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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bridged
metallocene catalyst
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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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Petrochina Co Ltd
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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

Synthesis method of non-bridged symmetrical metallocene catalyst, product and application thereof
Technical Field
The invention relates to a synthesis method of a non-bridged symmetrical metallocene catalyst, a product and application thereof.
Background
Metallocene compounds generally refer to a class of organic complexes consisting of a transition metal or rare earth metal and at least one cyclopentadiene or derivative thereof as ligands. Two identical metallocene rings coordinate to a central metal atom, thus forming a sandwich structure, a so-called non-bridged symmetric dual metallocene catalyst, such as: cp 2 MCl 2 、(Ind) 2 MCl 2 (M is titanium, zirconium, hafnium; cp is cyclopentadienyl; ind is indenyl).
Currently, there are two methods by which non-bridged symmetric metallocene catalysts can be synthesized efficiently. Method 1: reacting cyclopentadiene derivative with strong alkaline compound to generate cyclopentadiene ligand salt, and then reacting the ligand salt with transition metal halide or complex thereof to prepare catalyst; method 2: the preparation method comprises the steps of firstly reacting cyclopentadiene derivative with a strong alkaline compound to generate cyclopentadiene ligand salt, then reacting with trimethylchlorosilane to obtain trimethylsilyl cyclopentadiene derivative, and finally reacting with transition metal halide to obtain the target product.
Although the method can effectively prepare the non-bridged symmetrical metallocene catalyst, the method has the defects of multiple reaction steps, complex operation and the like. Because of the poor solubility of the cyclopentadienyl derivative ligand salt or transition metal halide in the organic solvent, solid or slurry feeds are often required during the reaction, and the reaction is carried out under anhydrous and anaerobic conditions, which further increases the difficulty and safety risks of the reaction operation.
In 2001 Eisch et al (Organometallics 2001,20,4132-4134) reported a novel process for preparing non-bridged symmetrical metallocene compounds. The method adopts a one-pot two-step method, firstly, 2 equivalents of n-butyllithium and zirconium tetrachloride react to obtain dibutyl zirconium dichloride, and then, the dibutyl zirconium dichloride and 2 equivalents of cyclopentadiene react to obtain bis (cyclopentadienyl) zirconium dichloride, and the yield is more than 95 percent. Compared with the traditional method, the process has the advantages of few reaction steps, simple operation, low safety risk and the like. However, in the synthetic process of symmetrical metallocene compounds by using the method, although the process can effectively prepare non-bridged symmetrical metallocene compounds such as bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride, the reaction result is poor and the yield is only 20-35% for preparing non-bridged symmetrical metallocene compounds such as bis (pentamethylcyclopentadienyl) titanium dichloride, bis (2-phenylindenyl) zirconium dichloride, bis (1-methylindenyl) zirconium dichloride, bis (trimethylsilyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride or bis (pentamethylcyclopentadienyl) hafnium dichloride.
Disclosure of Invention
The present invention has been made in order to solve, at least in part, the technical drawbacks existing in the prior art.
As one aspect of the invention, the invention relates to a method for preparing the non-bridged symmetrical metallocene catalyst, which takes fourth subgroup metal chloride, a C1-C3 alkyl metal reagent and cyclopentadiene derivatives as raw materials, and the non-bridged symmetrical metallocene catalyst is obtained through one-pot two-step reaction in an organic solvent under the environment of nitrogen or argon.
In particular, the method of preparing a non-bridged symmetric metallocene catalyst comprises:
(1) Firstly, adding 2 equivalents of C1-C3 alkyl metal reagent into a mixture of fourth subgroup metal chloride and an organic solvent at a certain feeding temperature, and reacting at room temperature to obtain a mixture;
(2) At a certain feeding temperature, 2 equivalents of cyclopentadiene derivative are added to the mixture obtained in the step (1), and the mixture is reacted at a certain reaction temperature.
In one embodiment, the fourth group metal chloride has the formula MCl 4 Wherein M is the elements titanium, zirconium and hafnium.
In one embodiment, the C1-C3 alkyl metal reagent is RLi, R 2 Zn or RMgX; wherein R is C1-C3 normal alkylX is halogen chlorine, bromine or iodine.
In a specific embodiment, the cyclopentadiene derivative may be selected from the following compounds:
Figure BDA0003450943420000031
wherein R is 1 Alkyl with C2-C4 carbon chain, benzyl and trimethylsilyl; n is an integer from 2 to 5; when R is 3 When hydrogen, R 2 Alkyl, benzyl and trimethylsilyl groups with C1-C4 carbon chains can be adopted; when R is 2 When hydrogen, R 3 Alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl which may be C1-C4 carbon chain; r is R 2 And R is 3 Can be methyl and ethyl at the same time; r is R 4 Can be hydrogen, methyl or phenyl.
In a specific embodiment, the certain feeding temperature is-78-0 ℃, preferably-40-10 ℃; the certain reaction temperature is 25-140 ℃, preferably 60-110 ℃.
In one embodiment, the organic solvent is n-hexane, n-heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, or ethylene glycol dimethyl ether.
In a specific embodiment, the reaction time of step (1) is from 4 to 8 hours; the reaction time of the step (2) is 5-10 hours.
As another aspect of the invention, it relates to non-bridged symmetric metallocene catalysts prepared by the above-described methods.
As another aspect of the invention, it relates to the use of the non-bridged symmetric metallocene catalysts described above in olefin polymerization reactions.
As a further aspect of the invention, it relates to olefin polymerization using the non-bridged symmetric metallocene catalyst as described in claim 10. Specifically, the olefin polymerization is a 1-decene polymerization.
The di-n-butyl dichloro metal intermediate obtained in the reaction process is unstable and is easy to decompose into a dichloro metal compound, and the compound cannot continuously react with the cyclopentadiene derivative to obtain a target product. When the polysubstituted cyclopentadiene derivative or the trimethylsilyl cyclopentadiene derivative is used for the symmetrical metallocene compound preparation reaction, the electronic effect and the steric hindrance effect of the substituent affect the reactivity of the cyclopentadiene derivative, and when the reactivity of the cyclopentadiene derivative is lower, the probability of side reaction is increased, the dichloro metal compound is obtained, the target reaction cannot occur, and the product yield is lower.
Through reaction process exploration, when a C1-C3 alkyl metal reagent such as methyl lithium, ethyl lithium, methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride or diethyl zinc is used for reaction, the stability of a dialkyl metal intermediate is increased, the occurrence probability of side reaction is reduced, the yield of a target product non-bridged symmetrical metallocene compound is improved, and the substrate application range of the original method is expanded.
The invention takes the fourth subgroup metal chloride, the C1-C3 alkyl metal reagent and the cyclopentadiene derivative as raw materials, prepares the non-bridged symmetrical metallocene catalyst under the environment of certain temperature, nitrogen or argon through one-pot two-step reaction, and has the advantages of less reaction steps, simple and convenient operation, high efficiency, strong substrate applicability and the like.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus or methods used in the examples of the invention, the instruction not specifying the source of the supply, are all conventional products commercially available or available from the applicant.
Summary of the invention:
the invention adopts one-pot two-step reaction, and in an organic solvent under the nitrogen or argon environment, the first step reaction: firstly, adding 2 equivalents of C1-C3 alkyl metal reagent (RM') into a mixture of fourth subgroup metal chloride and solvent at a certain feeding temperature, and reacting at room temperature to prepare a dialkyl metal intermediate; and the second step of reaction: the dialkyl metal intermediate is not required to be separated and purified, 2 equivalents of cyclopentadiene derivative (Cp' H) is added into the mixture at a certain feeding temperature, and the mixture reacts at a certain reaction temperature to prepare the non-bridged symmetrical metallocene catalyst; the synthetic route is shown in the following reaction formula:
Figure BDA0003450943420000041
the invention solves the problem by adopting the preferable technical scheme:
in one embodiment, the fourth subgroup metal chloride has the formula MCl 4 Wherein M is the element titanium, zirconium or hafnium.
In one embodiment, the metal alkyl reagent (RM') is a lithium alkyl (RLi), zinc dialkyl (R) 2 Zn), alkyl magnesium halides (RMgX); wherein R is C1-C3 normal alkyl, X is halogen chlorine, bromine or iodine.
In one embodiment, the cyclopentadiene derivative (Cp' H) is mono-substituted cyclopentadiene, poly-methyl-substituted cyclopentadiene, poly-substituted indene or fluorene, and has the following structural formula:
Figure BDA0003450943420000051
wherein R is 1 Alkyl with C2-C4 carbon chain, benzyl and trimethylsilyl; n is an integer from 2 to 5; when R is 3 When hydrogen, R 2 Alkyl, benzyl and trimethylsilyl groups with C1-C4 carbon chains can be adopted; when R is 2 When hydrogen, R 3 Alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl which may be C1-C4 carbon chain; r is R 2 And R is 3 Can be methyl and ethyl at the same time; r is R 4 Can be hydrogen, methyl or phenyl.
In a specific embodiment, the feeding temperature is-78-0 ℃, preferably-40-10 ℃; the reaction temperature is 25-140 degrees celsius, preferably 60-110 degrees celsius.
In one embodiment, the organic solvent is n-hexane, n-heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, or ethylene glycol dimethyl ether.
In one embodiment, the first reaction time is from 4 to 8 hours; the second reaction time is 5-10 hours.
Example 1
The first step of reaction: zirconium tetrachloride (2.33 g,10 mmol) was added to toluene (80 mL) under nitrogen, a solution of methyllithium/2-methyltetrahydrofuran (1.0 mol/L) (20 mL) was added at-78 degrees Celsius (addition temperature), the reaction system warmed to room temperature (25 degrees Celsius), and the reaction was continued with stirring for 4 hours to give a dialkylmetal intermediate. And the second step of reaction: to the mixture was added pentamethylcyclopentadiene (2.72 g,20 mmol) at-78 degrees Celsius (feed temperature) without isolation of the dialkyl metal intermediate. After the addition, the reaction system is heated to room temperature (25 ℃) and then heated to 110 ℃ for continuous reaction for 10 hours. After the reaction, cooling to room temperature, and carrying out post-treatment operation: filtration, distillation under reduced pressure, recrystallization, and vacuum drying gave a pale yellow powdery solid, which was the target product bis (pentamethylcyclopentadienyl) zirconium dichloride 1a (3.67 g, yield 85%).
Example 2
The reaction steps and operations were the same as in example 1, except that the gaseous atmosphere was argon. The reaction was stopped, and the desired product 1a (3.76 g, yield 87%) was obtained by working up.
Example 3
The reaction procedure and operation were as in example 1, except that the reaction solvent was o-xylene. The reaction was stopped, and the desired product 1a (3.61 g, yield 84%) was obtained by working up.
Example 4
The reaction procedure and operation were as in example 1, except that the reaction solvent was n-heptane and the reaction temperature was 98 degrees celsius. The reaction was stopped, and the desired product 1a (3.76 g, yield 87%) was obtained by working up.
Example 5
The reaction procedure and operation were as in example 1, except that the reaction solvent was n-hexane and the reaction temperature was 69 degrees celsius. The reaction was stopped, and the desired product 1a (3.33 g, yield 77%) was obtained by working up.
Example 6
The reaction procedure and operation were as in example 1, except that the reaction solvent was tetrahydrofuran and the reaction temperature was 66 ℃. The reaction was stopped, and the desired product 1a (3.24 g, yield 75%) was obtained by working up.
Example 7
The reaction procedure and operation were as in example 1, except that the reaction solvent was diethyl ether at a reaction temperature of 25 degrees celsius, as in example 1. The reaction was stopped, and the desired product 1a (1.86 g, yield 43%) was obtained by working up.
Example 8
The reaction steps and operations were the same as in example 1, except that the reaction time in the first step was 8 hours. The reaction was stopped, and the desired product 1a (3.80 g, yield 88%) was obtained by working up.
Example 9
The reaction step and operation were the same as in example 1, except that the second-step reaction time was 5 hours. The reaction was stopped, and the desired product 1a (2.72 g, yield 63%) was obtained by working up.
Example 10
The reaction step and operation were the same as in example 8, except that the second-step reaction time was 5 hours. The reaction was stopped, and the desired product 1a (2.94 g, yield 68%) was obtained by working up.
Example 11
The reaction procedure and operation were as in example 1, except that the feed temperature was-40 degrees celsius. The reaction was stopped, and the desired product 1a (3.54 g, yield 82%) was obtained by working up.
Example 12
The reaction procedure and operation were as in example 1, except that the feed temperature was-10 degrees celsius. The reaction was stopped, and the desired product 1a (3.19 g, yield 74%) was obtained by working up.
Example 13
The reaction procedure and operation were as in example 1, except that the feed temperature was 0 degrees celsius. The reaction was stopped, and the desired product 1a (2.82 g, yield 65%) was obtained by working up.
Example 14
The reaction steps and operations were the same as in example 1, except that the reaction temperature was 25 degrees celsius. The reaction was stopped, and the desired product 1a (1.73 g, yield 40%) was obtained by working up.
Example 15
The reaction steps and operations were the same as in example 1, except that the reaction temperature was 60 degrees celsius. The reaction was stopped, and the desired product 1a (3.07 g, yield 71%) was obtained by working up.
Example 16
The reaction procedure and operation were as in example 1, except that the reaction solvent was o-xylene and the reaction temperature was 140 degrees celsius. The reaction was stopped, and the desired product 1a (3.73 g, yield 86%) was obtained by working up.
Example 17
The procedure and operation were as in example 1, except that the metal alkyl reagent was a dimethyl zinc/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the desired product 1a (3.76 g, yield 87%) was obtained by working up.
Example 18
The procedure and operation were as in example 1, except that the alkylmetal reagent was an ethyllithium/cyclohexane solution (0.5 mol/L) (40 mL). The reaction was stopped, and the desired product 1a (3.16 g, yield 73%) was obtained by working up.
Example 19
The procedure and operation were as in example 1, except that the metal alkyl reagent was diethyl zinc/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the desired product 1a (3.02 g, yield 70%) was obtained by working up.
Example 20
The procedure and operation were as in example 1, except that the metal alkyl reagent was n-propyllithium/n-hexane solution (1.0 mol/L) (20 mL). The reaction was stopped, and the desired product 1a (2.73 g, yield 63%) was obtained by working up.
Example 21
The procedure was as in example 1, except that the metal alkyl reagent was a solution of methyl magnesium iodide in diethyl ether (3.0 mol/L) (6.68 mL). The reaction was stopped, and the desired product 1a (3.58 g, yield 83%) was obtained by working up.
Example 22
The procedure and operation were as in example 1, except that the metal alkyl reagent was methyl magnesium chloride/tetrahydrofuran solution (3.0 mol/L) (6.68 mL). The reaction was stopped, and the desired product 1a (3.72 g, yield 86%) was obtained by working up.
Example 23
The procedure was as in example 1, except that the metal alkyl was a methyl magnesium bromide/tetrahydrofuran solution (3.0 mol/L) (6.68 mL). The reaction was stopped, and the desired product 1a (3.50 g, yield 81%) was obtained by working up.
Example 24
The procedure was as in example 1, except that the metal alkyl reagent was ethyl magnesium bromide/tetrahydrofuran solution (1.0 mol/L) (20 mL). The reaction was stopped, and the desired product 1a (3.02 g, yield 70%) was obtained by working up.
Example 25
The procedure and operation were as in example 1, except that the metal alkyl reagent was n-propyl magnesium chloride/diethyl ether solution (2.0 mol/L) (10 mL). The reaction was stopped, and the desired product 1a (2.68 g, yield 62%) was obtained by working up.
Example 26
The procedure was as in example 1, except that the fourth group metal chloride was titanium tetrachloride (1.90 g,10 mmol). The reaction was stopped, and the desired product 1b (2.49 g, yield 64%) was obtained by working up.
Example 27
The procedure and operation were as in example 1, except that the fourth group metal chloride was hafnium tetrachloride (3.20 g,10 mmol). The reaction was stopped, and the desired product 1c (3.80 g, yield 73%) was obtained by working up.
Example 28
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 5-trimethylsilylcyclopentadiene (2.76 g,20 mmol). The reaction was stopped, and the desired product 1d (3.84 g, yield 88%) was obtained by working up.
Example 29
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 5-n-butylcyclopentadiene (2.44 g,20 mmol). The reaction was stopped, and the desired product 1e (3.03 g, yield 75%) was obtained by working up.
Example 30
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 5-benzylcyclopentadiene (3.12 g,20 mmol). The reaction was stopped, and the desired product 1f (3.44 g, yield 73%) was obtained by working up.
Example 31
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1, 2-dimethyl-1, 3-cyclopentadiene (1.88 g,20 mmol). The reaction was stopped, and the desired product (1 g, 3.03g, yield 87%) was obtained by working up.
Example 32
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1, 3-dimethyl-1, 3-cyclopentadiene (1.88 g,20 mmol). The reaction was stopped, and the desired product was obtained by working up for 1h (3.06 g, yield 88%).
Example 33
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was fluorene (3.32 g,20 mmol). The reaction was stopped, and the desired product 1i (2.95 g, yield 60%) was obtained by working up.
Example 34
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 2-phenylindene (3.84 g,20 mmol). The reaction was stopped, and the desired product 1j (3.92 g, yield 72%) was obtained by working up.
Example 35
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1-methylindene (2.60 g,20 mmol). The reaction was stopped, and the desired product 1k (2.94 g, yield 70%) was obtained by working up.
Example 36
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1-trimethylsilylindene (3.77 g,20 mmol). The reaction was stopped, and the desired product 1l (3.87 g, yield 72%) was obtained by working up.
Example 37
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1,2, 3-trimethyl-1, 3-cyclopentadiene (2.16 g,20 mmol). The reaction was stopped, and the desired product 1m (3.12 g, yield 83%) was obtained by working up.
Example 38
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1,2, 4-trimethyl-1, 3-cyclopentadiene (2.16 g,20 mmol). The reaction was stopped, and the desired product 1n (3.20 g, yield 85%) was obtained by working up.
Example 39
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene (2.44 g,20 mmol). The reaction was stopped, and the desired product 1o (3.60 g, yield 89%) was obtained by working up.
Example 40
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 5-ethylcyclopentadiene (1.88 g,20 mmol). The reaction was stopped, and the desired product 1p (2.51 g, yield 72%) was obtained by working up.
Example 41
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1-n-butylindene (3.44 g,20 mmol). The reaction was stopped, and the desired product 1q (3.58 g, yield 71%) was obtained by working up.
Example 42
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1-benzylindene (4.12 g,20 mmol). The reaction was stopped, and the desired product 1r (3.90 g, yield 68%) was obtained by working up.
Example 43
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 2-n-butylindene (3.44 g,20 mmol). The reaction was stopped, and the desired product 1s (3.28 g, yield 65%) was obtained by working up.
Example 44
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 2-benzylindene (4.12 g,20 mmol). The reaction was stopped, and the desired product 1t (4.01 g, yield 70%) was obtained by working up.
Example 45
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 2- (4-methoxyphenyl) indene (4.44 g,20 mmol). The reaction was stopped, and the desired product 1u (4.54 g, yield 75%) was obtained by working up.
Example 46
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 2- (4-methylphenyl) indene (4.12 g,20 mmol). The reaction was stopped, and the desired product 1v (4.13 g, yield 72%) was obtained by working up.
Example 47
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1, 2-dimethylindene (2.88 g,20 mmol). The reaction was stopped, and the desired product 1w (2.92 g, yield 65%) was obtained by working up.
Example 48
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1,2, 5-trimethylindene (3.16 g,20 mmol). The reaction was stopped and the desired product 1x (3.57 g, 75% yield) was obtained by work-up.
Example 49
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was 1, 2-dimethyl-5-phenylindene (4.41 g,20 mmol). The reaction was stopped, and the desired product 1y (3.67 g, yield 61%) was obtained by working up.
Example 50
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was cyclopentadiene (1.32 g,20 mmol). The reaction was stopped, and the desired product 1z (2.81 g, yield 96%) was obtained by working up.
Example 51
The procedure was as in example 1, except that the cyclopentadiene derivative (Cp' H) was indene (2.32 g,20 mmol). The reaction was stopped and the desired product 1aa (2.76 g, yield 70%) was obtained by work-up.
Example 52
The procedure was as in example 5, except that the cyclopentadiene derivative (Cp' H) was indene (2.32 g,20 mmol). The reaction was stopped and the desired product 1aa (3.36 g, 86% yield) was obtained by work-up.
Comparative example 1
The preparation of bis (pentamethylcyclopentadienyl) zirconium dichloride 1a is carried out as described in the reference (Organometallics 2001,20,4132-4134). The reaction steps are as follows: in the first reaction step, zirconium tetrachloride (2.33 g,10 mmol) was added to toluene (80 mL) under nitrogen, and at-78 degrees Celsius, an n-butyllithium/n-hexane solution (2.5 mol/L) (8 mL) was added and the system was slowly restored to 20 degrees Celsius over 8 hours. In the second reaction step, the reaction system was again cooled to-78℃and pentamethylcyclopentadiene (3.40 g,25 mmol) was added to the mixture. After the addition, the reaction system is continuously stirred at-78 ℃ for reaction for 1 hour, then the reaction system is recovered to room temperature and is heated to 110 ℃ for continuous stirring for reaction for 4 hours. After the reaction, cooling to room temperature, and carrying out post-treatment operation: filtration, distillation under reduced pressure, recrystallization, and vacuum drying to obtain pale yellow powdery solid, which is the target product, bis (pentamethylcyclopentadienyl) zirconium dichloride 1a (0.86 g, yield 20%).
Comparative example 2
The reaction procedure and procedure were the same as in comparative example 1, except that the reaction solvent was n-hexane (80 mL), and the second reaction was continued at 69℃for 4 hours. The reaction was stopped, and the desired product 1a (0.43 g, yield 10%) was obtained by working up.
Comparative example 3
The reaction procedure and procedure were the same as in comparative example 1, except that the reaction solvent was n-hexane (80 mL), and the second reaction was continued at 69℃for 10 hours. The reaction was stopped, and the desired product 1a (0.52 g, yield 12%) was obtained by working up.
Comparative example 4
The reaction step and procedure were the same as in comparative example 1, except that the second reaction was continued at 110℃for 10 hours, unlike comparative example 1. The reaction was stopped, and the desired product 1a (1.38 g, yield 32%) was obtained by working up.
Comparative examples 5 to 6
The reaction procedure and operation were the same as in comparative example 4, except that a fourth group metal chloride was used, unlike comparative example 4:
comparative example Group IV metal chloride (MCl) 4 ) Product(s) Yield (%)
5 Titanium tetrachloride (1.90 g,10 mmol) 1b 13
6 Hafnium tetrachloride (3.20 g,10 mmol) 1c 28
Comparative examples 7 to 20
The reaction procedure and operation were the same as in comparative example 4, except that a cyclopentadiene derivative (Cp' H) was used as in comparative example 4:
comparative example Cyclopentadiene derivative (Cp' H) Product(s) Yield (%)
7 5-trimethylsilylcyclopentadiene (2.76 g,20 mmol) 1d 27
8 5-Benzylcyclopentadiene (3.12 g,20 mmol) 1f 22
9 1, 3-dimethyl 1, 3-cyclopentadiene (1.88 g,20 mmol) 1h 33
10 Fluorene (3.32 g,20 mmol) 1i 17
11 2-phenylindene (3.84 g,20 mmol) 1j 32
12 1-methylindene (2.60 g,20 mmol) 1k 35
13 1-trimethylsilylindene (3.77 g,20 mmol) 1l 33
14 1,2, 4-trimethyl 1, 3-cyclopentadiene (2.16 g,20 mmol) 1n 28
15 1,2,3, 4-tetramethyl 1, 3-cyclopentadiene (2.44 g,20 mmol) 1o 33
16 1-n-butylindene (3.44 g,20 mmol) 1q 27
17 1-Benzylindane (4.12 g,20 mmol) 1r 28
18 2-n-butylindene (3.44 g,20 mmol) 1s 25
19 1, 2-dimethylindene (2.88 g,20 mmol) 1w 21
20 1,2, 5-trimethylindene (3.16 g,20 mmol) 1x 20
Application example 1
By using the non-bridged symmetrical metallocene complex as a catalyst, oligomerization of 1-decene can be effectively promoted, and a low-viscosity poly-alpha-olefin product can be obtained. Specific applications are as follows:
preparing a metallocene catalyst: bis (1-methylindenyl) zirconium dichloride (1 k) (13.5 mg,0.032 mmol) was weighed and dissolved in 10ml of toluene solution (metallocene amount 0.0086 mol%), 6.0ml of 1.5M methylaluminoxane toluene solution (cocatalyst) (cocatalyst/(metallocene (1 k) =281 (molar ratio)) was added, and stirred for 30 minutes for use.
Polymerization reaction: the 250 ml Schlenk flask was evacuated/replaced 3 times with nitrogen and nitrogenUnder air conditions, anhydrous anaerobic treated 1-decene (70 mL,51.9g,370 mmol) was added. The reaction system is heated to 90 ℃ and after 15 minutes, a pre-prepared metallocene catalyst is added, and the reaction is started under stirring. After the reaction was carried out under nitrogen atmosphere for 2 hours, the raw material conversion was 99.1% and the dimer selectivity was 23.4% by analysis by gas chromatography internal standard method. The reaction was stopped, 5% ethanol hydrochloride (10 mL) was added to the system, stirring was continued for 30 minutes, the reaction was quenched, and filtered through celite to give a crude product solution, which was distilled off under reduced pressure to remove the solvent, unreacted 1-decene and low boiling components, to give an oligomerization product (36.4 g), yield 70.1%. Hydrogenation of oligomerization products is carried out in a 500 ml high-pressure reaction kettle, the hydrogenation catalyst is nickel catalyst, the reaction temperature is 130 ℃, the reaction pressure is 4MPa, the reaction time is 4 hours, the metallocene PAO products are obtained after post treatment, and the kinematic viscosity (100 ℃) is 4.4mm according to the corresponding standard 2 Viscosity index 134, pour point-57 degrees celsius.
The test method for each adhesive temperature performance of PAO in the application example is as follows:
a. petroleum product kinematic viscosity measurement and kinematic viscosity calculation methods: GB/T265-88
b. Petroleum product viscosity index calculation method: GB/T1995-1998
c. Petroleum product pour point determination: GB/T3535-2006
Application example 2
The reaction steps and the operation are the same as in application example 1, and the difference from application example 1 is that the metallocene catalyst in the reaction is bis (pentamethylcyclopentadienyl) zirconium dichloride (1 a), after the reaction is finished, the raw material conversion rate is 98.9%, the dimer selectivity is 29.6% and the oligomerization product yield is 66.2% by gas chromatography internal standard method detection. The metallocene PAO kinematic viscosity (100 ℃ C.) was determined to be 4.1mm 2 Viscosity index 135, pour point-54 degrees celsius.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (13)

1. A method for preparing a non-bridged symmetrical metallocene catalyst is characterized in that fourth subgroup metal chloride, a C1-C3 alkyl metal reagent and a cyclopentadiene derivative are taken as raw materials to react in an organic solvent in a nitrogen or argon environment, and the non-bridged symmetrical metallocene catalyst is obtained through one-pot two-step reaction.
2. The method of preparing a non-bridged symmetrical metallocene catalyst according to claim 1, comprising:
(1) Firstly, adding 2 equivalents of C1-C3 alkyl metal reagent into a mixture of fourth subgroup metal chloride and an organic solvent at a certain feeding temperature, and reacting at room temperature to obtain a mixture;
(2) At a certain feeding temperature, 2 equivalents of cyclopentadiene derivative are added to the mixture obtained in the step (1), and the mixture is reacted at a certain reaction temperature.
3. The process for preparing a non-bridged symmetrical metallocene catalyst as claimed in claim 2, wherein the fourth group metal chloride has the formula MCl 4 Wherein M is the elements titanium, zirconium and hafnium.
4. The process for preparing a non-bridged symmetrical metallocene catalyst as claimed in claim 2, wherein the C1-C3 alkyl metal reagent is RLi, R 2 Zn or RMgX; wherein R is C1-C3 normal alkyl, X is halogen chlorine, bromine or iodine.
5. The method of preparing a non-bridged symmetrical metallocene catalyst according to claim 2, wherein said cyclopentadiene derivative is selected from the group consisting of:
Figure FDA0003450943410000011
wherein R is 1 Alkyl with C2-C4 carbon chain, benzyl and trimethylsilyl; n is an integer from 2 to 5; when R is 3 When hydrogen, R 2 Alkyl, benzyl and trimethylsilyl groups with C1-C4 carbon chains can be adopted; when R is 2 When hydrogen, R 3 Alkyl, benzyl, phenyl, 4-methylphenyl, 4-methoxyphenyl which may be C1-C4 carbon chain; r is R 2 And R is 3 Can be methyl and ethyl at the same time; r is R 4 Can be hydrogen, methyl or phenyl.
6. The method for preparing a non-bridged symmetrical metallocene catalyst as claimed in claim 2, wherein the certain feeding temperature is-78 to 0 ℃; the certain reaction temperature is 25-140 ℃.
7. The method for preparing a non-bridged symmetrical metallocene catalyst according to claim 6, wherein the certain feeding temperature is-40 to-10 ℃; the certain reaction temperature is 60-110 ℃.
8. The method for preparing a non-bridged symmetrical metallocene catalyst according to claim 2, wherein said organic solvent is n-hexane, n-heptane, toluene, o-xylene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.
9. The process for preparing a non-bridged symmetrical metallocene catalyst as claimed in claim 2, wherein the reaction time of step (1) is 4 to 8 hours; the reaction time of the step (2) is 5-10 hours.
10. The non-bridged symmetric metallocene catalyst prepared by the method of any one of claims 1 to 9.
11. Use of the non-bridged symmetric metallocene catalyst of claim 10 in olefin polymerization reactions.
12. Olefin polymerization, characterized in that the non-bridged symmetrical metallocene catalyst as claimed in claim 10 is used.
13. The olefin polymerization of claim 12 wherein said olefin polymerization is a 1-decene polymerization.
CN202111665284.2A 2021-12-31 2021-12-31 Synthesis method of non-bridged symmetrical metallocene catalyst, product and application thereof Pending CN116410237A (en)

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