水杨醛亚胺型镍金属烯烃聚合催化剂研究进展

非茂金属烯烃聚合催化剂作为新型烯烃聚合催化剂,具有配体可修饰及过渡金属可选择的优势,拓宽了烯烃聚合催化剂研究领域。综述了水杨醛亚胺型镍金属配合物催化烯烃聚合近二十年研究进展,阐述了配体上取代基电子效应、空间结构及催化乙烯聚合或烯烃共聚性能关系,分析了水杨醛亚胺型镍金属配合物催化烯烃聚合或者共聚特点,指明了此类烯烃聚合催化剂发展应用前景。     

中国专利

一种含有二齿配体的过渡金属化合物及其在烯烃聚合中的应用本发明涉及一种含有二齿配体的过渡金属化合物,由通式(I)表示,式中:M为钛、锆或铪;X为卤素原子或含有1~30个碳原子的烃基或含有1~30个碳原子的烃氧基,以及由这种过渡金属化合物和有机铝化合物组成的烯烃聚合催化体系。该聚合体系催化乙烯聚合,可得到较高的聚合活性。     

中国专利

[N^O]型双齿配体与锆金属配位的烯烃聚合催化剂及其制备方法本发明为一种[N^O]型双齿配体与锆金属配位的烯烃聚合催化剂及其制备方法。该催化剂表达式为ZrL_2Cl_2,其中L表示一种含有可与金属配位的N,O原子的配体。该催化剂不仅具有独特新颖的结构,催化乙烯聚合具有较高的催化活性,并且催化剂制备简单。该催化剂作为A,B组分配合,可用于催化乙烯聚合,制备高相对分子质量聚乙烯产品。公开号CN 101824109公开日2010年9月8日申请人复旦大学     

中国专利目次

74 74 74 74 74 74 74 74 75 75 75 75 7575烯烃聚合用固体催化剂成分、烯烃聚合用催化剂及烯烃聚合物的制备方法双位烯烃聚合催化剂组合物用于在不同聚合催化剂之间转变的方法【CN]型双齿配体与后过渡金属配位的烯烃聚合催化剂及其制备方法一种西佛碱配位WB族的烯烃聚合催化剂     

乙烯聚合用树枝状过渡金属催化剂研究进展

树枝状过渡金属催化剂是在树枝状大分子上负载上过渡金属活性中心,因此,此类催化剂既具有树枝状大分子特有的艺术结构,同时还具有过渡金属配合物的功能化性能,使其两者能够协同发挥作用,兼具均相和非均相催化体系的特点,在催化烯烃聚合方面具有较高的催化活性和良好的催化稳定性,近年来备受关注,催化乙烯聚合就是其中的研究热点之一。本文按其过渡金属活性中心进行分类,综述了近年来国内外树枝状过渡金属催化剂在这乙烯聚合方面的进展,阐述了多种树枝状效应产生的原因,并且对乙烯聚合用树枝状过渡金属催化剂的发展前景进行了展望。     

中国专利目次

一种含有二齿配体的过渡金属化合物及其在烯烃聚合中的应用?85
　　一种用于乙烯聚合的催化剂组分及其催化剂?85
　　用于贵金属催化剂原位固载的磁性聚合物微球的制备方法?85
　　一种丙烯聚合催化剂及其制备和应用?85
　　丙烯聚合用固体催化剂的制备方法及由其制备的催化剂?85
　　一种以聚烯烃为载体制备苯乙烯/异戊二烯/马来酸酐多嵌段聚合物的方法?85
　　一种高氢调敏感性聚烯烃催化剂组分、制备方法和烯烃聚合方法?85
　　一种烯烃聚合催化剂组分、烯烃聚合方法及应用?86
　　一种用于烯烃高温聚合的催化剂组分及制备方法?86
　　用于烯烃聚合的催化剂组合物以及利用该催化剂组合物的聚烯烃的制备方法?86
　　制备新型催化剂组合物的方法以及使用该催化剂组合物的烯烃聚合物?86
　　用于烯烃聚合的负载型催化剂以及利用该催化剂的聚烯烃的制备方法?86
　　一种外给电子体组分、含有该组分的烯烃聚合催化剂及其应用?86
　　一种气相聚合装置及烯烃聚合方法?86     

非茂双核烯烃聚合催化剂研究和应用进展

综述了非茂双核烯烃催化剂近十年的研究进展。重点阐述了配体上各种取代基电子效应和空间结构与催化乙烯聚合性能关系,分析了双核非茂金属烯烃催化剂催化聚合特点,指出了烯烃聚合用双核非茂催化剂发展方向。     

非茂双核烯烃聚合催化剂研究和应用进展(续)

综述了非茂双核烯烃催化剂近十年的研究进展。重点阐述了配体上各种取代基电子效应和空间结构与催化乙烯聚合性能关系,分析了双核非茂金属烯烃催化剂催化聚合特点,指出了烯烃聚合用双核非茂催化剂发展方向。     

乙烯选择性三聚催化剂的研究进展

对乙烯选择性三聚反应进行了论述，着重分析了催化剂的组成、活性、成本和1-己烯的总选择性，并展望了烯烃选择性齐聚反应的发展。研究表明，一个具有高选择性的三聚催化剂需要选择具有合适氧化态的前过渡金属，以及具有合适电子结构、空间位阻与介稳定性的配体。此外，可选择的配体越来越多，涵盖了芳香族、杂原子和多齿配体，并且活性中心也不再局限于铬，扩展到钛等其他前过渡金属。     

烯烃配位活性聚合催化剂的研究进展

综述了茂/单茂金属催化剂、二元胺前过渡金属催化剂、α-二亚胺后过渡金属催化剂和水杨醛亚胺前过渡金属催化剂在烯烃配位活性聚合中的研究进展,以及各种催化剂催化烯烃配位活性聚合的实例和影响配位活性聚合的关键因素。这四种烯烃配位活性聚合催化剂中,茂/单茂金属催化剂的研究结果最成熟,但其他三种非茂体系的催化剂具有制备容易、催化烯烃配位活性聚合的条件温和、在实际应用中易实现的优势。此外,采用多重活性聚合的方法能解决配位活性聚合时催化剂利用率低的问题。     

不同形貌介孔材料催化剂的制备及在乙烯聚合中的应用

利用面包圈状、棒状、高比表面积球状和空心球状4种不同形貌的介孔材料作为载体负载甲基铝氧烷和茂金属双（正丁基环戊二烯基）二氯化锆（BuCp）制备负载型茂金属催化剂,并在2 L不锈钢高压聚合釜进行高压乙烯聚合小试试验。文中研究了4种反应器的组成、结构和微观形貌。扫描电镜、小角X光粉晶衍射、氮气吸附-脱附测试结果表明,4种不同形貌介孔材料在负载茂金属后仍然保持较好微观形貌及其特有的介孔材料孔道结构,负载茂金属后反应器的孔结构参数较负载前有所减小,孔壁厚度有所增强,表明茂金属成功进入介孔材料孔道中。元素分析结果表明,所得催化剂表面的Al元素质量分数范围为16%～22%,Zr元素质量分数范围为0.4%～0.7%。聚合试验结果表明,催化剂对乙烯均聚和共聚的活性均优于当前工业用载体955硅胶负载同样茂金属后的乙烯均聚和乙烯和己烯共聚的活性,其中空心球状介孔材料反应器为最适合乙烯聚合的催化剂。     

Integrating Catalyst and Co‐Catalyst Design in Olefin Polymerization Catalysis: Transferable Dianionic Ligands for the Activation of Late Transition Metal Polymerization Catalysts

Treatment of nickel and palladium α‐diimine catecholate complexes with alkylaluminum catecholates leads to active ethylene polymerization catalysts. Comparison of the catalytic activities achieved with combinations of α‐diimine catecholate or halide complexes as catalyst precursors with different activators (MMAO or alkylaluminum catecholates) reveals that the presence of the catecholate ligand in both catalyst components is beneficial for achieving high activity levels at very low M/Al ratios.     

乙烯聚合双功能催化剂概述

乙烯在一个以应器中同时进行齐聚和共聚反应的新工艺，是近年来乙烯聚合研究领域中的热点之一，本文以混合型有机铬／氧化铬催化剂和钛系催化剂为例，介绍了乙烯聚合双功能催化剂的制备方法，技术特点，聚合动力学以及所合成树脂的性能等，综述了该研究领域的一些新进展，并对两种不同类型的双功能催化进行了简单评述。     

Metallophosphate-supported Ziegler–Natta catalysts for ethylene polymerization

Several catalysts for ethylene polymerization were obtained by TiCl₄ deposition on a series of mixed metallophosphates at 100°C and were evaluated in suspension polymerization at 70°C and 14.6-atm ethylene pressure. Kinetic parameters of these polymerization reactions (initial activity, rate of deactivation, stability, etc.) were compared with properties of supports and catalysts themselves. Statistical analysis of the correlations between catalyst performance and properties shows that, in the case of Al-containing supports, the principal property of a catalyst influencing its activity is its specific surface area. An inverse dependence was found between catalyst activity and stability in ethylene polymerization. The presence of aluminium in the supports is essential for high catalytic activity, whereas the addition of other metals (non-transition or transition) does not influence the catalysts to any significant degree.     

FI Catalysts: A New Family of High Performance Catalysts for Olefin Polymerization

This paper reviews a new family of olefin polymerization catalysts. The catalysts, named FI catalysts, are based on non‐symmetrical phenoxyimine chelate ligands combined with group 4 transition metals and were developed using “ligand‐oriented catalyst design”. FI catalysts display very high ethylene polymerization activities under mild conditions. The highest activity exhibited by a zirconium FI catalyst reached an astonishing catalyst turnover frequency (TOF) of 64,900 s ^–1 atm ^–1, which is two orders of magnitude greater than that seen with Cp₂ZrCl₂ under the same conditions. In addition, titanium FI catalysts with fluorinated ligands promote exceptionally high‐speed, living ethylene polymerization and can produce monodisperse high molecular weight polyethylenes (M_w/M_n<1.2, max. M_n>400,000) at 50 °C. The maximum TOF, 24,500 min ^–1 atm ^–1, is three orders of magnitude greater than those for known living ethylene polymerization catalysts. Moreover, the fluorinated FI catalysts promote stereospecific room‐temperature living polymerization of propylene to provide highly syndiotactic monodisperse polypropylene (max. [rr] 98%). The versatility of the FI catalysts allows for the creation of new polymers which are difficult or impossible to prepare using group 4 metallocene catalysts. For example, it is possible to prepare low molecular weight (M_v∼10³) polyethylene or poly(ethylene‐co‐propylene) with olefinic end groups, ultra‐high molecular weight polyethylene or poly(ethylene‐co‐propylene), high molecular weight poly(1‐hexene) with atactic structures including frequent regioerrors, monodisperse poly(ethylene‐co‐propylene) with various propylene contents, and a number of polyolefin block copolymers [e.g., polyethylene‐b‐poly(ethylene‐co‐propylene), syndiotactic polypropylene‐b‐poly(ethylene‐co‐propylene), polyethylene‐b‐poly(ethylene‐co‐propylene)‐b‐syndiotactic polypropylene]. These unique polymers are anticipated to possess novel material properties and uses.     

新型后过渡金属烯烃催化剂的研究进展

综述了近年来－系列新型α－二亚胺型后过渡金属（Ni、Pd、Fe、Co）催化剂在烯烃聚合、极性单体共聚、烯烃齐聚、环烯烃加成聚合、烯烃活性聚合和聚烯烃纳米复合物等方面的最新进展。系统地阐述了不同的中心过渡金属离子、α－二亚胺骨架、骨架上的取代基和不同的聚合条件（温度、压力）分别对催化剂的聚合活性、聚烯烃支化率、聚合物分子量和分子量分布以及聚合产物的性质等影响，并且简要说明了这一类催化剂的制备方法和新特点。     

FI Zr-type catalysts for ethylene polymerization

Two FI-type catalysts of Bis[N-(3,5-dicumylsalicylidene)-naphthylaminato]zirconium(IV) dichloride (catalyst (a)) and Bis[N-(3,5-dicumylsalicylidene)-anthracylaminato]zirconium(IV) dichloride (catalyst (b)) were prepared and used for ethylene polymerization comparatively. Methylaluminoxane (MAO) was used as cocatalyst. Polymerization reactions of ethylene using the prepared catalysts at the different conditions of polymerization were carried out. Plurality of the fused aromatic rings on the N atom of the imine in the catalyst structure affected the polymerization activity and molecular weight of the resulting polymer as well. Productivity of the prepared catalysts increased with the addition of [Al]/[Zr] molar ratio. The highest activity was observed at about 35–40 °C for the catalysts. The catalyst (b) produced higher viscosity average molecular weight (M_v) of the obtained polyethylene, while generally the activity of the catalyst (a) was higher than the catalyst (b). Similar behavior was observed for the polymerization carried out at the monomer pressure of 2 to 6 bars using the catalysts. The higher the pressure the more activity of the catalysts obtained, in the range studied. Crystallinity and melting point of the obtained polymer were between 55–65% and 120–135 °C respectively. Higher pressure increased both the crystallinity and the M_v values of the resulting polymer. The polymerization was carried out using different amounts of hydrogen. Higher amount of hydrogen could increase the activity of the catalysts. A linear dependence between the polymerization time and the molar weight was observed, however the polydispersity was broadened with the time.     

Self-assembled heterogeneous late transition–metal catalysts for ethylene polymerization; New approach to simple preparation of iron and nickel complexes immobilized in clay mineral interlayer

To develop heterogeneous catalysts for ethylene polymerization, bis(imino)pyridineiron(III), α-diiminenickel(II), and iminopyridinenickel(II) complexes were immobilized in the clay mineral (montmorillonite, fluorotetrasilicic mica or saponite) interlayers by a one-pot preparation method. In this method, the Fe^3 +- and Ni^2 +-exchanged clay minerals as an acid catalyst promoted the ligand formation from a ketone derivative and an aniline derivative, and then the formed ligand simultaneously coordinated to the metal ions located in the clay mineral interlayer. The obtained heterogeneous catalysts showed 100–3,000 g-PE g-cat^− 1 h^− 1 as activities for the ethylene polymerization/oligomerization.     

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.     

单茂金属化合物催化烯烃聚合

综述了单茂金属化合物催化烯烃聚合的机理及研究进展，指出IVB族元素钛、锆、铪的单茂金属化合物催化烯烃及α－烯烃的均聚和共聚的活性很好，并通过改变配体结构及聚合条件可得到立构规整性的聚合物，桥联的单茂金属化合物催化乙烯，丙烯聚合的活性相当高，可得到高间规度的聚丙烯和支化的超低密度聚乙烯，但催化苯乙烯的活性很低，VB族元素钒，铌、钽的单茂金属化合物作为烯烃催化剂可得到分子量分布相当窄（1．05）的聚烯烃，另外，单茂铬化合物在很低的Al/Cr(45-100)下具有相当高的催化活性，单茂镍化合物由于其亲氧性小，可催化极性单体（如甲基丙烯酸甲酯等）聚合。