全密度聚乙烯生产工艺进展及市场现状

综述了全密度聚乙烯(PE)的生产工艺,包括气相法的Unipol工艺,Innovene工艺,Spherilene工艺和Borealis工艺,溶液法的Sclair工艺和Dowlex工艺,淤浆法的Phillips环管工艺;分析了国内全密度PE的生产情况,以及2017年国内高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯的进出口情况,指出国内PE的月度进口量均远大于出口量,开发能够替代进口PE的高端产品有很大空间;最后,对国内全密度PE的发展前景进行了预测。     

聚乙烯接枝技术研究进展

综述了溶液接枝法、熔融接枝法、固相接枝法等常用的聚乙烯(PE)接枝改性方法,介绍了丙烯酸、马来酸酐等通用的PE接枝单体,分析了单体浓度、引发剂浓度、助剂及反应温度等因素对PE接枝反应的影响,预测了PE接枝技术的开发前景。     

多壁碳纳米管改性聚乙烯超薄膜的制备与性能研究

以多壁碳纳米管(MWCNT)和聚乙烯(PE)为原料,采用溶液拉伸法制备了一种新型复合材料薄膜PE/MWCNT。研究了拉膜温度、转筒转速和对二甲苯溶液浓度等因素对PE/MWCNT成膜性能的影响,获得了最佳的成膜条件。通过扫描电镜、差示扫描量热仪、热重分析仪与微机控制万能试验机对其结构和性能进行表征。PE/MWCNT超薄膜填补了复合材料的空白。     

聚乙烯单聚合物复合材料研究进展

聚乙烯(PE)单聚合物复合材料(SPC)是基体和增强体同为PE的复合材料,具有密度小、易回收、界面黏结性好的优点。简要介绍了SPC的成型机理,综述了PE SPC的研究进展,主要包括热压纤维法、溶液浸渍热压法、膜层热压法等制备方法和制备得到的PE SPC的性能,同时指出了这些方法中存在的问题和缺陷,为PE SPC的进一步发展奠定了基础。最后展望了PE SPC的发展趋势。     

环保型聚乙烯-丙烯酸吸水树脂的合成

利用聚乙烯（PE）回收料和具有亲水性基团的丙烯酸（AA）,通过反相乳液聚合法接枝共聚合成了环保型PE—AA吸水树脂。探讨了原料配比、NaOH溶液用量、反应温度、反应时间、引发剂种类及其用量、交联剂用量等因素对吸水树脂吸水率的影响。实验结果表明,在m（AA）：m（PE）为8：1、AA用量32g、质量分数25％的NaOH溶液40mL、反应温度70℃、反应时间3h、引发剂（过硫酸铵／亚硫酸氢钠）6mL、交联剂（环氧氯丙烷）2mL的条件下,制备的PE—AA吸水树脂的吸水率为455．3g／g。PE、聚丙烯、聚苯乙烯与AA接枝共聚所得吸水树脂中,PE—AA吸水树脂的性能较优。     

阿根廷将新建金属茂基聚乙烯装置

Dow化学公司将在阿根廷Bahia Blaanca新建一套溶液法聚乙烯(PE)装置,生产Dow开发的金属茂基Affinity聚合物。     

溶液法聚乙烯特点及发展前景

概述了NOVA(诺瓦)公司的Sclairtech溶液法聚乙烯生产工艺特点,介绍了溶液法工艺总体发展及辛烯聚乙烯的应用领域,提出了抚顺乙烯溶液法聚乙烯工艺的发展方向.     

发展中的中国石油化学工业（九）

1 聚乙烯(PE)的技术发展目前世界上PE生产工艺具有代表性的有5种:(1)、美国联合碳化物公司(UCC)的Umipol气相流化床工艺.特点是工艺简单,操作温度80～100℃,压力低(2.1MPa),产品范围宽.我国到1997年止有9家生产厂应用此工艺,生产能力达96万吨,占总PE能力的42.29%.(2)、英国石油化学公司(BP)的气相流化床工艺.此工艺比UCC技术多一个预聚工序,设备多一套旋风分离器及冷却器,减少了堵塞和结块的毛病,既可用改良的齐格勒-纳塔催化剂生产分子量分布相对较窄的PE,也可用铬系催化剂生产分子量分布相对较宽的PE.我国目前有3家生产厂应用此工艺,生产能力达30.5万吨,占总PE能力的13.44%.(3)、杜邦公司的溶液聚合法工艺.此工艺反应快、单程转化率高、产品质量好、操作易控制,但反应温度为     

热粘合复合纤维PP/PE的研究

应用声速法、密度法等测试手段研究了以低熔点PE纤维为皮层，以高熔点PP纤维为芯层的PP／PE热粘合复合纤维的结构特性，对纺丝、拉伸工艺取得了一系列数据，所得结果对制取性能优良的热粘合复合纤维具有理论指导意义。     

新型气相法聚乙烯催化剂的开发及工业应用

在我国聚乙烯(PE)生产装置中,气相法聚合工艺占有十分重要的地位。自20世纪70年代起,我国先后引进了8套Unipol工艺的气相流化床PE生产装置,生产能力已超过900kt/a。其中,茂名石化乙烯工业公司(简称茂名石化)、中原石油化工有限责任公司(简称中原乙烯)、中国石油化工股份有限公司广州分公司(简称广州石化)、中国石油吉林石化分公司(简称吉林石化)和扬子石油化工股份有限公司(简称扬子石化)等企业未引进催化剂生产配置装置,每年需花费大量外汇进口催化剂,而且催化剂质量不稳、价格高,导致PE生产成本增加。因此,需尽快研制出具有自主知识产权的气相法PE催化剂。     

Two‐stage grafting onto polyethylene fiber by radiation‐induced graft polymerization and atom transfer radical polymerization

Two‐stage graft polymerization onto polyethylene (PE) fiber was demonstrated. The graft side chain was formed by radiation‐induced graft polymerization. A PE fiber was irradiated with an electron beam and immersed in a vinyl monomer solution. The terminal of the formed graft chain was halogenated using N‐bromosuccinimide. The halogenated graft chain was then extended by atom transfer radical polymerization to obtain block‐copolymer grafted PE fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚苯胺/PE复合材料的制备探究

采用原位化学氧化聚合法制备苯胺/PE导电复合材料,使苯胺在基体高分子PE的水溶液中进行聚合,研究反应体系中聚苯胺的含量、反应时间、温度对复合材料电导率的影响,确定了较佳的聚合反应条件,并且通过红外对光谱复合材料的结构、光电性能和稳定性进行了表征和分析。     

溶液法聚乙烯产品的应用

介绍了Ｄｕ Ｐｏｎｔ公司溶液法产品的应用情况及开发方向,对溶液法聚乙烯产品在开发应用提出了建议。     

The architecture of hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE via one‐pot strategy combining living free radical polymerization with coordination polymerization

The copolymerization of styrene with ethylene was promoted by CpTiCl₃/BDGE/Zn/MAO catalyst system combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one‐pot. The effect of polymerization conditions such as temperature, time, ethylene pressure, and Al/Ti molar ratio on the polymerization performance was investigated. The hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE triblock copolymer was obtained by solvent extraction and determined by GPC, DSC, WAXD, and ¹³C‐NMR. The DSC result indicated that the aPS‐b‐random copolymer‐b‐PE had a T_g at 87°C and a T_m at 119°C which attributed to the T_g of aPS segment and the T_m of PE segment, respectively. The microstructure of the hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE was further confirmed by WAXD, ¹³C‐NMR, and ¹H‐NMR analysis; and these results demonstrated that the obtained block copolymer consisted of aPS segment, S‐E random copolymer segment, and crystalline PE segment. The connection polymerization of the hydroxy‐functionalized aPS with random copolymer‐b‐PE was revealed by GPC results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

BCE催化剂制备双峰PE的研究

研究开发了BCE高效聚乙烯催化剂．并模拟超临界工艺制备出双峰聚乙烯树脂。BCE催化剂具有较高的活性（约为参考催化剂的2倍）和良好的氢调敏感性;与参考催化剂相比,该催化剂制备的聚乙烯树脂具有较高的堆积密度（0．39g／cm^3）和较窄的相对分子质量分布,重均分子量低于1000的部分较少。     

Atom transfer radical polymerization of graft chains onto polyethylene film initiated at tribromomethyl unit introduced by electron beam irradiation

A novel process for graft polymerization onto a polyethylene (PE) film using atom transfer radical polymerization (ATRP) was examined. First, a PE film irradiated with an electron beam was treated with carbon tetrabromide, thereby introducing tribromomethyl groups. The number of tribromomethyl groups introduced onto the film could be controlled by adjusting the electron beam irradiation dose. Methyl methacrylate (MMA) was then graft‐polymerized by ATRP in the initiator‐introduced PE film in the presence of a copper catalyst. Based on FTIR spectra from the PMMA grafted films, the behavior of graft polymerization reactions on the film surface and inside the film are discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

水杨醛亚胺镍配合物在甲苯中催化乙烯聚合

研究了水杨醛亚胺中性镍配合物在甲苯中催化乙烯聚合。在膦捕捉剂乙酰丙酮乙烯基铑[Rh(acac) (C_2H_4)_2]存在下,聚合活性和聚乙烯(PE)的相对分子质量均随乙烯压力的升高呈递增趋势,但随聚合温度升高而降低。由双(1,5-环辛二烯)合镍[Ni(COD)_2]作助催化剂,乙烯聚合的活性较高,但所得PE的相对分子质量、熔点和结晶度较低。动态流变研究表明,助催化剂可增加PE的支化度和降低其相对分子质量,以提高其高温加工性能。核磁共振氢谱、碳谱和广角X射线衍射研究表明,不同助催化剂所得PE的结构类似,而支化度分别为每1000个C中8和16个支链。     

茂金属催化剂应用于丙烯的聚合

本文论述茂金属催化剂的结构对丙烯聚合活性以及所形成的聚丙烯的立构规整度等的影响, 讨论丙烯聚合机理, 介绍聚丙烯弹性体的聚合。     

PE/OMMT nanocomposites catalyzed by the OMMT‐intercalated Et[Ind]2ZrCl2 in slurry polymerization: Effects of organic solvent on ethylene polymerization behaviors and the nanocomposite structures

In situ intercalative polymerization for ethylene monomers was carried out to produce PE‐based hybrids through a slurry polymerization method. In this approach, organic solvent for olefin polymerization was found to be one of the most significant factors for the dispersion of the OMMT‐intercalated Et[Ind]₂ZrCl₂ catalysts, which determines that whether olefin monomers polymerize is in a well‐defined confinement environment or not. Understanding the olefin polymerization occurring in between the nanoscale silicate layers of OMMT as well as the corresponding structure of OMMT in an organic polymerization solvent is a critical step toward tailoring and characterizing nanocomposites formed by OMMT in a polyolefin matrix. As we know, the Et[Ind]₂ZrCl₂ catalyst and MAO are both better dissolved in toluene than that in hexane because of the larger polarity of toluene. Thus, in hexane the active sites of the OMMT/Et[Ind]₂ZrCl₂ catalyst exist in the silicate layers of OMMT and the PE chains grow in the middle of them, while in toluene the active specimens are exposed in the gel formed by the OMMT‐intercalated catalyst with MAO, which cause that the PE chains propagated in the mixture liquids. Consequently, when hexane is selected as the polymerization solvent, the formed PE‐based nanocomposites have a good dispersion of OMMT and the nanofiller content (TGA measurement residue at 600°C) is thus higher (>7.0 wt %). However, in toluene, most of the silicate layers of OMMT are agglomerated in the PE matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011