properties of novel thermoplastic elastomer gels composed of a selectively solvated olefinic block copolymer that not only microphase-separates but also crystallizes upon cooling from the solution state. While these materials possess remarkable mechanical attributes (e.g., giant strains in excess of 4000%), their ability to be strain-conditioned enables huge anisotropic actuation levels, measured to be greater than 30 from the ratio of orthogonal actuation strains. This work establishes that crystallization-induced anisotropic actuation can be achieved with these DEs.     

Structure–property relations of nylon‐6 and polytetramethylene glycol based multiblock copolymers with microphase separation prepared through reactive processing

A series of poly(urethane‐urea‐amide) thermoplastic elastomers (PUUAs) based on polytetrahydrofuran (polytetramethylene glycol, PTMG), nylon‐6 and 4,4′‐diphenylmethane diisocyanate were synthesized through reactive processing. This method solved the incompatibility of nylon‐6 and PTMG, and these model elastomers were used to gain insight into the structure–property relations of block polymers. The target products were solvent resistant, transparent and melting‐processable. Fourier transform infrared spectroscopy, XRD, DSC, TEM, dynamic mechanical analysis, tensile testing and TGA were used to study the structure, crystallization, morphology, mechanical properties and thermostability of the PUUAs. The Fourier transform infrared results proved the successful preparation of PUUAs from nylon‐6 and PTMG. TEM examination showed that all samples exhibit microphase separated morphology with the nylon‐6 domain dispersed in the PTMG phase. The results of tensile testing indicated that the elastomers exhibit excellent mechanical properties with stress at break and strain at break exceeding 40 MPa and 600% respectively. The TGA results implied that the PUUAs can be fabricated by transitional processing at proper temperature without any thermodegradation. These favorable features were related to the microphase separated structure of the PUUAs. © 2016 Society of Chemical Industry     

聚烯烃弹性体技术进展

聚烯烃弹性体为一类新型乙烯与高级α-烯烃共聚物，由于应用茂金属催化技术且分子结构中引入大量高级α-烯烃共聚单体并保留一定聚乙烯结晶相而兼备可塑性和弹性，具有良好的机械性能、加工性能和热性能。聚烯烃弹性体主要生产商有Exxon公司、Dow化学公司、Mitsui公司和LG公司，均采用溶液法聚合工艺及茂金属催化技术，其中,以Dow化学公司的Insite聚合工艺与CGC茂金属催化技术为代表，限定几何构型（CGC）催化剂为桥联单茂结构催化剂，其自身结构变化对催化性能影响较大，改变桥基团、Cp环上的烷基取代基和配位基团均可得到不同结构和性能的催化剂。Exxon公司采用Exxpol茂金属催化剂开发Exact塑性体［密度(0.860~0.915) g·cm^-3］，包括乙烯-辛烯共聚物、乙烯-己烯共聚物和乙烯-丁烯共聚物;采用同种催化技术，溶液法生产丙烯基弹性体，商品名为Vitamaxx。2003年，日本Mitsui公司-三井弹性体新加坡公司100 kt·a-1的乙丙橡胶弹性体装置投产，装置采用茂金属催化技术和独有的溶液法聚合工艺，商品名为Tafmer［密度(0.862~0.905) g·cm^-3］。韩国LG公司将独特的茂金属催化剂与溶液法聚合工艺相结合，生产聚烯烃弹性体［密度(0.865~0.903) g·cm^-3］，商品名为LUCENE。我国目前没有聚烯烃弹性体生产企业，开展过一些高共聚性能茂金属催化剂的研发，应用于聚烯烃弹性体技术开发。     

Influence of maleated elastomer on filler dispersion,mechanical and antimicrobial properties of hybrid HDPE/clay/silver nanocomposites

This work analyses the effect of using ethylene-propylene-diene-monomer-grafted maleic anhydride (EPDM-g-MA) as compatibilizer to improve the interfacial properties and toughness of high-density polyethylene–organoclay–silver (HDPE/clay/silver) nanocomposites. EPDM-g-MA was reacted using ultrasound with a solution of AgNO₃ 0.04 M and ethylene glycol using ammonium hydroxide to obtain the silver ammonium complex. This silver-coated maleated EPDM was then melt mixed with HDPE and organoclay (Nanomer I28E) using a twin-screw extruder. Transmission electron microscopy (STEM) and X-ray diffraction (XRD) results confirmed the filler dispersion of both organoclay and silver nanoparticles into HDPE matrix when maleated EPDM was used. Both fillers were better dispersed and exfoliated by using this compatibilizer. The thermal stability enhancement of nanocomposites was confirmed using thermogravimetric analysis. Mechanical and antimicrobial properties demonstrated that better dispersed filler obtained with maleated EPDM enhanced the toughness and antimicrobial behaviour of HDPE/clay/silver hybrid nanocomposites. This confirmed that maleated EPDM was an efficient compatibilizer to obtain hybrid nanocomposites with enhanced properties to be used for several HDPE applications.     

剪切速率对动态硫化PP/EPDM热塑性弹性体相态结构及性能的影响

采用动态硫化法,在双螺杆挤出机中制备以聚丙烯(PP)/三元乙丙橡胶(EPDM)为基体材料的热塑性弹性体,研究螺杆转速对PP/EPDM热塑性弹性体相态结构及性能的影响;采用差示扫描量热(DSC)仪分析了PP/EPDM热塑性弹性体的结晶性能,通过扫描电子显微镜(SEM)分析PP/EPDM热塑性弹性体的微观相态结构,并用万能试验机等对其力学性能进行测试。结果表明,随着螺杆转速的增加,PP/EPDM热塑性弹性体的结晶温度降低,凝胶含量、拉伸强度和断裂伸长率先增大后减小,压缩永久变形先减小后增大,而螺杆转速对硬度的影响不明显。当螺杆转速为180 r/min时,PP/EPDM热塑性弹性体的凝胶含量、拉伸强度和断裂伸长率均达到最大值,分别为56.8%,15.9 MPa和634%,压缩永久变形和硬度(邵A)均达到最小值,分别为68.8%,88。     

PVC／胶粉热塑性弹性体的制备与性能研究

以聚氯乙烯(PVC)和胶粉为主要原料,采用共混的方法制备了PVC／胶粉热塑性弹性体,研究了胶粉的改性剂、PVC的改性剂和胶粉的用量等对PVC／胶粉热塑性弹性体性能的影响,并与国标GB／T 18173.1–2012所要求的性能进行比对。研究结果表明,使用橡胶再生剂RV改性胶粉所制得的PVC／胶粉热塑性弹性体综合性能最优;使用乙烯–乙酸乙烯酯塑料(EVAC)、苯乙烯–丁二烯–苯乙烯塑料(SBS)改性PVC时,EVAC的改性效果优于SBS,使用15份EVAC所制得的PVC／胶粉热塑性弹性体具有更佳的力学性能、耐老化性能,且满足国标要求;随着胶粉用量的增加,PVC／胶粉热塑性弹性体的综合力学性能下降,耐老化性能提高,使用30份改性胶粉时性价比最高,同时满足国标GB／T 18173.1–2012要求。     

On the inhomogeneous hydration kinetics and stiffness evolution of HNBR‐MgO reactive elastomer composites

Swellable elastomers are widely used in oilfield industry for sealing and zonal isolation applications. These materials need to sustain a large amount of external load after swelling. A newly developed reactive hydrogenated nitrile butadiene rubber (HNBR) based elastomer composite with magnesium oxide (MgO) as filler can swell and stiffen when exposed to water, which makes it ideal for oil field applications. However, both the filler hydration and the stiffness evolution inside this composite material are observed to be highly inhomogeneous even for samples on the length scale of millimeters. To understand this coupled diffusion‐hydration process is critical for applications of these materials with larger length scales. In this work, the hydration kinetics and stiffness evolution of the HNBR‐MgO composite are quantitatively studied on microscopic level. The extent of MgO hydration along the thickness of the sample are measured at the different stage of swelling. These results are used to determine the diffusion coefficient of water inside the composite. The diffusivity increases orders of magnitude after the filler hydration. In addition, the modulus change is non‐proportional to the degree of filler hydration as demonstrated by instrumented grid indentation on the hydrated composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43420.