多孔有机聚合物中试制备及其在聚烯烃催化剂中的应用

多孔有机聚合物广泛应用在吸附、分离、催化等领域。本文采用分散聚合工艺,中试制备得到形貌及流动性良好的POP3120T和POP3100载体,POP3120T载体堆密度为0.29g/cm³,比表面积为282m²/g,与无机硅胶载体相当,颗粒粒径23.4μm,粒径分布1.00;POP3100载体堆密度为0.34g/cm³,比表面积约503m²/g,均高于无机硅胶载体,颗粒粒径36.0μm,粒径分布0.93。负载的POP型Z-N聚丙烯催化剂具有良好的丙烯聚合活性,其活性可达到1.0×10⁷g/(mol·h)以上。得到的聚合物堆密度可以达到0.36g/cm³,聚合物细粉含量小于1%,达到商业催化剂的水平,此外负载的POP型Z-N聚丙烯催化剂具有高的立构规整选择性及宽的分子量分布,采用DIBP作为内给电子体制备的催化剂,丙烯聚合制备的聚合物等规度可达97.5%以上,分子量分布可达11以上。     

淤浆法聚乙烯催化剂的研究

在催化剂的制备过程中引入给电子体,不同的给电子体对催化剂的性能有不同的影响。尤其在90℃时加入二苯基二甲氧基硅烷给电子体化合物（给电子体与MgCl2的摩尔比为0.3）,所制备的催化剂各方面的性能较好。将加入上述给电子体所得的催化剂用于乙烯淤浆聚合实验,结果表明,聚乙烯树脂堆密度明显提高,粒度分布集中,细粉含量明显减少。     

乙烯淤浆聚合用Ziegler-Natta催化剂的制备及催化性能

通过加入新型给电子体制备了适用于乙烯淤浆聚合工艺的Ziegler-Natta催化剂。采用激光粒径分析仪、扫描电子显微镜、比表面吸附仪及X射线衍射仪分析和表征了催化剂的粒径、形态和物理结构等。采用乙烯淤浆聚合法研究了该催化剂的乙烯淤浆聚合性能,并与进口参比催化剂进行了比较。结果表明:在氢气分压为0.28 MPa、乙烯分压为0.45 MPa、反应温度为80℃、反应时间为2 h的条件下,催化剂活性达到21.3 kg/(g·h),聚合物堆密度达到0.34 g/cm3,粒径小于100μm的细粉含量为1.87%,催化剂的综合指标优于参比催化剂。     

PE-UHMW聚合用氧基硅烷内给电子体Ziegler-Natta催化剂的制备及应用

采用实验室自制的两种复合型氧基硅烷内给电子体：二甲基二(2-酚基乙氧基)硅烷(IED1)和二甲基二(2-氯乙氧基)硅烷(IED2),将两种内给电子体配置Ziegler-Natta催化剂并进行乙烯的催化聚合以制备超高分子量聚乙烯(PE-UHMW)。考察了两种内给电子体加入对Ziegler-Natta催化剂的载钛量、催化剂活性、催化剂的微观形貌及聚合物分子量等因素的影响,并考察催化剂加入量、聚合温度、聚合时间、助催化剂加入量对PE-UHMW聚合效果的影响。由于IED1结构中含有4个含氧基团,电子云密度高于IED2,因此IED1对催化剂活性以及聚合物分子量影响较大。最终确定PE-UHMW聚合工艺条件为：以IED1为内给电子体,催化剂加入量为12 mg/L,IED1与载体氯化镁的物质的量之比为1∶4,聚合温度为75℃,聚合时间为2 h,催化剂中Al/Ti物质的量之比为80。在此工艺条件下催化剂的催化效率为17.1 kg/(g·h),催化剂载钛量为5.8%,PE-UHMW堆密度为0.3 g/cm³,PE-UHMW分子量为4.0×10⁶。     

酮/酯复配内给电子体催化剂的制备及其乙烯聚合评价

用酮类和二酯类为复配内给电子体制备了一种高效乙烯聚合催化剂,用FTIR分析了单个内给电子和复配内给电子体对催化剂结构的影响,结果表明3种催化剂中给电子性能为邻苯二甲酸邻苯二甲酸/二异丁酯乙酰丙酮二异丁酯乙酰丙酮。用凝胶渗透色谱(GPC)和差示扫描量热仪(DSC)对3种催化剂所制备的聚乙烯进行了表征,与单个内给电子体催化剂制备的聚乙烯相比,复配内给电子体催化剂所制备的聚乙烯具有更高的聚合活性,更明显的"共单体效应"和更宽的相对分子量分布。     

LH-1型催化剂催化乙烯聚合的性能

评价了LH-1型催化剂催化乙烯均聚合,乙烯-丙烯、乙烯-1-丁烯共聚合的性能.与国内工业化生产的催化剂进行对比,研究了LH-1型催化剂的粒径分布、催化活性、氢调敏感性.结果表明:LH-1型催化剂的粒径分布均匀,细粉含量少,且具有较高的氢调敏感性;在聚合温度80℃、压力0.8 MPa、氢气分压0.2 MPa的乙烯淤浆聚合工艺下聚合2h,LH-1型催化剂的活性较高,达5.36×104 g/g,优于对比催化剂;用LH-1型催化剂制备的高密度聚乙烯的堆密度较大,达0.350g/cm3,乙烯-丙烯、乙烯-1-丁烯共聚合性能好.     

二醚类Ziegler-Natta催化剂催化1-丁烯聚合

采用相同的工艺,制备了含有不同内给电子体[2-甲基-2-丙基-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷(BIBIMP)、邻苯二甲酸二异丁酯]以及不含内给电子体的MgCl2负载型Ziegler-Natta催化剂,研究了给电子体结构对催化剂活性的影响以及用该催化剂合成的聚1-丁烯(PB)的等规指数、熔点、相对分子质量及其分布。结果表明:未加入外给电子体时,加入BIBIMP的催化剂活性最高,用其所制PB的等规指数最高,分别为539 g/g和84%;加入氢气可进一步提高催化剂活性和PB等规指数;加入外给电子体后,催化剂的活性均降低,二醚类Z-N催化剂活性降低最多,而使用二异丙基二甲氧基硅烷为外给电子体更有助于提高PB的等规指数。     

硅胶负载钛镁催化剂获专利

由中国石油化工研究院开发的硅胶负载钛镁催化剂的制备工艺获得国家发明专利授权。该技术具有聚合活性高、聚合产品松堆密度大、细粉少等优点,可用于生产高质量的聚乙烯树脂。     

新型负载型硅/镁复合Z-N催化剂的制备及其催化1-丁烯聚合

采用9,9-双(甲氧基甲基)芴为内给电子体,制备了高效新型负载型硅/镁复合Ziegler-Natta催化剂。考察了助催化剂烷基铝用量、聚合温度、外给电子体种类及用量,以及H2加入量等对该催化剂催化1-丁烯聚合活性及产品性能的影响。结果表明:当催化剂复合载体中镁的质量分数为15.0%,n(Al)∶n(Ti)为30,反应温度为30℃时,催化剂活性达最大,为76.9 g/(g·h);当外给电子体二环戊基二甲氧基硅烷与Ti的摩尔比为4时,聚1-丁烯等规指数最大,为97.8%;当n(Si)∶n(Ti)为1,H_2用量为2 mL时,催化剂活性为65.2 g/(g·h),显示出很好的氢调性能。     

聚合温度对乙烯聚合用钒系催化剂FVC-01性能的影响

采用MgCl_2/AlCl_3复合载体负载钒化合物制备了乙烯聚合用催化剂FVC-01,以三异丁基铝为助催化剂,氢气为相对分子质量调节剂,研究了淤浆工艺中聚合温度对催化剂活性及聚合物性能的影响。结果表明:FVC-01解决了钒系催化剂对聚合温度敏感性高的问题,催化剂聚合性能稳定;聚合温度为82~84℃时,催化乙烯聚合的活性达5.22 kg/(g·h),聚乙烯的表观密度大于0.38 g/cm~3,细粉质量分数小于1.00%,相对分子质量分布(MWD)为16.5~21.5,较用钛系催化剂生产的聚乙烯的MWD宽,可在单反应器内开发宽MWD的聚乙烯。     

Effect of diether as internal donor on MgCl2‐supported Ziegler–Natta catalyst for propylene polymerization

This article demonstrates the influence of the molar ratio between diether as internal donor and Magnesium dichloride in processing of the catalyst preparation on the catalytic performance for propylene polymerization with MgCl₂‐supported Ziegler–Natta catalyst. The effect of electron donor on catalyst is investigated. The experimental data find that diether content on catalyst increases and Ti content on catalyst decreases with the increase of diether/Mg molar ratio. This result indicates that diether as internal donor is not coordinated to Ti species but to Mg species on catalyst. The introduction of diether remarkably improves the catalytic activity. The extents of improvement closely connect with diether/Mg molar ratio. The stereospecificity of catalyst intensively depends on the structure of diether as internal donor. The possible model of multi‐active sites on heterogeneous Ziegler–Natta catalyst is proposed to explain these phenomena. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1399–1404, 2006     

Prepolymerization of ethylene with a Ziegler–Natta catalyst

The slurry prepolymerization of ethylene using TiCl₄/MgCl₂ as a catalyst was investigated. A 2³‐factorial experimental design method was employed to study the effects of the temperature, hydrogen, and active cocatalyst‐to‐catalyst molar ratio (Al/Ti) on the catalyst activity, prepolymer melt flow index, and powder bulk density. All dependent variables increased when the active Al/Ti ratio increased from 1 to 2. The hydrogen–Al/Ti interaction had a significant effect on the prepolymer melt flow index and catalyst activity. The hydrogen (partial pressure ranging from 0.5 to 1.5 bar) and temperature (ranging from 60 to 80°C) variables as well as the hydrogen–temperature and hydrogen–temperature–Al/Ti interactions increased the prepolymer powder bulk density, which ranged from 0.11 to 0.373 g/cc. To find the reason for the prepolymer powder bulk density variation with the operating conditions, the particle size distribution and crystallinity of the prepolymers were determined. The increasing catalyst activity, ranging from 132 to 660 g of polyethylene/mmol of Ti, enhanced the weight percentage of fines, which ranged from 3 to 60, and decreased the average particle size, which ranged from 562 to 120 μm. This was the reason for the increasing prepolymer powder bulk density and could be due to the breakup of the prepolymer particles during prepolymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

HM型高效催化剂的乙烯聚合应用研究

研究组分为TiCl4/MgCl2-SiO2/AlR3的HM型高效催化剂的乙烯聚合，发现催化剂组分SiCl4有促进乙烯聚合的作用，并可以通过调节SiCl4用量控制催化剂Ti含量。ZnCl2有调节分子量的作用。由MgCl2-ZnCl2-SiO2复合载体组成的Ti系催化剂乙烯均聚催化效率为7．1014．0kg/g，聚合产物表观密度为0．23－0．30g.cm^2,20-200目颗粒质量为90％－95％。乙烯与1－丁烯共聚时催化效率大大提高，当1－丁烯的体积分数为10％时，效率高26．0kg/g，共聚产物熔点、结晶度随1-丁烯的体积分数增加而下降，而支化度则随之上升。HM催化剂1m^3反应釜工业试生产的试验结果表明，在05MPa下催化效率达152－241kg/g，聚合产物表观密度为0．33－0．34g/cm^3，20－200目颗粒质量为60．6％－84．3％，小于200目颗粒占1％以下。工业试生产的HM催化剂具有催化效率高、颗粒度均匀、极少细粉、表现密度大等优点，达到或超过了实验室研制的技术指标，具有优良的聚合性能。     

丙烯聚合用BCZ型催化剂的开发

在MgCl2溶解过程中加入内给电子体,开发了一种新型丙烯聚合用BCZ型催化剂,并在5 L聚合釜中进行了本体聚合考核评价,在12 m3小本体工艺装置上进行工业应用试验,在25 kg/h的连续法Innovene气相工艺装置进行中试试验。研究表明:用BCZ型催化剂制备聚丙烯(PP)时,催化剂活性高出国产同类催化剂近50%,氢调敏感性好,同样氢气用量下,PP的熔体流动速率可提高25%左右;所制PP的相对分子质量分布大于7.5,等规指数高;BCZ型催化剂可用于小本体法工艺、连续法气相工艺装置制备均聚和共聚PP。     

镁醇体系聚丙烯催化剂制备技术进展

简述了Ziegler–Natta催化剂的发展概况,并指出镁醇体系催化剂颗粒形态优良,活性高、等规度高、氢调敏感,催化剂的制备成本较低,且适用于气相法、环管法等多种工艺,具有广阔的研究前景。深入调研了国内外相关单位的研究动向,从催化剂的活性,聚合物的堆积密度、立体定向性、颗粒形态等多个研究方向,阐述了当前镁醇体系催化剂的研究进展。提出应该从载体的制备、给电子体的种类和制备工艺三方面来改进催化剂的性能。     

聚丙烯催化剂性能评价

通过熔体流动速率和等规指数测试、扫描电子显微镜观察评价了国内外几种聚丙烯(PP)催化剂,考察了催化剂的活性、流动性、氢调敏感性等.结果表明:1#催化剂具有较高的活性,可达38.92 kg/g,且氢调敏感性和抗杂质能力较强,但用其生产的PP粉料中存在粒子开裂和大量粉末;2#和3#催化剂活性较低,但工艺可操作性好.PP粉料的粒子大小均匀、致密、粉末少;5#催化剂活性最高,但PP灰分高、细粉较多;6#催化剂聚合活性较高,但PP灰分最高、细粉含量大.     

Polymerization of liquid propylene with a fourth‐generation Ziegler–Natta catalyst: Influence of temperature,hydrogen, monomer concentration,and prepolymerization method on powder morphology

Liquid propylene was polymerized in a 5‐L autoclave batch reactor using a commercially available TiCl₄/MgCl₂/Al(ethyl)₃/DCPDMS Ziegler–Natta catalyst, with a phthalate ester as internal electron donor. The powders from these polymerizations were characterized using laser diffraction particle size distribution (PSD) analysis, scanning electron microscopy (SEM), and bulk density measurements. These characteristics were analyzed as a function of the process conditions, including hydrogen and monomer concentration, polymerization temperature, and the prepolymerization method. It was shown that polymerization temperature influences the powder morphology to a large extent. At low temperatures, high‐density particles were obtained, showing regular shaped particle surfaces and low porosities. With increasing temperature, the morphology gradually was transferred into a more open structure, with irregular surfaces and poor replication of the shape of the catalyst particle. When using a prepolymerization step at a relatively low temperature, the morphology obtained was determined by this prepolymerization step and was independent from conditions in main polymerization. The morphology obtained was the same as that observed after a full polymerization at temperature. Even when using a short polymerization at an increasing temperature, the morphology was strongly influenced by the initial conditions. The effect of variation in hydrogen concentration supported the conclusion that the initial polymerization rate determines the powder morphology. In the absence of hydrogen, high bulk densities, and regularly shaped particles were obtained, even at high temperatures. With increasing hydrogen concentration, the reaction rates increased rapidly, and with that changed the morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1421–1435, 2003     

水热处理对体相加氢催化剂活性的影响

体相催化剂经水热处理后,催化剂孔结构发生了改变,孔容、孔径和比表面积增加。采用小型加氢装置加工处理不同超深度脱硫难度的柴油原料,对水热处理后的催化剂进行超深度加氢脱硫活性评价。评价结果表明,体相催化剂经水热处理后,提高体相催化剂的超深度加氢脱硫活性和芳烃饱和性能,加工处理超深度脱硫难度大的劣质柴油时,加氢活性提高更加明显。以直馏柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,对比没经水热处理的催化剂,水热处理后催化剂的反应温度降低了5℃。而以催化柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,水热处理后催化剂的反应温度比水热处理前的反应温度降低了13℃。水热处理后的体相催化剂具有良好的活性稳定性。