CN116410237A - Synthesis method of non-bridged symmetrical metallocene catalyst, product and application thereof - Google Patents

Synthesis method of non-bridged symmetrical metallocene catalyst, product and application thereof Download PDF

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CN116410237A
CN116410237A CN202111665284.2A CN202111665284A CN116410237A CN 116410237 A CN116410237 A CN 116410237A CN 202111665284 A CN202111665284 A CN 202111665284A CN 116410237 A CN116410237 A CN 116410237A
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刘通
余正坤
曹媛媛
吴凯凯
李洪鹏
王连弟
徐显明
吴苹
汲永刚
赵思萌
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Abstract

The invention discloses a synthesis method of a non-bridged symmetrical metallocene catalyst, a product and application thereof, wherein the method takes fourth subgroup metal chloride, a C1-C3 alkyl metal reagent and cyclopentadiene derivatives as raw materials to react in an organic solvent under the environment of nitrogen or argon. The invention has the advantages of few reaction steps, simple and convenient operation, high efficiency, strong substrate applicability and the like.

Description

非桥联对称茂金属催化剂的合成方法及其产物和应用Synthetic method of non-bridged symmetrical metallocene catalyst and its product and application

技术领域technical field

本发明涉及非桥联对称茂金属催化剂的合成方法及其产物和应用。The invention relates to a synthesis method of a non-bridged symmetrical metallocene catalyst, a product and an application thereof.

背景技术Background technique

茂金属化合物一般指过渡金属或稀土金属与至少一个环戊二烯或其衍生物作为配体组成的一类有机配合物。两个相同茂环与中心金属原子配位,从而形成夹心结构,即所谓的非桥联对称双茂金属催化剂,如:Cp2MCl2、(Ind)2MCl2(M为钛、锆、铪;Cp为环戊二烯基;Ind为茚基)。Metallocene compounds generally refer to a class of organic complexes composed of transition metals or rare earth metals and at least one cyclopentadiene or its derivatives as ligands. Two identical rings coordinate with the central metal atom to form a sandwich structure, which is the so-called non-bridged symmetrical double metallocene catalyst, such as: Cp 2 MCl 2 , (Ind) 2 MCl 2 (M is titanium, zirconium, hafnium ; Cp is cyclopentadienyl; Ind is indenyl).

目前,有两种方法可以有效合成非桥联对称茂金属催化剂。方法1:将环戊二烯衍生物与强碱性化合物反应生成环戊二烯配体盐,然后再将该配体盐与过渡金属卤化物或其配合物反应制得催化剂;方法2:先将环戊二烯衍生物与强碱性化合物反应生成环戊二烯配体盐,然后与三甲基氯硅烷反应得到三甲基硅基环戊二烯衍生物,最后再与过渡金属卤化物反应制得目标产物。Currently, there are two approaches for the efficient synthesis of unbridged symmetric metallocene catalysts. Method 1: react cyclopentadiene derivatives with strong basic compounds to generate cyclopentadiene ligand salts, and then react the ligand salts with transition metal halides or their complexes to prepare catalysts; method 2: first React cyclopentadiene derivatives with strong basic compounds to generate cyclopentadiene ligand salts, then react with trimethylchlorosilane to obtain trimethylsilyl cyclopentadiene derivatives, and finally react with transition metal halides The reaction produces the target product.

上述方法虽然可以有效制备非桥联对称茂金属催化剂,但是却存在着反应步骤多、操作繁琐等缺点。由于环戊二烯衍生物配体盐或过渡金属卤化物在有机溶剂中的溶解度较差,因此,反应过程中常需要采用固体加料或泥浆式加料,而且反应又需要在无水无氧的条件下进行,这就进一步增加了反应操作的难度和安全风险。Although the above method can effectively prepare non-bridged symmetrical metallocene catalysts, it has the disadvantages of many reaction steps and cumbersome operation. Due to the poor solubility of cyclopentadiene derivative ligand salts or transition metal halides in organic solvents, solid feeding or slurry feeding is often required during the reaction, and the reaction needs to be carried out under anhydrous and oxygen-free conditions. This further increases the difficulty and safety risks of the response operation.

2001年,Eisch等人(Organometallics 2001,20,4132-4134.)报道了一种制备非桥联对称茂金属化合物的新方法。该方法采用一锅两步法,先通过2当量的正丁基锂与四氯化锆反应得到二丁基二氯化锆,然后再与2当量的环戊二烯反应得到双(环戊二烯基)二氯化锆,收率大于95%。与传统方法相比较,该工艺具有反应步骤少、操作简单、安全风险低等优点。然而,在我们应用该方法进行对称茂金属化合物的合成过程中发现,该工艺虽然可以有效制备双(环戊二烯基)二氯化锆、双(茚基)二氯化锆、双(甲基环戊二烯基)二氯化锆,但对于制备双(五甲基环戊二烯基)二氯化钛、双(2-苯基茚基)二氯化锆、双(1-甲基茚基)二氯化锆、双(三甲基硅基环戊二烯基)二氯化锆、双(五甲基环戊二烯基)二氯化锆或双(五甲基环戊二烯基)二氯化铪等非桥联对称茂金属化合物,则反应结果较差,收率仅为20~35%。In 2001, Eisch et al. (Organometallics 2001, 20, 4132-4134.) reported a new method for preparing non-bridged symmetrical metallocene compounds. The method adopts a one-pot two-step method, first reacting 2 equivalents of n-butyl lithium with zirconium tetrachloride to obtain dibutyl zirconium dichloride, and then reacting with 2 equivalents of cyclopentadiene to obtain bis(cyclopentadiene Alkenyl) zirconium dichloride, the yield is greater than 95%. Compared with traditional methods, this process has the advantages of less reaction steps, simple operation, and low safety risk. However, in our application of this method for the synthesis of symmetrical metallocene compounds, we found that although this process can effectively prepare bis(cyclopentadienyl) zirconium dichloride, bis(indenyl) zirconium dichloride, bis(formyl) Cyclopentadienyl) zirconium dichloride, but for the preparation of bis(pentamethylcyclopentadienyl) titanium dichloride, bis(2-phenylindenyl) zirconium dichloride, bis(1-methyl Indenyl) zirconium dichloride, bis(trimethylsilylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) zirconium dichloride or bis(pentamethylcyclopentadienyl) zirconium dichloride For non-bridged symmetrical metallocene compounds such as dienyl) hafnium dichloride, the reaction results are relatively poor, and the yield is only 20-35%.

发明内容Contents of the invention

为了至少部分地解决现有技术存在的技术缺陷,发明人作出本发明。In order to at least partly solve the technical deficiencies in the prior art, the inventors made the present invention.

作为本发明的一个方面,涉及一种制备非桥联对称茂金属催化剂的方法,以第四副族金属氯化物、C1-C3烷基金属试剂和环戊二烯衍生物为原料,在氮气或氩气环境下、有机溶剂中反应,通过一锅两步反应获得非桥联对称茂金属催化剂。As an aspect of the present invention, it relates to a method for preparing a non-bridged symmetrical metallocene catalyst, using the fourth subgroup metal chloride, C1-C3 alkyl metal reagent and cyclopentadiene derivative as raw materials, under nitrogen or Under an argon atmosphere and in an organic solvent, a non-bridged symmetric metallocene catalyst is obtained through a one-pot two-step reaction.

具体来讲,所述制备非桥联对称茂金属催化剂的方法包括:Specifically, the method for preparing a non-bridged symmetrical metallocene catalyst comprises:

(1)先在一定加料温度下,将2当量C1-C3烷基金属试剂加入第四副族金属氯化物与有机溶剂的混合物中,并在室温下反应得混合物;(1) At a certain feed temperature, 2 equivalents of C1-C3 alkyl metal reagents are added to the mixture of the fourth subgroup metal chloride and the organic solvent, and react at room temperature to obtain the mixture;

(2)在一定加料温度下,往步骤(1)所得混合物中加入2当量的环戊二烯衍生物,并在一定反应温度下反应。(2) At a certain feed temperature, add 2 equivalents of cyclopentadiene derivatives to the mixture obtained in step (1), and react at a certain reaction temperature.

在一个具体实施例中,所述第四副族金属氯化物的通式为MCl4,其中M为元素钛、锆、铪。In a specific embodiment, the general formula of the fourth subgroup metal chloride is MCl 4 , wherein M is an element titanium, zirconium, hafnium.

在一个具体实施例中,所述C1-C3烷基金属试剂为RLi、R2Zn或RMgX;其中,R为C1-C3的正构烷基,X为卤素氯、溴或碘。In a specific embodiment, the C1-C3 alkyl metal reagent is RLi, R 2 Zn or RMgX; wherein, R is a C1-C3 normal alkyl group, and X is a halogen chlorine, bromine or iodine.

在一个具体实施例中,所述环戊二烯衍生物可选自如下化合物:In a specific embodiment, the cyclopentadiene derivative can be selected from the following compounds:

Figure BDA0003450943420000031
Figure BDA0003450943420000031

其中,R1为C2-C4碳链的烷基、苄基、三甲基硅基;n为2-5的整数;当R3为氢时,R2可以为C1-C4碳链的烷基、苄基、三甲基硅基;当R2为氢时,R3可以为C1-C4碳链的烷基、苄基、苯基、4-甲基苯基、4-甲氧基苯基;R2和R3可以同时为甲基、乙基;R4可以为氢、甲基、苯基。Wherein, R 1 is C2-C4 carbon chain alkyl, benzyl, trimethylsilyl; n is an integer of 2-5; when R 3 is hydrogen, R 2 can be C1-C4 carbon chain alkyl , benzyl, trimethylsilyl; when R 2 is hydrogen, R 3 can be C1-C4 carbon chain alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl ; R 2 and R 3 can be methyl, ethyl at the same time; R 4 can be hydrogen, methyl, phenyl.

在一个具体实施方式中,所述一定加料温度为-78~0摄氏度,优选-40~-10摄氏度;所述一定反应温度为25~140摄氏度,优选60~110摄氏度。In a specific embodiment, the certain feed temperature is -78 to 0 degrees Celsius, preferably -40 to -10 degrees Celsius; the certain reaction temperature is 25 to 140 degrees Celsius, preferably 60 to 110 degrees Celsius.

在一个具体实施方式中,所述有机溶剂为正己烷、正庚烷、甲苯、邻二甲苯、四氢呋喃、2-甲基四氢呋喃、乙醚或乙二醇二甲醚。In a specific embodiment, the organic solvent is n-hexane, n-heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.

在一个具体实施方式中,步骤(1)的反应时间为4-8小时;步骤(2)的反应时间5-10小时。In a specific embodiment, the reaction time of step (1) is 4-8 hours; the reaction time of step (2) is 5-10 hours.

作为本发明的另一个方面,涉及上述方法制备的非桥联对称茂金属催化剂。As another aspect of the present invention, it relates to the non-bridged symmetrical metallocene catalyst prepared by the above method.

作为本发明的另一个方面,涉及上述非桥联对称茂金属催化剂在烯烃聚合反应中的应用。As another aspect of the present invention, it relates to the application of the above-mentioned non-bridged symmetrical metallocene catalyst in olefin polymerization.

作为本发明的另一个方面,涉及烯烃聚合反应,使用权利要求10所述非桥联对称茂金属催化剂。具体来说,所述烯烃聚合反应为1-癸烯聚合反应。As another aspect of the present invention, it relates to olefin polymerization, using the non-bridged symmetrical metallocene catalyst described in claim 10. Specifically, the olefin polymerization reaction is 1-decene polymerization reaction.

在反应过程中得到双正丁基二氯金属中间体并不稳定,易分解为二氯金属化合物,该化合物无法与环戊二烯衍生物继续反应得到目标产物。当使用多取代环戊二烯衍生物或三甲基硅基环戊二烯衍生物进行对称茂金属化合物制备反应时,由于取代基的电子效应和空间位阻效应,从而影响了环戊二烯衍生物的反应活性,当环戊二烯衍生物反应活性较低时,则会使得副反应发生几率增大,得到二氯金属化合物,导致目标反应无法发生,产物收率较低。The bis-n-butyl dichloride metal intermediate obtained during the reaction is not stable and is easily decomposed into a dichloro metal compound, which cannot continue to react with the cyclopentadiene derivative to obtain the target product. When using multi-substituted cyclopentadiene derivatives or trimethylsilyl cyclopentadiene derivatives for the preparation of symmetrical metallocene compounds, due to the electronic effect and steric hindrance effect of the substituents, the cyclopentadiene The reactivity of derivatives, when the reactivity of cyclopentadiene derivatives is low, the probability of side reactions will increase, and dichlorometal compounds will be obtained, resulting in the failure of target reactions and low product yields.

通过反应工艺探索,我们发现当使用甲基锂、乙基锂、甲基氯化镁、乙基氯化镁、丙基氯化镁或二乙基锌等C1-C3烷基金属试剂进行反应时,会增加双烷基金属中间体的稳定性,减少了副反应的发生几率,从而提高目标产物非桥联对称茂金属化合物的产率,扩展了原有方法的底物适用范围。Through the exploration of the reaction process, we found that when C1-C3 alkyl metal reagents such as methyllithium, ethyllithium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride or diethylzinc are used for the reaction, dialkyl The stability of the metal intermediate reduces the probability of side reactions, thereby improving the yield of the target product non-bridged symmetrical metallocene compound, and expanding the scope of substrate application of the original method.

本发明以第四副族金属氯化物、C1-C3烷基金属试剂和环戊二烯衍生物为原料,通过一锅两步反应,在一定温度、氮气或氩气环境下制备非桥联对称茂金属催化剂,具有反应步骤少、操作简便、效率高、底物适用性强等优点。The invention uses the fourth subgroup metal chlorides, C1-C3 alkyl metal reagents and cyclopentadiene derivatives as raw materials to prepare non-bridging symmetric The metallocene catalyst has the advantages of fewer reaction steps, simple operation, high efficiency, and strong substrate applicability.

具体实施方式Detailed ways

下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。本发明实施例所用试剂或仪器或方法指导未注明提供来源者,均为可以通过市购获得的常规产品或可从申请人处获得。Embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. Reagents or instruments or method guides used in the examples of the present invention are not indicated to provide sources, all are commercially available conventional products or can be obtained from the applicant.

发明概述:Summary of the invention:

本发明采用一锅两步反应,在氮气或氩气环境下、有机溶剂中,第一步反应:先在一定加料温度下,将2当量C1-C3烷基金属试剂(RM')加入第四副族金属氯化物与溶剂的混合物中,并在室温下反应制备得到双烷基金属中间体;第二步反应:双烷基金属中间体不用分离纯化,在一定加料温度下,往其混合物中加入2当量的环戊二烯衍生物(Cp'H),并在一定反应温度下反应制备得到非桥联对称茂金属催化剂;合成路线如下述反应式所示:The present invention adopts one-pot two-step reaction, under the environment of nitrogen or argon, in the organic solvent, the first step reaction: first add 2 equivalents of C1-C3 alkyl metal reagent (RM') into the fourth step at a certain feeding temperature In the mixture of subgroup metal chloride and solvent, and react at room temperature to obtain the double alkyl metal intermediate; the second step reaction: the double alkyl metal intermediate does not need to be separated and purified. Add 2 equivalents of cyclopentadiene derivatives (Cp'H), and react at a certain reaction temperature to obtain a non-bridged symmetrical metallocene catalyst; the synthetic route is shown in the following reaction formula:

Figure BDA0003450943420000041
Figure BDA0003450943420000041

本发明解决问题的优选技术方案:The preferred technical scheme of the present invention to solve the problem:

一具体实施方式中,第四副族金属氯化物的通式为MCl4,其中M为元素钛、锆或铪。In a specific embodiment, the general formula of the fourth subgroup metal chloride is MCl 4 , wherein M is the element titanium, zirconium or hafnium.

一具体实施方式中,烷基金属试剂(RM')为烷基锂(RLi)、二烷基锌(R2Zn)、烷基卤化镁(RMgX);其中,R为C1-C3的正构烷基,X为卤素氯、溴或碘。In a specific embodiment, the alkyl metal reagent (RM') is alkyllithium (RLi), dialkylzinc (R 2 Zn ), alkylmagnesium halide (RMgX); wherein, R is the normal structure of C1-C3 Alkyl, X is halogen chlorine, bromine or iodine.

一具体实施方式中,环戊二烯衍生物(Cp'H)为单取代环戊二烯、多甲基取代环戊二烯、多取代茚或芴,结构式如下:In a specific embodiment, the cyclopentadiene derivative (Cp'H) is monosubstituted cyclopentadiene, polymethyl substituted cyclopentadiene, polysubstituted indene or fluorene, and the structural formula is as follows:

Figure BDA0003450943420000051
Figure BDA0003450943420000051

其中,R1为C2-C4碳链的烷基、苄基、三甲基硅基;n为2-5的整数;当R3为氢时,R2可以为C1-C4碳链的烷基、苄基、三甲基硅基;当R2为氢时,R3可以为C1-C4碳链的烷基、苄基、苯基、4-甲基苯基、4-甲氧基苯基;R2和R3可以同时为甲基、乙基;R4可以为氢、甲基、苯基。Wherein, R 1 is C2-C4 carbon chain alkyl, benzyl, trimethylsilyl; n is an integer of 2-5; when R 3 is hydrogen, R 2 can be C1-C4 carbon chain alkyl , benzyl, trimethylsilyl; when R 2 is hydrogen, R 3 can be C1-C4 carbon chain alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl ; R 2 and R 3 can be methyl, ethyl at the same time; R 4 can be hydrogen, methyl, phenyl.

一具体实施方式中,加料温度为-78~0摄氏度,优选为-40~-10摄氏度;反应温度为25~140摄氏度,优选为60~110摄氏度。In a specific embodiment, the feeding temperature is -78 to 0 degrees Celsius, preferably -40 to -10 degrees Celsius; the reaction temperature is 25 to 140 degrees Celsius, preferably 60 to 110 degrees Celsius.

一具体实施方式中,有机溶剂为正己烷、正庚烷、甲苯、邻二甲苯、四氢呋喃、2-甲基四氢呋喃、乙醚或乙二醇二甲醚。In a specific embodiment, the organic solvent is n-hexane, n-heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.

一具体实施方式中,第一步反应时间为4-8小时;第二步反应时间5-10小时。In a specific embodiment, the reaction time of the first step is 4-8 hours; the reaction time of the second step is 5-10 hours.

实施例1Example 1

第一步反应:在氮气环境下,将四氯化锆(2.33g,10mmol)加入到甲苯(80mL)中,在-78摄氏度(加料温度)下,加入甲基锂/2-甲基四氢呋喃溶液(1.0mol/L)(20mL),反应体系升温至室温(25摄氏度),并继续搅拌反应4小时得到二烷基金属中间体。第二步反应:二烷基金属中间体不用分离,在-78摄氏度(加料温度)下,往其混合物中加入五甲基环戊二烯(2.72g,20mmol)。加料完毕,反应体系升温至室温(25摄氏度)后,再加热至110摄氏度(反应温度)继续反应10小时。反应结束后,冷却至室温,进行后处理操作:过滤、减压蒸馏、重结晶、真空干燥,得淡黄色粉末状固体,为目标产物双(五甲基环戊二烯基)二氯化锆1a(3.67g,收率85%)。The first step reaction: under nitrogen atmosphere, zirconium tetrachloride (2.33g, 10mmol) was added to toluene (80mL), and at -78 degrees Celsius (addition temperature), methyllithium/2-methyltetrahydrofuran solution was added (1.0mol/L) (20mL), the reaction system was warmed up to room temperature (25 degrees Celsius), and continued to stir for 4 hours to obtain a dialkyl metal intermediate. The second step reaction: the dialkyl metal intermediate was not separated, and pentamethylcyclopentadiene (2.72 g, 20 mmol) was added to the mixture at -78 degrees Celsius (feeding temperature). After the addition, the reaction system was warmed up to room temperature (25 degrees Celsius), and then heated to 110 degrees Celsius (reaction temperature) to continue the reaction for 10 hours. After the reaction, cool to room temperature and perform post-processing operations: filtration, vacuum distillation, recrystallization, and vacuum drying to obtain a light yellow powdery solid, which is the target product bis(pentamethylcyclopentadienyl)zirconium dichloride 1a (3.67 g, 85% yield).

实施例2Example 2

反应步骤与操作同实施例1,与实施例1不同之处在于,气体环境为氩气。停止反应,经后处理得到目标产物1a(3.76g,收率87%)。The reaction steps and operations are the same as in Example 1, except that the gas environment is argon. The reaction was stopped, and the target product 1a (3.76 g, yield 87%) was obtained after post-treatment.

实施例3Example 3

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为邻二甲苯。停止反应,经后处理得到目标产物1a(3.61g,收率84%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is o-xylene. The reaction was stopped, and the target product 1a (3.61 g, yield 84%) was obtained after post-processing.

实施例4Example 4

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为正庚烷,反应温度98摄氏度。停止反应,经后处理得到目标产物1a(3.76g,收率87%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is n-heptane, and the reaction temperature is 98 degrees Celsius. The reaction was stopped, and the target product 1a (3.76 g, yield 87%) was obtained after post-treatment.

实施例5Example 5

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为正己烷,反应温度69摄氏度。停止反应,经后处理得到目标产物1a(3.33g,收率77%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is n-hexane, and the reaction temperature is 69 degrees Celsius. The reaction was stopped, and the target product 1a (3.33 g, yield 77%) was obtained after post-processing.

实施例6Example 6

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为四氢呋喃,反应温度66摄氏度。停止反应,经后处理得到目标产物1a(3.24g,收率75%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is tetrahydrofuran, and the reaction temperature is 66 degrees Celsius. The reaction was stopped, and the target product 1a (3.24 g, yield 75%) was obtained after post-processing.

实施例7Example 7

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为乙醚,反应温度25摄氏度。停止反应,经后处理得到目标产物1a(1.86g,收率43%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is diethyl ether, and the reaction temperature is 25 degrees Celsius. The reaction was stopped, and the target product 1a (1.86 g, yield 43%) was obtained after post-processing.

实施例8Example 8

反应步骤与操作同实施例1,与实施例1不同之处在于,第一步反应时间为8小时。停止反应,经后处理得到目标产物1a(3.80g,收率88%)。The reaction steps and operations are the same as those in Example 1, except that the reaction time of the first step is 8 hours. The reaction was stopped, and the target product 1a (3.80 g, yield 88%) was obtained after post-processing.

实施例9Example 9

反应步骤与操作同实施例1,与实施例1不同之处在于,第二步反应时间为5小时。停止反应,经后处理得到目标产物1a(2.72g,收率63%)。The reaction steps and operation are the same as in Example 1, except that the second step reaction time is 5 hours. The reaction was stopped, and the target product 1a (2.72 g, yield 63%) was obtained after post-processing.

实施例10Example 10

反应步骤与操作同实施例8,与实施例8不同之处在于,第二步反应时间为5小时。停止反应,经后处理得到目标产物1a(2.94g,收率68%)。The reaction steps and operations are the same as in Example 8, except that the second step reaction time is 5 hours. The reaction was stopped, and the target product 1a (2.94 g, yield 68%) was obtained after post-processing.

实施例11Example 11

反应步骤与操作同实施例1,与实施例1不同之处在于,加料温度为-40摄氏度。停止反应,经后处理得到目标产物1a(3.54g,收率82%)。The reaction steps and operations are the same as in Example 1, except that the feeding temperature is -40 degrees Celsius. The reaction was stopped, and the target product 1a (3.54 g, yield 82%) was obtained after post-processing.

实施例12Example 12

反应步骤与操作同实施例1,与实施例1不同之处在于,加料温度为-10摄氏度。停止反应,经后处理得到目标产物1a(3.19g,收率74%)。The reaction steps and operations are the same as those in Example 1, except that the feeding temperature is -10 degrees Celsius. The reaction was stopped, and the target product 1a (3.19 g, yield 74%) was obtained after post-processing.

实施例13Example 13

反应步骤与操作同实施例1,与实施例1不同之处在于,加料温度为0摄氏度。停止反应,经后处理得到目标产物1a(2.82g,收率65%)。The reaction steps and operations are the same as in Example 1, except that the feeding temperature is 0 degrees Celsius. The reaction was stopped, and the target product 1a (2.82 g, yield 65%) was obtained after post-treatment.

实施例14Example 14

反应步骤与操作同实施例1,与实施例1不同之处在于,反应温度为25摄氏度。停止反应,经后处理得到目标产物1a(1.73g,收率40%)。The reaction steps and operations are the same as in Example 1, except that the reaction temperature is 25 degrees Celsius. The reaction was stopped, and the target product 1a (1.73 g, yield 40%) was obtained after post-processing.

实施例15Example 15

反应步骤与操作同实施例1,与实施例1不同之处在于,反应温度为60摄氏度。停止反应,经后处理得到目标产物1a(3.07g,收率71%)。The reaction steps and operations are the same as in Example 1, except that the reaction temperature is 60 degrees Celsius. The reaction was stopped, and the target product 1a (3.07 g, yield 71%) was obtained after post-processing.

实施例16Example 16

反应步骤与操作同实施例1,与实施例1不同之处在于,反应溶剂为邻二甲苯,反应温度为140摄氏度。停止反应,经后处理得到目标产物1a(3.73g,收率86%)。The reaction steps and operations are the same as in Example 1, except that the reaction solvent is o-xylene, and the reaction temperature is 140 degrees Celsius. The reaction was stopped, and the target product 1a (3.73 g, yield 86%) was obtained after post-processing.

实施例17Example 17

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为二甲基锌/正己烷溶液(1.0mol/L)(20mL)。停止反应,经后处理得到目标产物1a(3.76g,收率87%)。The reaction steps and operations are the same as in Example 1, except that the metal alkyl reagent is dimethyl zinc/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the target product 1a (3.76 g, yield 87%) was obtained after post-treatment.

实施例18Example 18

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为乙基锂/环己烷溶液(0.5mol/L)(40mL)。停止反应,经后处理得到目标产物1a(3.16g,收率73%)。The reaction steps and operations are the same as in Example 1, except that the metal alkyl reagent is ethyl lithium/cyclohexane solution (0.5 mol/L) (40 mL). The reaction was stopped, and the target product 1a (3.16 g, yield 73%) was obtained after post-processing.

实施例19Example 19

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为二乙基锌/正己烷溶液(1.0mol/L)(20mL)。停止反应,经后处理得到目标产物1a(3.02g,收率70%)。The reaction steps and operations are the same as in Example 1, except that the alkyl metal reagent is diethylzinc/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the target product 1a (3.02 g, yield 70%) was obtained after post-processing.

实施例20Example 20

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为正丙基锂/正己烷溶液(1.0mol/L)(20mL)。停止反应,经后处理得到目标产物1a(2.73g,收率63%)。The reaction steps and operations are the same as in Example 1, except that the metal alkyl reagent is n-propyllithium/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the target product 1a (2.73 g, yield 63%) was obtained after post-processing.

实施例21Example 21

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为甲基碘化镁/乙醚溶液(3.0mol/L)(6.68mL)。停止反应,经后处理得到目标产物1a(3.58g,收率83%)。The reaction steps and operations were the same as in Example 1, except that the metal alkyl reagent was methylmagnesium iodide/ether solution (3.0 mol/L) (6.68 mL). The reaction was stopped, and the target product 1a (3.58 g, yield 83%) was obtained after post-processing.

实施例22Example 22

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为甲基氯化镁/四氢呋喃溶液(3.0mol/L)(6.68mL)。停止反应,经后处理得到目标产物1a(3.72g,收率86%)。The reaction steps and operations were the same as in Example 1, except that the alkyl metal reagent was a methylmagnesium chloride/tetrahydrofuran solution (3.0 mol/L) (6.68 mL). The reaction was stopped, and the target product 1a (3.72 g, yield 86%) was obtained after post-processing.

实施例23Example 23

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为甲基溴化镁/四氢呋喃溶液(3.0mol/L)(6.68mL)。停止反应,经后处理得到目标产物1a(3.50g,收率81%)。The reaction steps and operations were the same as in Example 1, except that the alkyl metal reagent was a methylmagnesium bromide/tetrahydrofuran solution (3.0 mol/L) (6.68 mL). The reaction was stopped, and the target product 1a (3.50 g, yield 81%) was obtained after post-processing.

实施例24Example 24

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为乙基溴化镁/四氢呋喃溶液(1.0mol/L)(20mL)。停止反应,经后处理得到目标产物1a(3.02g,收率70%)。The reaction steps and operations were the same as in Example 1, except that the metal alkyl reagent was ethylmagnesium bromide/tetrahydrofuran solution (1.0 mol/L) (20 mL). The reaction was stopped, and the target product 1a (3.02 g, yield 70%) was obtained after post-processing.

实施例25Example 25

反应步骤与操作同实施例1,与实施例1不同之处在于,烷基金属试剂为正丙基氯化镁/乙醚溶液(2.0mol/L)(10mL)。停止反应,经后处理得到目标产物1a(2.68g,收率62%)。The reaction steps and operations are the same as in Example 1, except that the metal alkyl reagent is n-propylmagnesium chloride/ether solution (2.0 mol/L) (10 mL). The reaction was stopped, and the target product 1a (2.68 g, yield 62%) was obtained after post-treatment.

实施例26Example 26

反应步骤与操作同实施例1,与实施例1不同之处在于,第四副族金属氯化物为四氯化钛(1.90g,10mmol)。停止反应,经后处理得到目标产物1b(2.49g,收率64%)。The reaction steps and operations are the same as in Example 1, except that the fourth subgroup metal chloride is titanium tetrachloride (1.90 g, 10 mmol). The reaction was stopped, and the target product 1b (2.49 g, yield 64%) was obtained after post-processing.

实施例27Example 27

反应步骤与操作同实施例1,与实施例1不同之处在于,第四副族金属氯化物为四氯化铪(3.20g,10mmol)。停止反应,经后处理得到目标产物1c(3.80g,收率73%)。The reaction steps and operations are the same as in Example 1, except that the fourth subgroup metal chloride is hafnium tetrachloride (3.20 g, 10 mmol). The reaction was stopped, and the target product 1c (3.80 g, yield 73%) was obtained after post-processing.

实施例28Example 28

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为5-三甲基硅基环戊二烯(2.76g,20mmol)。停止反应,经后处理得到目标产物1d(3.84g,收率88%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 5-trimethylsilylcyclopentadiene (2.76 g, 20 mmol). The reaction was stopped, and the target product 1d (3.84 g, yield 88%) was obtained after post-processing.

实施例29Example 29

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为5-正丁基环戊二烯(2.44g,20mmol)。停止反应,经后处理得到目标产物1e(3.03g,收率75%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 5-n-butylcyclopentadiene (2.44 g, 20 mmol). The reaction was stopped, and the target product 1e (3.03 g, yield 75%) was obtained after post-processing.

实施例30Example 30

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为5-苄基环戊二烯(3.12g,20mmol)。停止反应,经后处理得到目标产物1f(3.44g,收率73%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 5-benzylcyclopentadiene (3.12 g, 20 mmol). The reaction was stopped, and the target product 1f (3.44 g, yield 73%) was obtained after post-processing.

实施例31Example 31

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2-二甲基-1,3-环戊二烯(1.88g,20mmol)。停止反应,经后处理得到目标产物1g(3.03g,收率87%)。The reaction steps and operations are the same as in Example 1, except that the difference from Example 1 is that the cyclopentadiene derivative (Cp'H) is 1,2-dimethyl-1,3-cyclopentadiene (1.88g, 20mmol). The reaction was stopped, and the target product 1g (3.03g, yield 87%) was obtained after post-processing.

实施例32Example 32

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,3-二甲基-1,3-环戊二烯(1.88g,20mmol)。停止反应,经后处理得到目标产物1h(3.06g,收率88%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1,3-dimethyl-1,3-cyclopentadiene (1.88g, 20mmol). The reaction was stopped, and the target product 1h (3.06 g, yield 88%) was obtained after post-processing.

实施例33Example 33

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为芴(3.32g,20mmol)。停止反应,经后处理得到目标产物1i(2.95g,收率60%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is fluorene (3.32 g, 20 mmol). The reaction was stopped, and the target product 1i (2.95 g, yield 60%) was obtained after post-processing.

实施例34Example 34

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为2-苯基茚(3.84g,20mmol)。停止反应,经后处理得到目标产物1j(3.92g,收率72%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 2-phenylindene (3.84 g, 20 mmol). The reaction was stopped, and the target product 1j (3.92 g, yield 72%) was obtained after post-processing.

实施例35Example 35

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1-甲基茚(2.60g,20mmol)。停止反应,经后处理得到目标产物1k(2.94g,收率70%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1-methylindene (2.60 g, 20 mmol). The reaction was stopped, and the target product 1k (2.94 g, yield 70%) was obtained after post-processing.

实施例36Example 36

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1-三甲基硅基茚(3.77g,20mmol)。停止反应,经后处理得到目标产物1l(3.87g,收率72%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1-trimethylsilylindene (3.77 g, 20 mmol). The reaction was stopped, and the target product 1l (3.87 g, yield 72%) was obtained after post-processing.

实施例37Example 37

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2,3-三甲基-1,3-环戊二烯(2.16g,20mmol)。停止反应,经后处理得到目标产物1m(3.12g,收率83%)。The reaction steps and operation are the same as in Example 1, and the difference from Example 1 is that the cyclopentadiene derivative (Cp'H) is 1,2,3-trimethyl-1,3-cyclopentadiene (2.16 g, 20mmol). The reaction was stopped, and the target product 1m (3.12 g, yield 83%) was obtained after post-processing.

实施例38Example 38

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2,4-三甲基-1,3-环戊二烯(2.16g,20mmol)。停止反应,经后处理得到目标产物1n(3.20g,收率85%)。The reaction steps and operation are the same as in Example 1, and the difference from Example 1 is that the cyclopentadiene derivative (Cp'H) is 1,2,4-trimethyl-1,3-cyclopentadiene (2.16 g, 20mmol). The reaction was stopped, and the target product 1n (3.20 g, yield 85%) was obtained after post-processing.

实施例39Example 39

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2,3,4-四甲基-1,3-环戊二烯(2.44g,20mmol)。停止反应,经后处理得到目标产物1o(3.60g,收率89%)。The reaction steps and operation are the same as in Example 1, and the difference from Example 1 is that the cyclopentadiene derivative (Cp'H) is 1,2,3,4-tetramethyl-1,3-cyclopentadiene (2.44g, 20mmol). The reaction was stopped, and the target product 1o (3.60 g, yield 89%) was obtained after post-processing.

实施例40Example 40

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为5-乙基环戊二烯(1.88g,20mmol)。停止反应,经后处理得到目标产物1p(2.51g,收率72%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 5-ethylcyclopentadiene (1.88 g, 20 mmol). The reaction was stopped, and the target product 1p (2.51 g, yield 72%) was obtained after post-processing.

实施例41Example 41

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1-正丁基茚(3.44g,20mmol)。停止反应,经后处理得到目标产物1q(3.58g,收率71%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1-n-butylindene (3.44 g, 20 mmol). The reaction was stopped, and the target product 1q (3.58 g, yield 71%) was obtained after post-processing.

实施例42Example 42

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1-苄基茚(4.12g,20mmol)。停止反应,经后处理得到目标产物1r(3.90g,收率68%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1-benzylindene (4.12 g, 20 mmol). The reaction was stopped, and the target product 1r (3.90 g, yield 68%) was obtained after post-processing.

实施例43Example 43

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为2-正丁基茚(3.44g,20mmol)。停止反应,经后处理得到目标产物1s(3.28g,收率65%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 2-n-butylindene (3.44 g, 20 mmol). The reaction was stopped, and the target product 1s (3.28 g, yield 65%) was obtained after post-processing.

实施例44Example 44

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为2-苄基茚(4.12g,20mmol)。停止反应,经后处理得到目标产物1t(4.01g,收率70%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 2-benzylindene (4.12 g, 20 mmol). The reaction was stopped, and the target product 1t (4.01 g, yield 70%) was obtained after post-processing.

实施例45Example 45

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为2-(4-甲氧基苯基)茚(4.44g,20mmol)。停止反应,经后处理得到目标产物1u(4.54g,收率75%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 2-(4-methoxyphenyl)indene (4.44g, 20mmol). The reaction was stopped, and the target product 1u (4.54 g, yield 75%) was obtained after post-processing.

实施例46Example 46

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为2-(4-甲基苯基)茚(4.12g,20mmol)。停止反应,经后处理得到目标产物1v(4.13g,收率72%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 2-(4-methylphenyl)indene (4.12g, 20mmol). The reaction was stopped, and the target product lv (4.13 g, yield 72%) was obtained after post-processing.

实施例47Example 47

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2-二甲基茚(2.88g,20mmol)。停止反应,经后处理得到目标产物1w(2.92g,收率65%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1,2-dimethylindene (2.88 g, 20 mmol). The reaction was stopped, and the target product 1w (2.92 g, yield 65%) was obtained after post-processing.

实施例48Example 48

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2,5-三甲基茚(3.16g,20mmol)。停止反应,经后处理得到目标产物1x(3.57g,收率75%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1,2,5-trimethylindene (3.16 g, 20 mmol). The reaction was stopped, and the target product 1x (3.57 g, yield 75%) was obtained after post-processing.

实施例49Example 49

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为1,2-二甲基-5-苯基茚(4.41g,20mmol)。停止反应,经后处理得到目标产物1y(3.67g,收率61%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is 1,2-dimethyl-5-phenylindene (4.41 g, 20 mmol). The reaction was stopped, and the target product 1y (3.67g, yield 61%) was obtained after post-processing.

实施例50Example 50

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为环戊二烯(1.32g,20mmol)。停止反应,经后处理得到目标产物1z(2.81g,收率96%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is cyclopentadiene (1.32 g, 20 mmol). The reaction was stopped, and the target product 1z (2.81 g, yield 96%) was obtained after post-processing.

实施例51Example 51

反应步骤与操作同实施例1,与实施例1不同之处在于,环戊二烯衍生物(Cp'H)为茚(2.32g,20mmol)。停止反应,经后处理得到目标产物1aa(2.76g,收率70%)。The reaction steps and operations are the same as in Example 1, except that the cyclopentadiene derivative (Cp'H) is indene (2.32 g, 20 mmol). The reaction was stopped, and the target product 1aa (2.76 g, yield 70%) was obtained after post-processing.

实施例52Example 52

反应步骤与操作同实施例5,与实施例5不同之处在于,环戊二烯衍生物(Cp'H)为茚(2.32g,20mmol)。停止反应,经后处理得到目标产物1aa(3.36g,收率86%)。The reaction steps and operations are the same as in Example 5, except that the cyclopentadiene derivative (Cp'H) is indene (2.32 g, 20 mmol). The reaction was stopped, and the target product 1aa (3.36 g, yield 86%) was obtained after post-processing.

对照例1Comparative example 1

参考文献(Organometallics 2001,20,4132-4134.)所述方法,进行双(五甲基环戊二烯基)二氯化锆1a的制备。反应步骤:第一步反应,在氮气环境下,将四氯化锆(2.33g,10mmol)加入到甲苯(80mL)中,在-78摄氏度下,加入正丁基锂/正己烷溶液(2.5mol/L)(8mL),体系经过8小时缓慢恢复至20摄氏度。第二步反应,反应体系再次冷却至-78摄氏度,往其混合物中加入五甲基环戊二烯(3.40g,25mmol)。加料完毕,反应体系在-78摄氏度下继续搅拌反应1小时,然后恢复至室温并升温至110摄氏度,继续搅拌反应4小时。反应结束后,冷却至室温,进行后处理操作:过滤、减压蒸馏、重结晶、真空干燥,得淡黄色粉末状固体,为目标产物,双(五甲基环戊二烯基)二氯化锆1a(0.86g,收率20%)。The method described in the literature (Organometallics 2001, 20, 4132-4134.) was used to prepare bis(pentamethylcyclopentadienyl)zirconium dichloride 1a. Reaction steps: In the first step of reaction, under nitrogen atmosphere, zirconium tetrachloride (2.33g, 10mmol) was added in toluene (80mL), and at -78 degrees Celsius, n-butyllithium/n-hexane solution (2.5mol /L) (8mL), the system slowly returned to 20 degrees Celsius after 8 hours. In the second step reaction, the reaction system was cooled to -78 degrees Celsius again, and pentamethylcyclopentadiene (3.40 g, 25 mmol) was added to the mixture. After the addition, the reaction system continued to stir and react at -78 degrees Celsius for 1 hour, then returned to room temperature and raised the temperature to 110 degrees Celsius, and continued to stir and react for 4 hours. After the reaction, cool to room temperature and perform post-processing operations: filtration, vacuum distillation, recrystallization, and vacuum drying to obtain a light yellow powdery solid, which is the target product, bis(pentamethylcyclopentadienyl) dichloride Zirconium 1a (0.86 g, 20% yield).

对照例2Comparative example 2

反应步骤与操作同对照例1,与对照例1不同之处在于,反应溶剂为正己烷(80mL),第二步反应在69摄氏度下继续反应4小时。停止反应,经后处理得到目标产物1a(0.43g,收率10%)。The reaction steps and operations are the same as those of Comparative Example 1, except that the reaction solvent is n-hexane (80 mL), and the second step reaction is continued at 69 degrees Celsius for 4 hours. The reaction was stopped, and the target product 1a (0.43 g, yield 10%) was obtained after post-processing.

对照例3Comparative example 3

反应步骤与操作同对照例1,与对照例1不同之处在于,反应溶剂为正己烷(80mL),第二步反应在69摄氏度下继续反应10小时。停止反应,经后处理得到目标产物1a(0.52g,收率12%)。The reaction steps and operations are the same as those of Comparative Example 1, except that the reaction solvent is n-hexane (80 mL), and the second step reaction is continued at 69 degrees Celsius for 10 hours. The reaction was stopped, and the target product 1a (0.52 g, yield 12%) was obtained after post-processing.

对照例4Comparative example 4

反应步骤与操作同对照例1,与对照例1不同之处在于,第二步反应在110摄氏度下继续反应10小时。停止反应,经后处理得到目标产物1a(1.38g,收率32%)。The reaction steps and operations are the same as those of Comparative Example 1, except that the second step reaction was continued at 110 degrees Celsius for 10 hours. The reaction was stopped, and the target product 1a (1.38 g, yield 32%) was obtained after post-processing.

对照例5至对照例6Comparative Example 5 to Comparative Example 6

反应步骤与操作同对照例4,与对照例4不同之处在于使用第四副族金属氯化物不同:Reaction steps and operation are the same as comparative example 4, and difference with comparative example 4 is to use the fourth subgroup metal chloride difference:

对照例Comparative example 第四副族金属氯化物(MCl4)Subgroup IV Metal Chlorides (MCl 4 ) 产物product 收率(%)Yield (%) 55 四氯化钛(1.90g,10mmol)Titanium tetrachloride (1.90g, 10mmol) 1b1b 1313 66 四氯化铪(3.20g,10mmol)Hafnium tetrachloride (3.20g, 10mmol) 1c1c 2828

对照例7至对照例20Comparative Example 7 to Comparative Example 20

反应步骤与操作同对照例4,与对照例4不同之处在于使用环戊二烯衍生物(Cp'H)不同:Reaction steps and operation are the same as Comparative Example 4, and the difference from Comparative Example 4 is that the use of cyclopentadiene derivatives (Cp'H) is different:

对照例Comparative example 环戊二烯衍生物(Cp'H)Cyclopentadiene Derivatives (Cp'H) 产物product 收率(%)Yield (%) 77 5-三甲基硅基环戊二烯(2.76g,20mmol)5-Trimethylsilylcyclopentadiene (2.76g, 20mmol) 1d1d 2727 88 5-苄基环戊二烯(3.12g,20mmol)5-Benzylcyclopentadiene (3.12g, 20mmol) 1f1f 22twenty two 99 1,3-二甲基1,3-环戊二烯(1.88g,20mmol)1,3-Dimethyl-1,3-cyclopentadiene (1.88g, 20mmol) 1h1h 3333 1010 芴(3.32g,20mmol)Fluorene (3.32g, 20mmol) 1i1i 1717 1111 2-苯基茚(3.84g,20mmol)2-Phenylindene (3.84g, 20mmol) 1j1j 3232 1212 1-甲基茚(2.60g,20mmol)1-Methylindene (2.60g, 20mmol) 1k1k 3535 1313 1-三甲基硅基茚(3.77g,20mmol)1-Trimethylsilylindene (3.77g, 20mmol) 1l1l 3333 1414 1,2,4-三甲基1,3-环戊二烯(2.16g,20mmol)1,2,4-Trimethyl-1,3-cyclopentadiene (2.16g, 20mmol) 1n1n 2828 1515 1,2,3,4-四甲基1,3-环戊二烯(2.44g,20mmol)1,2,3,4-Tetramethyl-1,3-cyclopentadiene (2.44g, 20mmol) 1o1o 3333 1616 1-正丁基茚(3.44g,20mmol)1-n-Butylindene (3.44g, 20mmol) 1q1q 2727 1717 1-苄基茚(4.12g,20mmol)1-benzylindene (4.12g, 20mmol) 1r1r 2828 1818 2-正丁基茚(3.44g,20mmol)2-n-Butylindene (3.44g, 20mmol) 1s1s 2525 1919 1,2-二甲基茚(2.88g,20mmol)1,2-Dimethylindene (2.88g, 20mmol) 1w1w 21twenty one 2020 1,2,5-三甲基茚(3.16g,20mmol)1,2,5-Trimethylindene (3.16g, 20mmol) 1x1x 2020

应用例1Application example 1

利用非桥联对称茂金属配合物作为催化剂,可以有效促进1-癸烯发生齐聚反应,得到低黏度聚α-烯烃产物。具体应用例如下:Using the non-bridged symmetrical metallocene complex as a catalyst can effectively promote the oligomerization of 1-decene to obtain a low-viscosity polyα-olefin product. Specific application examples are as follows:

配制茂金属催化剂:称取双(1-甲基茚基)二氯化锆(1k)(13.5mg,0.032mmol)溶解于10ml甲苯溶液中(茂金属用量0.0086mol%),加入6.0ml浓度为1.5M的甲基铝氧烷甲苯溶液(助催化剂)(助催化剂/(茂金属(1k)=281(摩尔比)),搅拌30分钟待用。Preparation of metallocene catalyst: Weigh bis(1-methylindenyl)zirconium dichloride (1k) (13.5mg, 0.032mmol) and dissolve it in 10ml of toluene solution (the amount of metallocene is 0.0086mol%), add 6.0ml concentration of 1.5 M methylaluminoxane toluene solution (cocatalyst) (cocatalyst/(metallocene (1k)=281 (molar ratio)), stirred for 30 minutes and set aside.

聚合反应:将250毫升Schlenk反应瓶抽真空/充氮气置换3次,氮气条件下,加入经过无水无氧处理的1-癸烯(70mL,51.9g,370mmol)。反应体系升温至90摄氏度,15分钟后,加入预先配制好的茂金属催化剂,搅拌下开始反应。所述反应在氮气常压下进行2小时后,采样通过气相色谱内标法分析,原料转化率为99.1%,二聚体选择性为23.4%。停止反应,向体系中加入5%盐酸乙醇溶液(10mL),继续搅拌30分钟淬灭反应,经硅藻土过滤,得到粗产物溶液,减压蒸馏除去溶剂、未反应的1-癸烯和低沸点组分,得到齐聚产物(36.4g),产率70.1%。齐聚产物的氢化在500毫升高压反应釜中进行,加氢催化剂为镍催化剂,反应温度130摄氏度,反应压力4MPa,反应时间4h,经后处理得到茂金属PAO产品,按相应标准测定其运动黏度(100摄氏度)为4.4mm2/s,黏度指数134,倾点-57摄氏度。Polymerization reaction: Vacuumize/inflate a 250ml Schlenk reaction bottle with nitrogen for 3 times, and add 1-decene (70mL, 51.9g, 370mmol) that has been treated with anhydrous and anaerobic conditions under nitrogen. The temperature of the reaction system was raised to 90 degrees Celsius, and after 15 minutes, the pre-prepared metallocene catalyst was added, and the reaction was started under stirring. After the reaction was carried out under nitrogen atmospheric pressure for 2 hours, the samples were analyzed by gas chromatography internal standard method, the conversion rate of raw materials was 99.1%, and the dimer selectivity was 23.4%. Stop the reaction, add 5% hydrochloric acid ethanol solution (10mL) in the system, continue to stir for 30 minutes to quench the reaction, filter through diatomaceous earth to obtain the crude product solution, remove the solvent, unreacted 1-decene and low-pressure distillation Boiling point components, the oligomerized product (36.4 g) was obtained with a yield of 70.1%. The hydrogenation of the oligomerization product is carried out in a 500 ml high-pressure reactor, the hydrogenation catalyst is a nickel catalyst, the reaction temperature is 130 degrees Celsius, the reaction pressure is 4 MPa, and the reaction time is 4 hours. The metallocene PAO product is obtained after post-treatment, and its kinematic viscosity is measured according to the corresponding standard. (100 degrees Celsius) is 4.4mm 2 /s, viscosity index is 134, and pour point is -57 degrees Celsius.

应用例中PAO的各项黏温性能的测试方法如下:The test methods for the viscosity and temperature properties of PAO in the application examples are as follows:

a.石油产品运动黏度测定法和运动黏度计算法:GB/T 265-88a. Petroleum product kinematic viscosity determination method and kinematic viscosity calculation method: GB/T 265-88

b.石油产品黏度指数计算法:GB/T 1995-1998b. Calculation method of viscosity index of petroleum products: GB/T 1995-1998

c.石油产品倾点测定法:GB/T 3535-2006c. Determination of pour point of petroleum products: GB/T 3535-2006

应用例2Application example 2

反应步骤与操作同应用例1,与应用例1不同之处在于,反应中茂金属催化剂为双(五甲基环戊二烯基)二氯化锆(1a),反应结束后,经气相色谱内标法检测,原料转化率98.9%,二聚体选择性29.6%,齐聚产物产率66.2%。经测定,茂金属PAO运动粘度(100摄氏度)为4.1mm2/s,黏度指数135,倾点-54摄氏度。Reaction steps and operation are the same as Application Example 1, and the difference with Application Example 1 is that the metallocene catalyst is two (pentamethylcyclopentadienyl) zirconium dichloride (1a) in the reaction, after the reaction finishes, through gas chromatography As detected by the internal standard method, the conversion rate of raw materials is 98.9%, the selectivity of dimer is 29.6%, and the yield of oligomerization product is 66.2%. After measurement, the metallocene PAO has a kinematic viscosity (100 degrees Celsius) of 4.1 mm 2 /s, a viscosity index of 135, and a pour point of -54 degrees Celsius.

以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or transformations made by those skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention shall be determined by the claims.

Claims (13)

1.一种制备非桥联对称茂金属催化剂的方法,其特征在于,以第四副族金属氯化物、C1-C3烷基金属试剂和环戊二烯衍生物为原料,在氮气或氩气环境下、有机溶剂中反应,通过一锅两步反应获得非桥联对称茂金属催化剂。1. A method for preparing a non-bridged symmetric metallocene catalyst, characterized in that, using the fourth subgroup metal chloride, C1-C3 alkyl metal reagents and cyclopentadiene derivatives as raw materials, in nitrogen or argon Under ambient conditions and in an organic solvent, a non-bridged symmetric metallocene catalyst is obtained through a one-pot two-step reaction. 2.权利要求1所述制备非桥联对称茂金属催化剂的方法,其特征在于,包括:2. the method for preparing non-bridged symmetrical metallocene catalyst described in claim 1, is characterized in that, comprises: (1)先在一定加料温度下,将2当量C1-C3烷基金属试剂加入第四副族金属氯化物与有机溶剂的混合物中,并在室温下反应得混合物;(1) At a certain feed temperature, 2 equivalents of C1-C3 alkyl metal reagents are added to the mixture of the fourth subgroup metal chloride and the organic solvent, and react at room temperature to obtain the mixture; (2)在一定加料温度下,往步骤(1)所得混合物中加入2当量的环戊二烯衍生物,并在一定反应温度下反应。(2) At a certain feed temperature, add 2 equivalents of cyclopentadiene derivatives to the mixture obtained in step (1), and react at a certain reaction temperature. 3.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述第四副族金属氯化物的通式为MCl4,其中M为元素钛、锆、铪。3. The method for preparing a non-bridged symmetrical metallocene catalyst according to claim 2, wherein the general formula of the fourth subgroup metal chloride is MCl 4 , wherein M is the element titanium, zirconium, and hafnium. 4.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述C1-C3烷基金属试剂为RLi、R2Zn或RMgX;其中,R为C1-C3的正构烷基,X为卤素氯、溴或碘。4. The method for preparing non-bridged symmetrical metallocene catalysts according to claim 2, characterized in that, the C1-C3 alkyl metal reagent is RLi, R 2 Zn or RMgX; wherein, R is the normal structure of C1-C3 Alkyl, X is halogen chlorine, bromine or iodine. 5.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述环戊二烯衍生物可选自如下化合物:5. the method for preparing non-bridged symmetrical metallocene catalyst described in claim 2, is characterized in that, described cyclopentadiene derivative can be selected from following compound:
Figure FDA0003450943410000011
Figure FDA0003450943410000011
其中,R1为C2-C4碳链的烷基、苄基、三甲基硅基;n为2-5的整数;当R3为氢时,R2可以为C1-C4碳链的烷基、苄基、三甲基硅基;当R2为氢时,R3可以为C1-C4碳链的烷基、苄基、苯基、4-甲基苯基、4-甲氧基苯基;R2和R3可以同时为甲基、乙基;R4可以为氢、甲基、苯基。Wherein, R 1 is C2-C4 carbon chain alkyl, benzyl, trimethylsilyl; n is an integer of 2-5; when R 3 is hydrogen, R 2 can be C1-C4 carbon chain alkyl , benzyl, trimethylsilyl; when R 2 is hydrogen, R 3 can be C1-C4 carbon chain alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl ; R 2 and R 3 can be methyl, ethyl at the same time; R 4 can be hydrogen, methyl, phenyl.
6.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述一定加料温度为-78~0摄氏度;所述一定反应温度为25~140摄氏度。6. The method for preparing a non-bridging symmetrical metallocene catalyst according to claim 2, characterized in that, the certain feed temperature is -78-0 degrees Celsius; the certain reaction temperature is 25-140 degrees Celsius. 7.权利要求6所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述一定加料温度为-40~-10摄氏度;所述一定反应温度为60~110摄氏度。7. The method for preparing a non-bridged symmetric metallocene catalyst according to claim 6, characterized in that, the certain feed temperature is -40--10 degrees Celsius; the certain reaction temperature is 60-110 degrees Celsius. 8.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,所述有机溶剂为正己烷、正庚烷、甲苯、邻二甲苯、四氢呋喃、2-甲基四氢呋喃、乙醚或乙二醇二甲醚。8. the method for preparing non-bridged symmetrical metallocene catalyst described in claim 2, is characterized in that, described organic solvent is normal hexane, normal heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, ether or Ethylene glycol dimethyl ether. 9.权利要求2所述制备非桥联对称茂金属催化剂的方法,其特征在于,步骤(1)的反应时间为4-8小时;步骤(2)的反应时间5-10小时。9. The method for preparing a non-bridged symmetrical metallocene catalyst according to claim 2, characterized in that, the reaction time of step (1) is 4-8 hours; the reaction time of step (2) is 5-10 hours. 10.权利要求1-9任一项所述方法制备的非桥联对称茂金属催化剂。10. The non-bridged symmetric metallocene catalyst prepared by the method according to any one of claims 1-9. 11.权利要求10所述非桥联对称茂金属催化剂在烯烃聚合反应中的应用。11. The application of the non-bridged symmetrical metallocene catalyst in claim 10 in olefin polymerization. 12.烯烃聚合反应,其特征在于,使用权利要求10所述非桥联对称茂金属催化剂。12. Olefin polymerization, characterized in that the non-bridged symmetric metallocene catalyst according to claim 10 is used. 13.权利要求12所述烯烃聚合反应,其特征在于,所述烯烃聚合反应为1-癸烯聚合反应。13. The olefin polymerization reaction according to claim 12, characterized in that, the olefin polymerization reaction is 1-decene polymerization reaction.
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