聚乙烯催化剂用烷氧基镁载体的研究进展

基于烷氧基镁载体的Ziegler-Natta聚乙烯催化剂具有活性高、氢调性能好等优点,是目前聚烯烃工业中的研究热点。介绍了烷氧基镁载体的发展进程,综述了烷氧基镁载体的制备及改进方法,分析了烷氧基镁载体在催化剂制备过程中的作用,并对开发适用于乙烯聚合的烷氧基镁载体提出了展望。     

有机膦系预膜剂在碳钢表面的成膜机理

用旋转挂片法、极化曲线法、X射线光电子能谱法、原子力显微镜法等分析测试手段对以有机膦酸和Zn盐为主要成分的预膜剂在碳钢表面形成的缓蚀保护膜进行了综合表征.结果表明,有机膦酸和Zn盐成膜剂能够在碳钢表面形成致密的保护膜,对腐蚀的阴极和阳极过程都具有抑制作用;膜结构为磷酸盐螯合物颗粒的致密沉积,主要成分(mol%)为55%O、16?、14%P、5%Zn、7%C和2?.     

Microstructure of isotactic polypropylene obtained using Ziegler–Natta catalyst at high polymerization temperature

The microstructure of the isotactic polypropylene obtained with various MgCl₂‐supported catalyst systems at high polymerization temperature of 70–100°C is investigated by discussing the intrinsic relation between the different types of active centers and the polymerization temperatures via gel permeation chromatography, temperature rising elution fractionation, and ¹³C NMR. For the MgCl₂/TiCl₄/di‐n‐butyl phathalate‐AlEt₃/external donor and MgCl₂/TiCl₄/2,2‐diisobutyl‐1,3‐dimethoxypropane‐AlEt₃ catalyst systems, the differences in the isotactic productivity of polymers obtained at different polymerization temperatures mainly result from the variation of both the activity of the different isospecific active centers and the stability constants of the complex of catalyst/donor. The reaction rate of high isotactic active centers reaches maximum at 85–90°C, and this effect contributes to both the highest isotacticity and the narrowest molecular weight distribution. For the MgCl₂/TiCl₄/phthalate ester‐AlEt₃ catalyst system, the isotacticity of polypropylene remains approximately constant in the temperature range of experiments, which could be ascribed to elution of phthalate ester after the activation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42487.     

A facile one‐step method for spherical support preparation of Ziegler‐Natta catalyst

This study reports a novel one‐step method to synthesize a new spherical support for Ziegler‐Natta catalyst under moderate condition. The support is obtained from a dispersion system where the particle stabilizer polyvinylpyrrolidone plays a main role to stabilize the spherical particles. The new chemical of the support is CH₃CH₂OMgOCH(CH₂Cl)₂, which is first reported here, has been approved by newly filed patents and also confirmed by solution NMR, solid state NMR, pyrolysis‐gas chromatography‐mass spectrometry (Py‐GC‐MS), and ICP‐MS. The support and catalyst particles have uniform distributions. The catalyst prepared from this support has been evaluated with high activity. The polypropylene obtained has high isotacticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41014.     

长支链聚乳酸的结晶性能

通过均苯四甲酸酐(PMDA)和异氰尿酸三缩水甘油酯(TGIC)与聚乳酸的连续官能团反应,制备出了长支链聚乳酸,小振幅振荡剪切(SAOS)测试结果显示产物中存在长支链组分。通过差示扫描量热(DSC)实验对长支链聚乳酸的结晶行为进行了研究,结果表明:长支链聚乳酸比线形聚乳酸具有更高的成核密度,从而能够提高聚乳酸的结晶速率。在长支链和增塑剂的协同作用下,聚乳酸的结晶性能得到更大程度的改善。     

YN-1型催化剂在裂解汽油C_9~+选择加氢装置的工业应用

介绍了YN-1型镍系催化剂在新疆独山子天利实业总公司裂解汽油C+9馏分选择加氢装置的工业应用。结果表明,YN-1型镍系催化剂用于胶质含量100 mg·(100m L)-1和溴价95 g Br·(100g)-1的C+9馏分原料选择加氢,能够适应超过90℃的反应温升,并表现出低温活性高、稳定性好和容胶量大的优点。     

YN-1型镍系催化剂在裂解重C_9~+馏分一段加氢装置上长周期运行

介绍了中国石化催化剂北京燕山分公司的裂解重C+9馏分一段加氢工况,采用了低压、低空速、高氢油比和高循环比的加氢工艺。依据工业装置原料性质、反应温度和反应器进、出口压力变化情况,统计分析了使用YN-1型镍系催化剂没有经过再生进行一段加氢产品的溴价和双烯含量变化,工业应用结果表明,YN-1型镍系催化剂具有优异的加氢活性和长周期运行的稳定性。     

Synthesis of well‐defined comblike hydroxy‐functionalized atactic polystyrene promoted by metallocene/tin/poly(phenyl glycidyl ether)‐co‐formaldehyde

Well‐defined comblike atactic polystyrene functionalized with hydroxyl groups was synthesized via living/controlling radical polymerization promoted by metallocene complexes in the presence of poly(phenyl glycidyl ether)‐co‐formaldehyde as the initiator and Sn as a reducing agent. The effect of the polymerization conditions, such as the ratio of initiator to monomer, temperature, and polymerization time, and the structure of the metallocene complex on the polymerization process were investigated. The resulting polymers were characterized by gel permeation chromatography, multiangle laser light scattering, ¹H‐NMR, and ¹³C‐NMR. The results show that the polymer had a narrow molecular weight distribution in the range 1.1–1.4 and the number‐average molecular weight of the polymer linearly depended on the monomer conversion within the polymerization timescale, which confirmed that living radical polymerization characteristics prevailed in the polymerization process. Both the number of arms and the number of hydroxyl groups in each polymer molecule were about four, which suggested that they arose from the epoxy functional groups of the initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

无磷缓蚀阻垢剂YSW109的研制和工业应用

针对磷系缓蚀阻垢剂存在的富营养化问题,开发了一种无磷缓蚀阻垢剂YSW109和相应的水处理工艺。动态模拟实验和现场应用结果表明,采用YSW109可控制循环水的钙离子质量浓度为1 100 mg/L左右,浓缩倍数达到7倍,各项水质指标控制良好;旁路监测换热器碳钢试管的腐蚀速率和黏附速率分别为0.042 mm/a和10.3 mcm,均满足中国石化循环水处理标准。     

国内外聚丁二烯橡胶市场分析与展望

分析了国内外聚丁二烯橡胶的生产消费现状及发展前景。2013年全球聚丁二烯橡胶的总生产能力为470.3万吨/年,消费量为315.0万吨,预计2018年总生产能力将达到580.0万吨/年,总消费量将达到380.0万吨。近年来,我国聚丁二烯橡胶生产发展迅速,先后有多套新建或者扩建装置建成投产,截至2014年6月,总生产能力已经达到172.5万吨/年。2013年的表观消费量为101.0万吨,预计2018年生产能力将达到约215.0万吨/年,消费量将达到约115.0~120.0万吨。未来市场竞争将十分激烈,国内相关企业今后应该慎重新建装置,不断开发新技术,调整产品结构,积极扩大出口,以确保行业健康、快速发展。