Residual metal content in Ethylene‐Propylene‐Diene Monomers synthesized using vanadium‐ and zirconocene‐based catalysts

Ethylene‐propylene‐diene monomer (EPDM) terpolymers were prepared using either vanadium (VOCl₃/Al₂Et₃Cl₃) or zirconocene (Et(Ind)₂ZrCl₂/MAO) catalyst systems. Residual metal contents in EPDM films were determined by Rutherford backscattering spectrometry. Metallocene catalyst systems exhibited a higher activity, producing EPDM with lower molecular weight and narrower molecular weight distribution. The highest activity guaranteed lower residual metal content (Zr/C = 10⁻⁵) than in the case of EPDM produced by VOCl₃/Al₂Et₃Cl₃ (V/C = 10⁻⁴). Subsequent steps of dissolution of the polymer and its reprecipitation were seen to reduce the metal contents in both metal systems. Concerning the cocatalyst retention, despite initial use of a very high amount of methylaluminoxane/metallocene (Al/Zr = 3000) in the reactor, only about 4% of this initial concentration remained in the polymer. On the other hand, in the case of vanadium‐based catalyst, almost all Al present in the initial conditions (≃8.3) remained in the polymer. In both cases, the residual Al/M ratio was close to the value generally proposed for the generation/stabilization of the active species. In the case of vanadium systems, a test in the synthesis of ethylene propylene rubbers indicated that the absence of diene in the polymer structure leads to a reduction in the residual vanadium content, indicating that the diene double bond might be responsible for partially vanadium coordination. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1997–2003, 1999     

磺化三元乙丙橡胶离聚物的合成

用浓硫酸和醋酸酐为三元乙丙橡胶（EPDM）反应制备了磺化三元乙丙橡胶离聚物（S－EPDM）。探讨了浓硫酸用量、EPDM胶液浓度、磺化浓度、反应时间对磺化的影响以及磺化三元乙丙橡胶锌离聚物（S－EPDM－Zn)的应用。     

Dynamic simulation and experimental evaluation of EPDM terpolymerization with vanadium-based catalyst

The development of a simplified kinetic model describing some effects observed in catalyzed olefin terpolymerization is presented. Based on the method of moments, the model describes the influence of Al/V ratio and diene concentration on reaction yield and on polymer characteristics such as molecular weight, ethylene incorporation, and polydispersity. In order to verify the model validity, the terpolymerization reactions were performed using VOCl₃–Al₂Et₃Cl₃ systems and 2-ethylidenebi-cyclo[2.2.1]hept-5-ene (ENB) as diene. The results of dynamic simulation fit well the experimental data for Al/V up to 15, but the model fails under high diene concentration, where branching reactions, neglected by reason of simplification, become significant. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1173–1189, 1998     

磺化三元乙丙橡胶粘合剂的合成

合成了磺化三元乙丙橡胶(EPDM)粘合剂,研究了溶剂、增粘剂、固含量、磺化度对其粘合剂粘接性能的影响.结果表明:磺化EPDM粘合剂的剥离强度远大于未磺化的EPDM粘合剂的剥离强度.选用甲苯和甲醇为混合溶剂,古马隆树脂和氯化石蜡为增粘剂,胶液固含量为20％时,磺化EPDM的剥离强度最大.     

Electrochemical deposition of copper and ruthenium on titanium

Copper electrochemical deposition on titanium with a ruthenium seed layer was investigated. The chemicals for the acid-bath ruthenium electrochemical deposition were ruthenium(III) chloride hydrate (RuCl₃·3H₂O), hydrochloric acid (HCl), sulfamic acid (NH₂SO₃H), and polyethylene glycol. The chemicals for the acid-bath copper electrochemical depositions were copper(II) sulfate hydrate (CuSO₄·5H₂O), sulfuric acid (H₂SO₄), and polyethylene glycol. Results were analyzed by field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering spectrometry (RBS). Ruthenium thin film of ∼30 nm thickness, with equiaxial grains <10 nm, was deposited, on a blanket Ti with a root mean square roughness of 8.3 nm, at 2 V for 90 s. XPS and RBS analyses showed the presence of metallic Ru. The Ti substrate was found stable with respect to ECD of Ru but the Ru/Ti bilayer was not found stable in the Cu acid bath, resulting in the diffusion of Ti into Ru film. The depth profiling studies indicates that Ru film thickness ca. 1.4 nm and deposition time of 10 s can act as a good seed layer.     

Synthesis and characterization of ion‐conducting polymer systems based on EPDM blends

We report on the preparation and characterization of new polymeric ionomers based on EPDM with a high norbornene content. The sulfonation level is determined by means of X‐ray photoelectron spectroscopy and the microstructural characterization is obtained both through differential scanning calorimetry and dynamo‐mechanic analysis. In addition, the effects of certain plasticizers and polymers on the microstructure of these materials were studied, as well as their conducting properties, with special attention to this latter type of behavior, in view of the interest aroused by these materials as membranes in polymer fuel cells. From the obtained results, some of the synthesized membranes can be used for fuel cells because their high conductivity (≥10‐2 S/cm) and their good dimensional stability (any shrinkage observed). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3133–3141, 2001     

三元乙丙橡胶抗撕裂性能的研究

实验采用EPDM配方,通过对硫化体系、补强体系和填充体系的变量试验,采用正交试验法考察过氧化物、硫磺、炭黑以及填充纤维四个因子对EPDM抗撕裂性能的影响,具体分析了其差异以及产生的原因,制定了优化的EPDM抗撕裂配方和工艺条件。     

PS/EPDM反应性共混物的研究

在熔融状态下，利用Friedel-Crafts烷基化反应原位生成聚苯乙烯（PS）／EPDM共混物，考察路易斯酸品种、用量、混炼温度和混炼时间等对共混物性能的影响。结果表明，选择三氯化铝作为PS和EPDM大分子间形成接枝共聚物EPDM-g-PS的催化剂时效果较好；EPDM-g-PS的生成使PS／EPDM共混物的熔体质量流动速率和PS相的玻璃化温度下降，增大了PS和EPDM两相的界面结合力，从而提高了共混物的性能；当PS／EPDM共混比为60／40、三氯化铝用量为3份、混炼温度为140℃、混炼时间为5min时，共混物综合性能较好。     

三元乙丙橡胶新牌号J-3060P合成开发

采用从日本三井石油化工株式会社引进的年产2万t乙丙橡胶工业生产装置,成功开发了树脂改性用高档乙丙橡胶新牌号J-3060P。该牌号以V-Al为催化体系、己烷为溶剂,采用氢气为分子量调节剂,合成的工业化产品经北京橡胶工业研究设计院及国内代表性应用厂家检测,产品性能与国外同类产品质量水平相当,填补了国内空白。     

耐烧蚀EPDM胶料配方的研究

以耐烧蚀树脂和阻燃剂的配合为主，探讨固体火箭燃烧室用耐烧蚀EPDM胶料的配方设计。用正交试验法确定的胶料优化配方为；EPDM 100，白炭黑15-25，氧化锌5，硬脂酸0．6，纤维5，耐烧蚀硼树脂10，硼酸锌9，三氧化二锑15，固体氯化石蜡30，增塑剂DOS 8，硫化剂DCP 5。该配方胶料耐烧蚀性能和拉伸性能好，满足使用要求。     

EPDM绝缘自粘胶粘带的研究

研究以EPDM为主体材料的绝缘自粘胶粘带配方。具体考察炭黑、IIR、萜烯树脂和环烷油的用量以及硫化条件对胶粘带胶料性能的影响。结果表明 ,炭黑N2 2 0用量不宜超过 2 0份 ,IIR替用量 10～ 2 0份为宜 ,萜烯增粘树脂 5～ 10份为宜 ,环烷油 2 0份较好 ,较合理的硫化条件为 14 0℃ /10MPa× 10min。按此配方和工艺条件生产的自粘胶粘带可满足使用要求 ,但介电强度有待进一步提高。     

EPDM复合多功能胶粘带的研制

简要介绍EPDM基复合多功能胶粘带的研制情况。基材以EPDM／CPE为主体材料，轻质碳酸钙用量为60～80份，聚异丁烯用量为15～25份；胶层采用IIR为主体材料。采用双辊开炼机和三辊压延机制得复合胶粘带，其主要性能满足预定指标并达到参比产品水平。     

过氧化物硫化的EPDM汽车散热器胶管配方

汽车向节能和低污染的方向发展使得EPDM汽车散热器胶管的工作环境发生了很大的变化，原来经常采用的硫黄硫化体系正逐步被过氧化物硫化体系所代替。列举了几个不同含胶率的典型过氧化物硫化体系散热器胶管配方以供参考。     

无卤阻燃型EPDM材料的研制

以EPDM、氧化锌、促进剂TMTD、白炭黑、温石棉、磷酸三苯酯 (TPP)、聚磷酸铵 (APP)等为原材料制备无卤阻燃型EPDM材料 ,并研究配方中各主要组分用量变化对阻燃材料性能的影响。结果表明 ,采用如下配方 :EPDM　 10 0 ;氧化锌　 7 5 ;促进剂TMTD　 4;硫黄　 2 ;白炭黑　 3 0 ;温石棉　 3 0 ;TPP　 5 ;APP　 5 0 ,可以获得物理性能稳定、阻燃性能优异的无卤阻燃型EPDM材料     

可控长链支化EPDM的性能及应用

介绍可控长链支化(CLCB)EPDM的性能和应用.CLCB EPDM兼具窄相对分子质量分布和高长链支化度,炭黑分散性和抗炭黑焦烧性良好,抗坍塌性和耐压缩永久变形性能优异,挤出和硫化速度快.与门尼粘度和相对分子质量分布相当的传统EPDM相比,CLCB EPDM挤出性能优异,在密封条等挤出制品中应用具有很大潜力.     

改性EPDM以提高EPDM/NBR共硫化胶的耐臭氧性能

为了提高NBR抗臭氧解聚的稳定性,可以采用与EPDM并用的方法.文中叙述了在使用可保护大气臭氧层的硫磺硫化体系的条件下,利用高温处理来提高各种牌号EPDM与丁腈橡胶BHKC-28的相容性,从而改善其共硫化胶的力学性能和耐臭氧性.文章着重介绍了引入2,2,6,6-四甲基哌啶-1-氧基(TEMPO)自由基的作用,从而提高共...     

纳米氧化锌/EPDM复合材料的性能研究

试验研究纳米氧化锌/EPDM复合材料的物理性能和导热性能,并与炭黑和白炭黑补强的EPDM胶料进行对比.结果表明,纳米氧化锌的导热性能明显优于炭黑和白炭黑等传统补强填料,其对EPDM具有较好的补强作用,纳米氧化锌/EPDM复合材料的生热较低;采用偶联剂Si69对纳米氧化锌进行原位改性可以改善纳米氧化锌粒子与EPDM间的界面作用,提高其分散性,从而显著提高复合材料的物理性能,降低生热;改性纳米氧化锌/EPDM复合材料的物理性能和导热性能良好,可用于动态工况下使用的橡胶制品.     

EPDM耐高温潜油电缆胶料的研制

介绍了QYEQ型EPDM耐高温潜油电缆胶料的研制。用正交试验法确定的耐高温潜油电缆胶料配方为 :EPDM　 10 0 ;氧化锌　 5 ;防老剂　 2 ;硫化剂DCP　 4;煅烧陶土　 5 0 ;四氧化三铅　 5 ;石蜡　 4;滑石粉　 10 ;半补强炭黑　 1;偶联剂A 172　 2。用该配方胶料制备的QYEQ型耐高温潜油电缆性能达到GB/T 1675 0— 1997和IEEE10 18— 1997标准。     

OMMT/PP/EPDM纳米复合材料的结构与性能研究

研究机械共混法制备的有机蒙脱土(OMMT)/聚丙烯(PP)/EPDM纳米复合材料的亚微观结构、物理性能和热稳定性能。结果表明:采用十八烷基三甲基铵盐改性OMMT制备的OMMT/PP/EPDM纳米复合材料为插层型纳米复合材料,具有较优的物理性能;当OMMT用量较小时,复合材料的物理性能随着OMMT用量的增大而提高,且在OMMT用量为2份时表现出较好的综合物理性能;OMMT/PP/EPDM纳米复合材料具有优异的热稳定性能。     

无卤阻燃EVM/EPDM并用胶的性能研究

试验研究乙烯-乙酸乙烯酯橡胶（EVM）/EPDM并用胶的性能。结果表明,随着EPDM用量的增大,EVM/EPDM并用胶的物理性能变化不大,热空气老化后并用胶的邵尔A型硬度和拉伸强度增大,拉断伸长率减小,耐低温性能提高；EVM或EVM/EPDM并用胶的阻燃性能明显优于EPDM；添加阻燃剂和增塑剂的EVM/EPDM并用胶的相容性较未添加阻燃剂和增塑剂的并用胶有所改善。