用高效SiO2载体催化剂进行乙烯气相聚合

使用球形ＳｉＯ２负载ＭｇＣｌ２－ＴｉＣｌ４高活性催化剂进行乙烯气相聚合，考察了催化剂制备条件和添加剂对催化剂的组成、催化活性以及聚合表观动力学的影响．结果表明，ＳｉＯ２热处理温度和所用的醇对Ｍｇ和Ｔｉ的负载量及乙烯聚合活性有明显的影响．催化剂制备中添加Ｌｅｗｉｓ酸ＳｉＣｌ４或ＡｌＥｔ２Ｃｌ能大幅度提高催化剂的活性，其中以ＳｉＣｌ４的效果最为明显．随着ＳｉＣｌ４用量的增加，乙烯气相聚合的活性显著提高，聚合速度随时间变化由渐升平稳型转变为衰减型     

新型高活性催化剂乙烯气相聚合的研究（I）：气相均聚和共聚…

研究了新型高活性乙烯气相聚合催化剂ＴｉＣｌ４／ＭｇＣｌ２／ＺｎＣｌ２／ＳｉＣｌ４／醇／Ａｌ（ｉ－Ｂｕ）３体系中钛和醇组分含量对聚合反应和产物颗粒形态的影响。测定了乙烯气相聚合反应动力学曲线，确定了聚合动力学方程。用ＳＥＭ，ＤＳＣ，ＷＡＸＤ，＾１＾３ＣＮＭＲ对催化剂及聚合物的形态，结构和性能进行了分析和表征。     

单茂钛催化剂的丙烯无规聚合反应及其动力学研究

比较了不同钛化合物／甲基铝氧烷（ＭＡＯ）催化体系的丙烯无规聚合，催化活性次序为ＣｐＴｉ（ＯＲ）３＞ＣｐＴｉ（ＯＰｈ）３＞ＣｐＴｉＣｌ３＞Ｃｐ２ＴｉＣｌ２＞Ｔｉ（ＯＢｕ）４＞ＴｉＣｌ４＞Ｔｉ（ＯＢｕ）２Ｃｌ２，所得聚丙烯用沸庚烷抽提８ｈ，溶解９５％以上，可溶部分经１３Ｃ ＮＭＲ、ＷＡＤＸ、ＦＴＩＲ等分析证明为无规聚丙烯（ａＰＰ），是没有结晶性的弹性体．ＧＰＣ测出其分子量Ｍｗ＝８．０～１０．０×１０４，Ｍｗ／Ｍｎ≈２．０．探索了催化体系ＣｐＴｉ（Ｏ ｎ Ｐｒ）３／ＭＡＯ中钛的浓度、［Ａｌ］／［Ｔｉ］摩尔比，丙烯聚合压力，聚合温度和时间对丙烯聚合反应的影响．研究了该催化体系丙烯聚合反应动力学规律，表观聚合反应速率对催化剂浓度和单体压力（浓度）都呈一级反应关系，表观聚合速率常数ＫＰ＝２９２×１０５ｍｏｌ／Ｌ·ｈ（４０℃）．活化能ΔＥ＝－７．８８×１０３Ｊ·ｍｏｌ－１，碰撞因子Ａ＝１．４１×１０－４ｍｏｌ／Ｌ·ｈ．     

Co－Mo／TiO_2和C0－M0／γ－Al_2O_3加氢脱硫催化剂的研究

本文考察了ＣｏＭｏ／ＴｉＯ３和ＣｏＭｏ／γ－Ａｌ２Ｏ３催化剂的加氢脱硫性能及表面结构变化和预处理条件对其活性的影响．担体ＴｉＯ２（Ａ）和ＴｉＯ２（Ｂ）分别采用ＴｉＣｌ４中和法和ＴｉＯＳＯ４水解法制备．结果表明，催化剂的活性顺序为ＣｏＭｏ／ＴｉＯ２（Ａ）＞ＣｏＭｏ／ＴｉＯ２（Ｂ）＞ＣｏＭｏ／γ－Ａｌ２Ｏ３催化剂的预处理条件对催化剂的加氢脱硫（ＨＤＳ）和加氢（ＨＹＤ）活性有很大影响，ＴｉＯ２担体上Ｍｏ物种主要以八面体配位构型存在，Ｍｏ６＋更易于还原成低价态．     

CoMo／Al_2O_3和CoMo／TiO_2－Al_2O_3加氢脱硫催化剂的研

研究了ＣｏＭｏ／Ａｌ２Ｏ３和ＣｏＭｏ／ＴｉＯ２－Ａｌ２Ｏ３催化剂的加氢脱硫性能，并用ＬＲＳ，ＸＲＤ和ＴＰＳ等方法表征其表面相结构和硫化行为．结果表明，以ＴｉＯ２－Ａｌ２Ｏ３为担体的Ｍｏ和ＣｏＭｏ催化剂的活性均比相应的Ａｌ２Ｏ３为担体的高；少量Ｃｏ，Ｎｉ助剂的引入可显著提高ＭｏＯ３在担体上的分散度和改进催化剂的活性；Ｃｏ助剂还有降低Ｍｏ物种硫化温度的作用．     

Co-Mo/TiO2和Co-Mo/γ-Al2O3加氢脱硫催化剂的研究

本文考察了ＣｏＭｏ／ＴｉＯ２和ＣｏＭｏ／γ－Ａｌ２Ｏ３催化剂的加氢脱硫性能及表面结构变化和处理条件对其活性的影响，担体ＴｉＯ２（Ａ）和ＴｉＯ２（Ｂ）分别采用ＴｉＯＳＯ４水解法制备，结果表明，催化剂的活性顺序为ＣｏＭｏ／ＴｉＯ２（Ａ）＞ＣｏＭｏ／ＴｉＯ２（Ｂ）＞ＣｏＭｏ／γ－Ａｌ２Ｏ３，催化剂的预处理条件对催化剂的加氢脱硫和加氢活性有很大影响，ＴｉＯ２担体上Ｍｏ物种主要以八面体配位构型存在，Ｍｏ＾－     

SOCl2／SnCl4—DMSO／n—Bu4NCl引发体系苯乙烯活性阳离子聚合反应的研究

研究表明，ＳＯＣｌ２／ＳｎＣｌ４引发体系的苯乙烯聚合反应很快，但所得聚合产物的分子量分布宽（Ｍｗ／Ｍｎ＝４．３７），且其ＧＰＣ曲线呈多重峰；单独加入季铵盐（ｎ－Ｂｕ４ＮＣｌ）或二甲基亚砜（ＤＭＳＯ）可使聚合产物分子量分布明显变窄，并随浓度的增加而加强，但程度有限，不显示活性聚合特征；ＤＭＳＯ和ｎ－Ｂｕ４ＮＣｌ同时加入，表现出协同效应，不仅能保持较高的聚合反应活性，而且产物分子量分布很窄（Ｍｗ／Ｍｎ＝１．２７），分子量随单体转化率增加而增加，且线性关系良好，聚合物链数只与引发剂初始浓度相关，显示活性聚合特征。     

异丁烯的活性阳离子聚合反应

作者采用２ ,４ ,４ 三甲基 ２ 氯戊烷（ Ｔ Ｍ Ｐ Ｃｌ）／ Ｔｉ Ｃｌ４ 引发剂体系,在电子给体存在下,对异丁烯（ Ｉ Ｂ） 的活性阳离子聚合进行了研究．在 Ｔ Ｍ Ｐ Ｃｌ／ Ｔｉ Ｃｌ４／ Ｉ Ｂ 二氯甲烷／ 己烷（４０／６０ Ｖ／ Ｖ）／ － ８０ ℃聚合系统中,以 Ｎ, Ｎ 二甲基苯胺、吡啶及三乙胺为电子给体,对聚合反应速率及产物分子量分布的影响进行了研究．发现当 Ｎ, Ｎ 二甲基苯胺或三乙胺的浓度稍高于质子性杂质的浓度时,即能实现异丁烯的活性聚合,得到分子量分布较窄的聚合物．电子给体的主要作用是质子捕捉剂,抑制痕量水的引发,而且对阳离子具有稳定作用     

La2O3对Ni-Mo/γ-Al2O3催化剂CO和CO2甲烷化的影响

采用浸渍法制备了一系列Ｎｉ－Ｍｏ－Ｌａ／γ－Ａｌ２Ｏ３催化剂并测定了催化剂的ＣＯ和ＣＯ２甲 化活性采用ＴＥＭ,ＸＰＳ和ＣＯ化学吸附等手段研究了表面性质。结果表明,Ｌａ２Ｏ３的咖入提高了Ｎｉ－Ｍｏ／γ／Ａｌ２Ｏ３催化剂的ＣＯ和ＣＯ２甲烷化活性,增加了催化剂中Ｎｉ的分散度,活性表面积及催化剂表面Ｎｉ原子的浓度,降低了电子结合能。     

TiO_2调变对MoO_3/γ-Al_2O_3和CoO-MoO_3/γ-Al_2O_3表面结构及还原性能的影响

采用气相流动吸附法制ＴｉＯ２／γ－Ａｌ２Ｏ３，复合载体，浸渍法担载一定量ＭｏＯ３或ＣｏＯ－ＭｏＯ３，用ＸＲＤ，ＬＲＳ和ＴＰＲ等技术考察了Ｍｏ或Ｃｏ－Ｍｏ催化剂的表面结构和还原性能。结果表明，覆盖在γ－Ａｌ２Ｏ３上的ＴｉＯ２能减弱ＭｏＯ３与γ－Ａｌ２Ｏ３之间的相互作用，明显改善Ｍｏ催化剂的表面结构，促进ＭｏＯ３的还原。适量ＣｏＯ助剂的加入能促进ＭｏＯ３在载体表面的分散。     

用于丙烯聚合的MgCl2负载Ziegler-Natta催化剂研究进展

综述了用于丙烯聚合的MgCl2负载Ziegler-Natta催化剂研究进展,包括内给电子体的发展及其作用研究,催化剂活性中心的模型,用MgCl2负载的Z-N催化剂制备抗冲聚丙烯合金.     

Effect of EtOH/MgCl(2) molar ratios on the catalytic properties of MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalyst for ethylene polymerization

MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalysts for ethylene polymerization were prepared by impregnation of MgCl(2) on SiO(2) in heptane and further treatment with TiCl(4). MgCl(2)·nEtOH adduct solutions were prepared with various EtOH/MgCl(2) molar ratios for preparation of the MgCl(2)-supported and MgCl(2)-SiO(2)-supported catalysts in order to investigate the effect on polymerization performance of both catalyst systems. The catalytic activities for ethylene polymerization decreased markedly with increased molar ratios of [EtOH]/[MgCl(2)] for the MgCl(2)-supported catalysts, while for the bi-supported catalysts, the activities only decreased slightly. The MgCl(2)-SiO(2)-supported catalyst had relatively constant activity, independent of the [EtOH]/[MgCl(2)] ratio. The lower [EtOH]/[MgCl(2)] in MgCl(2)-supported catalyst exhibited better catalytic activity. However, for the MgCl(2)-SiO(2)-supported catalyst, MgCl(2) can agglomerate on the SiO(2) surface at low [EtOH]/[MgCl(2)] thus not being not suitable for TiCl(4) loading. It was found that the optimized [EtOH]/[MgCl(2)] value for preparation of bi-supported catalysts having high activity and good spherical morphology with little agglomerated MgCl(2) was 7. Morphological studies indicated that MgCl(2)-SiO(2)-supported catalysts have good morphology with spherical shapes that retain the morphology of SiO(2). The BET measurement revealed that pore size is the key parameter dictating polymerization activity. The TGA profiles of the bi-supported catalyst also confirmed that it was more stable than the mono-supported catalyst, especially in the ethanol removal region.     

球形氯化镁载体与四氯化钛反应的载钛过程研究

球形氯化镁载体型齐格勒-纳塔催化剂是目前常用的工业聚烯烃催化剂,由于制备工艺对催化剂性能影响很大,因此对此类催化剂制备过程的研究具有重要意义。本文利用自制球形氯化镁载体与四氯化钛反应制备球形聚烯烃催化剂,分析了载钛反应过程的中间产物。对球形氯化镁载体载钛过程中钛含量、比表面、比孔容、晶型等发生的变化进行分析,并研究了邻苯二甲酸二丁酯作为内给电子体在球形氯化镁载体载钛过程中的作用,为球形氯化镁载体型催化剂制备工艺的改进提供了重要参考依据。     

以聚丙二醇二苯甲酸酯为给电子体的丙烯聚合催化剂

 采用聚丙二醇二苯甲酸酯(PPGDB)为内给电子体制备了一种新的丙烯聚合催化剂MgCl2/PPGDB/TiCl4. 该催化剂用于丙烯聚合时,除了具有与以邻苯二甲酸二异丁酯为给电子体的催化剂相当的活性和立体定向性外,其特点在于所得产物的分子量分布较宽(Mw/Mn＞8.0). 采用红外光谱研究了催化剂中PPGDB与MgCl2的作用机制,结果表明PPGDB中的酯官能团和醚官能团可同时与MgCl2配位. 这种双官能团的配位作用是所得聚合物分子量分布较宽的主要原因.     

New penta-ether as the internal donor in the MgCl2-supported Ziegler-Natta catalysts for propylene polymerization

The penta-ether compound was synthesized by the reaction of di(trimethylolpropane) with sodium hydride as the strong base and methyl iodide as the alkyl halide. This compound was characterized by NMR, FTIR, and GC techniques. The MgCl₂-supported titanium catalysts were incorporated with varying amounts of penta-ether compound as the internal donor and also the catalysts without the internal donor were synthesized. The synthesized catalysts and the conventional Ziegler- Natta catalyst were characterized. The titanium contents were determined by spectrophotometry, magnesium by complexometric titration and chloride by argentometric titration. The effects of the new internal donor on propylene polymerization with the prepared MgCl₂-supported Ziegler-Natta catalysts were investigated and then these results were compared to the results obtained using the conventional diisobutyl phthalate-besed-Ziegler-Natta catalyst. The highest crystallinity degree, melting temperature, and isotacticity of polypropylene were obtained using the catalyst with a penta-ether/Mg molar ratio equal to 0.21.     

硅烷类外给电子体的取代基变化对丙烯聚合影响的研究

合成了2种新型硅烷化合物双环己基二甲氧基硅烷(Donor-H)、双哌啶二甲氧基硅烷(Donor-Py),将其与工业化的环己基甲基二甲氧基硅烷(Donor-C)分别作为外给电子体,用于MgCl2负载的Ziegler-Natta催化剂催化丙烯聚合,通过DSC、GPC、SSA和13C-NMR等分析手段研究了3种外给电子体取代基的变化对催化剂的催化活性、氢调敏感性、聚丙烯的等规度、分子量分布、结晶能力、等规序列分布的影响.结果表明,随着外给电子体取代基体积的增大,外给电子体的给电子能力逐渐增强.与Donor-C相比,随着外给电子体取代基体积的增大,合成的具有较大取代基的Donor-H和Donor-Py用于丙烯聚合时都表现优异的催化性能,特别是新型含有N杂原子的氨基硅烷类Donor-Py为外给电子体的催化剂的催化活性和制备的聚丙烯的等规度最高,聚丙烯的熔融指数可调范围最宽,结晶能力更强.氨基硅烷类Donor-Py制备的聚丙烯SSA热分级后的高等规组分含量最多,可高达64.5%,聚丙烯等规序列长度最长,聚丙烯的等规序列分布最窄,而且13C-NMR结果也表明聚丙烯等规序列长度MSL最长,聚丙烯的分子链最规整.     

Propylene Polymerization by TiCl_4 Supported on Mg(OEt)_2 Activating with Ethanol/CO_2 System

For the preparation of high-active and high-isospecific catalysts for propylenepolymerization,various supports such as Mg-alkyls[1 ] ,Mg( OH) 2 [2 ] ,Mg O[3] ,Mg Cl2 [4] .Grignard compounds[5] ,or magnesium alkoxide[6] had been used.Lately,Mg( OEt) 2 -supported Ti Cl4catalysts including an organic chloride and/ or an internal donor preparedby physical milling method and chemical reaction method were studied and it was foundthat Mg( OEt) 2 is converted to Mg Cl2 by reaction with Ti Cl4a…     

给电子体在丙烯聚合MgCl2载体催化剂体系中的作用

制备了3种含有不同内给电子体(邻苯二甲酸二异丁酯,9,9-二甲氧基甲基-芴和1,1-双甲氧基甲基-环丁烷)的MgCl2负载型丙烯聚合齐格勒-纳塔(Z-N)催化剂,研究了给电子体结构与聚合性能之间的关系,用红外光谱剖析了催化剂及其相关化合物的结构,结果发现催化剂中的内给电子体直接与MgCl2配位,而没有与TiCl4结合.内给电子体的加入,降低了Z-N催化剂中钛的含量,提高催化丙烯聚合的活性,使聚合物的分子量分布变窄.聚合物立构规整度的变化强烈依赖于内给电子体的结构.     

原位反应法制备CpTi(dbm)Cl2/MgCl2载体型催化剂及其催化乙烯聚合的研究

非茂催化剂对烯烃聚合显示出优异的催化特性,是继ziegler—Natta催化剂及茂金属催化剂之后的新一代烯烃聚合催化剂^[1],其中非环戊二烯基配体有含氮化合物[2-8]和含氧化合物^[9-15]等,这些非茂配合物可催化乙烯或丙烯聚合．将金属中心与一个环戊二烯基和一个非环戊二烯基配体而     

In situ ATR-FTIR studies on MgCl2-diisobutyl phthalate interactions in thin film Ziegler-Natta catalysts

To study the surface structure of MgCl(2) support and its interaction with other active components in Ziegler-Natta catalyst, such as electron donors, we prepared a thin film analogue for Ziegler-Natta ethylene polymerization catalyst support by spin-coating a solution of MgCl(2) in ethanol, optionally containing a diester internal donor (diisobutyl-ortho-phthalate, DIBP) on a flat Si crystal surface. The donor content of these films was quantified by applying attenuated total internal reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Changes in the interaction of DIBP with MgCl(2) at various temperatures were monitored by in situ ATR-FTIR. Upon increasing the temperature, a shift in the (C═O) band toward lower wavenumbers was observed together with the depletion of (O-H) stretching band due to the desorption of residual ethanol. We assign this shift to gradual redistribution of adsorbed DIBP from adsorption sites on the MgCl(2) (104) surface toward the more acidic MgCl(2) (110) surface. The morphologies of MgCl(2) and MgCl(2)/DIBP films were studied by transmission electron microscopy (TEM) revealing a preferential orientation of ClMgCl layers (001) parallel to the lateral film dimensions. This orientation becomes more pronounced upon annealing. In the absence of donor, the MgCl(2) grow in to large crystals aligned in large domains upon annealing. Both crystal growth and alignment is impeded by the presence of donor.