Ziegler-Natta催化剂制备宽/双峰分布PE的研究进展

综述了近年来Ziegler-Natta(Z-N)催化剂制备宽/双峰分布聚乙烯(PE)的研究状况,介绍了含有无机化合物和给电子体化合物的MgCl2载体型和复合载体型两种Z-N催化剂的各种制备方法对PE相对分子质量分布的影响,同时介绍了相关Z-N催化剂的一般制法.研究发现:MgCl2载体型Z-N催化利制备的PE相对分子质量...     

Z-N催化剂生产宽/双峰MWD聚乙烯的研究进展

介绍了Ziegler-Natta(Z-N)催化剂在单反应器中生产宽,双峰相对分子质量分布(MWD)聚乙烯(PE)的最新研究进展,概括了Z-N催化剂制备宽／双峰MWDPE的主要方法及特点,即传统的Ti系催化体系生产的双峰PE的MWD较窄,改进的Ti-V双金属催化体系活性高,可以调节MWD,但反应操作难度大。通过加入不同的配合物,调节并改进PE的MWD,取得了较好的实验结果。宽/双峰MWDPE的生产和开发是PE工业发展的一个重要方向。     

分子量宽峰分布聚乙烯茂金属催化剂的研究

以复合茂金属催化剂和双载体茂金属催化剂乙烯聚合、考察聚乙烯（ＰＥ）分子量分布变化情况。结果发现两者都使ＰＥ分子量分布加宽,其中复合茂金属催化剂Ｃｐ２ＺｒＣｌ２／ＹＢ３使分子量分布从２．３７增至９．１８。分子量分布增加幅度与不同复合茂经剂、催化剂配比、２载体量之比负载催化剂用量有关。     

宽相对分子质量分布PE钛系催化剂的研究

合成了一种钛系催化剂,可以在单反应器内催化乙烯聚合得到宽相对分子质量分布的聚合物.该催化剂具有很好的乙烯聚合活性,最高可在4.1 kg/(g·h)以上.在催化乙烯聚合过程中,通过调整助催化剂用量,控制温度、氢分压等可以得到不同相对分子质量及其分布的聚乙烯树脂.     

高效CM催化剂在UHMWPE生产中的应用

介绍了CM催化剂的制备、组成和结构,并与生产高密度聚乙烯用催化剂进行比较,发现CM催化剂具有较大孔容和孔径.将CM催化剂应用于超高相对分子质量聚乙烯(UHMWPE)工业生产,发现采用CM催化剂生产的UHMWPE产品颗粒分布集中,细粉含量少,从而证实了CM催化剂适合生产UHMWPE.     

Ziegler-Natta/茂金属复合催化剂制备双峰聚乙烯

通过把茂金属催化剂负载在Ziegler-Natta催化剂上制备了ZM复合催化剂,在单一聚合反应器内研究了ZM催化剂用于乙烯聚合制备双峰聚乙烯的性能。考察了催化剂中茂金属化合物的含量、聚合过程中反应温度、助催化剂的用量和共聚单体1-己烯的用量对催化剂乙烯聚合性能的影响规律。结果表明：采用ZM催化剂可以在单反应器内催化乙烯聚合得到分子量分布呈双峰的聚乙烯,聚乙烯的分子量分布达到155,聚合活性可达2.52×10⁷ g/molMt·h。     

新型改性Ziegler-Natta催化剂的制备及用于乙烯淤浆聚合

采用苯酚、2,4–二叔丁基苯酚和2,6–二叔丁基苯酚对传统钛系Ziegler-Natta催化剂进行改性,并进行了物性分析,考察了催化剂的均聚性能、氢调敏感性能、聚合动力学行为、乙烯与1–己烯以及乙烯与1–丁烯的共聚合性能。结果表明:通过酚类化合物改性后的催化剂钛含量较低,且比表面积较高,催化剂粒子呈类球形,径距更加集中,以2,6–二叔丁基苯酚改性的催化剂效果最佳。     

中分子量聚乙烯齐格勒-纳塔催化剂的研究

合成了一种钛系齐格勒-纳塔烯烃聚合催化剂，该催化剂具有较高的乙烯聚合活性，其乙烯聚合动力学平稳，氢调敏感,所得到的乙烯聚合物具有中等分子量分布。     

世界聚乙烯催化剂研究新进展

综述了国内外聚乙烯齐格勒-纳塔催化剂、茂金属催化剂、非茂金属催化剂、双功能催化剂、双峰或宽峰分子量分布聚乙烯复合催化剂等的研究开发新进展。     

高效MgCl2/SiO2复合载体型聚乙烯催化剂的研究

采用相同的工艺制备了两种不同的MgCl2/SiO2复合载体型Ziegler-Natta催化剂,考察了SiO2粒径对催化剂的形态结构及其催化乙烯聚合性能的影响,并利用BET测试仪和扫描电子显微镜(SEM)等对催化剂的形态和物性进行了表征。结果表明:加入小颗粒SiO2可以改善催化剂的颗粒形态和均匀程度,而且小颗粒SiO2制备的复合载体催化剂不仅具有较高的催化剂活性,还可使聚合产品的颗粒变得均匀,提高聚合物的堆密度,降低细粉含量,增强氢调敏感性。     

SiO2负载二亚胺镍/TiCl4催化乙烯聚合

合成了配合物N,N'-二[4-(4-氨基-3,5-二乙基苄基)-2,6-二乙基苯基]苊二亚胺二氯化镍(NiLCl2),将其与TiCl4复合负载在SiO2/MgCl2上制得负载催化剂.研究了该负载催化剂对乙烯聚合的催化活性, 考察了聚合条件对聚合反应及产物结构的影响.结果表明,负载的NiLCl2/TiCl4较之未负载的NiLCl2催化活性高,最高催化活性达到552 kg/(mol·h),而聚合需要的n(Al)/n(Ni)也较相应的NiLCl2低.     

TiCl4/MgCl2催化剂载体掺杂的研究进展

综述了用于烯烃配位聚合的MgCl_2载体掺杂负载型Ziegler-Natta(Z-N)催化剂的研究进展,讨论了此类催化剂用于烯烃聚合的催化活性、活性中心分布、聚合产物的相对分子质量分布及立构规整性的变化等。掺杂MgCl_2负载的Z-N催化剂比常规负载的Z-N催化剂生产的聚烯烃的相对分子质量分布宽,催化活性也有一定的改变。     

TiCl4/SiO2负载型催化剂用于丁二烯聚合Ⅱ.聚合条件及聚合动力学

使用以球磨法制备的 SiO2负载 TiCl4催化剂进行丁二烯溶液聚合,考察了聚合条件对催化效率的影响以及在 20～ 60℃下的聚合动力学。确定了适宜的聚合条件：以加氢汽油为溶剂, Al/Ti摩尔比为 20, Ti/Bd摩尔比为 2× 10－ 4, 50℃聚合 10 h以上。溶液聚合动力学研究结果表明,本体系在低转化率下为稳态聚合,其稳态聚合速率方程为 Rp=kpf[Ti]0[Bd],聚合的表观活化能为 11.4 kJ/mol。     

Effect of halocarbon promoters on polyethylene properties using MgCl2 (ethoxide type)/TiCl4/AlEt3/H2 catalyst system

In our previous study we found that addition of proper amount of halocarbons (HC) including chlorocyclohexane (CHC), chlorocyclopentane (CHP), butylchloride (BC), 1,4‐dichlorobutane (DCB), and chloroform (C) to the MgCl₂ (Ethoxide type)/TiCl₄/AlEt₃ catalytic system leads to a strong productivity improvement. In this study, the effect of these halocarbons on the properties of resulting polymers was investigated using H₂ as chain transfer agent at optimum HC/Ti molar ratio. The nature of halocarbon compound had a strong effect on polymer properties as well as on development of polymerization activity. Effect of halocarbon promoters on the polymer melt flow index (MFI), melt flow ratio (MFR), particle size distribution (PSD), bulk density, wax amount, crystallinity, and thermal properties of the polymers were studied. Results showed that, in the presence of halocarbons, polyethylenes with higher MFI and bulk density, broader MFR and lower wax amount have been obtained. Also, sieve analysis showed that, in the presence of halocarbons as promoter, polymers had better particle size distribution (PSD). DSC analysis showed that the T_m of PEs prepared with the different promoters were in the region commonly reported for HDPE and was not affected substantially by halocarbons, but, the crystallinity of the polymers has been improved using halocarbon promoters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinetics of ethylene polymerization over supported TiCl4SiO2 Ziegler catalyst modified with binary metal chlorides

The polymerization of ethylene over metal chloride-exchanged silica-gel has been studied. Basic, amphoteric and electropositive metals on the surface of the silica-gel were found to promote the polymerization reaction. I.r., e.s.r. and kinetic studies suggest that the active sites were highly dispersed in a solid solution of TiCl₃ and MCl₂ formed from the supporting TiCl₄. The influence of polymerization time, temperature and pressure on the polymerization rate were also investigated.     

MgCl2-BuOH/TiCl4催化剂催化乙烯聚合动力学

研究了MgCl2-正丁醇/TiCl4催化剂常压下催化乙烯聚合的性能和动力学行为.考察了n(Al)/n(Ti)、聚合温度、共聚单体浓度、氢气分压对催化剂性能的影响.研究表明:三乙基铝为助催化剂,n(Al)/n(Ti)为200,聚合压力为0.1 MPa,温度为50℃,聚合时间为2 h时,该催化剂具有较高的活性:聚合动力学行为平稳,活性衰减较慢,活性可达1 550.2 g/g;该催化剂具有良好的乙烯均聚合和共聚合性能以及氢调性能.     

Ethylene-propylene copolymers by a supported Ziegler-Natta catalyst based on TiCl4/MgCl2

Ethylene-propylene copolymers have been prepared by using Ziegler-Natta catalysts based on TiCl₄, MgCl₂, PCl₃ and (n-Bu)₃PO₄. The catalysts TiCl₄/MgCl₂/PCl₃ and TiCl₄/MgCl₂/(n-Bu)₃PO₄ were prepared by reacting TiCl₄ with pretreated MgCl₂. The support was prepared by ball milling of MgCl₂ with varied amounts of PCl₃ or (n-Bu)₃PO₄. The addition of PCl₃ has remarkably increased the MgCl₂ surface area in comparison with (n-Bu)₃PO₄. The effects of PCl₃ and (n-Bu)₃PO₄ on ethylene homopolymerization, ethylene-propylene copolymerization and on copolymer properties were evaluated. The catalyst system containing PCl₃ permitted to synthesize propylene-ethylene copolymers with up to 75% (w/w) of propylene and provided control of copolymer crystallinity. The reduction of the copolymer molecular weight distribution suggested that PCl₃ acted as an internal donor, poisoning some active catalytic sites. Received: 2 April 1997/Revised: 6 June 1997/Accepted: 18 June 1997     

The effect of SiO2 porosity on activity profiles and comonomer incorporation in slurry ethylene/butene‐1 polymerization by (SiO2/MgCl2/TEOS/TiCl4) catalyst system

To investigate the influence of support porosity parameters e.g., average pore volume (APV), pore diameter (PD), and pore surface area distribution (PSAD) on activity‐profile of catalyst and comonomer incorporation, a series of silica‐supports with different porosity were prepared through sol–gel method and used to synthesize corresponding (SiO₂/MgCl₂/TEOS/TiCl₄) catalysts. Polymerization of ethylene/butene‐1 showed that increasing of APV from 0.75 to 2.2 cm³ g increase initial activity from 120 to 400 (g_poly/g_cat.bar.hr) followed by appearance of secondary peaks in activity‐profile which could be attributed to the variation of PSAD. It is found that the effect of support in polymerization is a complicated issue which depends not only on the porosity parameters also on the comonomer concentration. The catalyst with PD of 300 Å gives higher comonomer incorporation and polymers with 15–20% lower crystallinity in contrast to catalyst with PD of 100 Å. Porosity effect was quantitatively studied by modifying of conventional Z‐N catalyst polymerization mechanism through introducing fragmentation term to achieve a new tool in designing and developing of polyolefin catalysts. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011