An olefin polymerization catalyst, its preparation method and application

Abstract

This invention discloses an olefin polymerization catalyst, its preparation method, and its application. The olefin polymerization catalyst is a compound of formula (1) with the structure shown below. This invention uses the compound of formula I as a starting material to synthesize the target product simply and efficiently, effectively reducing the synthesis difficulty of the compound of formula (1). At the same time, this catalyst exhibits high polymerization activity and good comonomer insertion rate in the homopolymerization of ethylene, copolymerization of ethylene and α-olefins, and copolymerization of ethylene and cyclic olefins.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to an olefin polymerization catalyst, its preparation method, and its application. Background Technology

[0002] Transition metal complex-catalyzed olefin polymerization is one of the most important processes in the chemical industry today, representing a significant achievement in organometallic chemistry and catalysis. Among these, metallocene catalysts have received increasing research and application due to their superior catalytic polymerization performance. By altering the ligand structure of metallocene catalysts, the microstructure of polyolefin materials can be controlled, thereby obtaining polymer products with different properties. In the polymerization reaction of ethylene and α-olefins, there exists a unique class of metallocene catalysts with controllable polymer molecular weight, stereoregular structure, and comonomer content—the restricted geometry catalyst. Its structure contains a cyclopentadienyl group (Cp) connected to another ligand via a bridging group, and simultaneously coordinated with the metal center, restricting the relative rotation between the metal center and the cyclopentadienyl ring; hence, it is called CGC, a bridged monometallocene structure. As early as the 1990s, Dow and Exxon first developed CGC-type catalysts, achieving great success in solution polymerization to prepare polyolefin elastomers (McKnight AL, Waymouth R M. Chem Rev, 1998, 98, 2587). Subsequently, an increasing number of companies and institutions have developed various types of metallocene catalysts based on the structure of CGC (Nova Chem IntSA.US6124487[P].1998-03-06; Sumitomo Chemical Company.EP842939[P].1998-05-20; Mitsui Chemicals Inc.WO2006022355[P].2006-03-02; LG Chem Ltd.US7932207B[P].2011-04-26). Compared with traditional Ziegler-Natta catalysts, CGC-type catalysts, when used in conjunction with co-catalysts, exhibit a narrower molecular weight distribution and better comonomer insertion rate in the polymerization reaction of ethylene and α-olefins. However, most metallocene silane-bridged CGC-type catalysts are water- and oxygen-sensitive compounds, posing certain challenges in their synthesis. For example, CN1495188A discloses a substituted indene-type feedstock intermediate, but this intermediate is unstable and easily decomposes. Summary of the Invention

[0003] To solve the above-mentioned technical problems, the first aspect of the present invention provides a compound of formula (1):

[0004]

[0005] A second aspect of the present invention provides a method for preparing a compound of formula (1) above, comprising the following steps:

[0006] Step 1: Using compound I as the starting material, react with silane compound to prepare compound II;

[0007]

[0008] Step 2: The compound of formula II is reacted with titanium trichloride tetrahydrofuran complex (1:3) to prepare compound of formula III;

[0009]

[0010] Step 3: The compound of formula III is reacted with alkyl magnesium chloride to prepare the compound of formula (1);

[0011]

[0012] According to an embodiment of the present invention, the reaction system of the first step includes tetrahydropyrrole and a molecular sieve. The compound of Formula I is free in the reaction system with tetrahydropyrrole as the base and the molecular sieve present, and the freed intermediate reacts with the silane compound.

[0013] According to an embodiment of the present invention, the reaction system of the first step further includes a solvent, for example, the solvent is selected from one or more of tetrahydrofuran, n-hexane and toluene.

[0014] According to an embodiment of the present invention, the reaction system of the first step further includes an alkyl metal reagent, such as n-butyllithium.

[0015] According to an embodiment of the present invention, the silamine compound may be selected from N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine.

[0016] According to an embodiment of the present invention, the molar ratio of the compound of formula I, tetrahydropyrrole, alkyl metal reagent and silane compound is 1:(0.8-1.2):(0.8-1.2):(0.8-1.2), preferably 1:1:1:1.

[0017] According to an embodiment of the present invention, the first step includes: first dissolving the compound of formula I in a solvent, adding a molecular sieve to it to obtain a mixture; adding a tetrahydropyrrole solution dropwise to the mixture to carry out a first reaction; after the reaction is completed, filtering the reaction system, adding an alkyl metal reagent dropwise to the filtrate to carry out a second reaction; and then adding a silane compound solution dropwise to the second reaction system to carry out a third reaction to obtain the compound of formula II.

[0018] According to an embodiment of the present invention, the temperature of the first reaction is 15-40°C, and the reaction time is 10-60 minutes;

[0019] According to an embodiment of the present invention, the temperature of the second reaction is 15-40°C, and the reaction time is 2-6 hours;

[0020] According to an embodiment of the present invention, the temperature of the third reaction is 15-40°C, and the reaction time is 8-20 hours.

[0021] According to an embodiment of the present invention, the alkyl metal reagent and the silane compound solution are added to the system under low temperature conditions, wherein the low temperature conditions refer to a temperature of -70 to -80°C, preferably -78°C.

[0022] According to an embodiment of the present invention, the first step further includes reducing the solvent by concentrating the product obtained from the third reaction under reduced pressure, extracting the residue, collecting the extract, and continuing the concentration under reduced pressure.

[0023] According to an embodiment of the present invention, the reaction system of the second step includes an alkyl metal reagent, lead chloride, and a solvent; preferably, the solvent is selected from n-hexane and / or tetrahydrofuran.

[0024] According to an embodiment of the present invention, the molar ratio of the compound of formula II, the alkyl metal reagent and the titanium trichloride tetrahydrofuran complex (1:3) is 1:(1.8-3):(0.8-1.2), preferably 1:2.4:1.

[0025] According to an embodiment of the present invention, the molar ratio of the compound of formula II to lead chloride is 1:(0.3-0.6), for example 1:0.5.

[0026] According to an embodiment of the present invention, the second step includes: dissolving the compound of formula II in n-hexane, adding an alkyl metal reagent thereto to carry out a first reaction, dissolving the reaction product obtained in tetrahydrofuran, adding titanium trichloride tetrahydrofuran complex (1:3) and lead chloride thereto to carry out a second reaction to obtain the compound of formula III;

[0027] According to an embodiment of the present invention, the temperature of the first reaction is 15-40°C, and the reaction time is 2-6 hours;

[0028] According to an embodiment of the present invention, the temperature of the second reaction is 15-40°C, and the reaction time is 10-30 hours.

[0029] According to an embodiment of the present invention, the second step further includes reducing the solvent by concentrating the product obtained from the second reaction under reduced pressure, extracting the residue, collecting the extract, and continuing the process of concentration under reduced pressure and washing.

[0030] According to an embodiment of the present invention, the third step includes: dissolving the compound of formula III in a solvent (e.g., diethyl ether), adding alkyl magnesium chloride thereto, and reacting to obtain the compound of formula (1);

[0031] For example, the alkyl magnesium chloride is added dropwise to a solution of the compound of formula III in its solution form;

[0032] For example, the reaction temperature is 15–40°C and the reaction time is 1–8 hours.

[0033] According to an embodiment of the present invention, the molar ratio of the compound of formula III and alkyl magnesium chloride is 1:(1.5-3), for example 1:2.2.

[0034] According to an embodiment of the present invention, the alkyl magnesium chloride is selected from C 1-6 Alkyl magnesium chloride, such as C 1-4 Alkyl magnesium chloride, selected as an example, is methyl magnesium chloride or ethyl magnesium chloride. According to an embodiment of the invention, the NMR purity of the compound of formula (1) is greater than 99%.

[0035] The present invention also provides the use of the compound of formula (1) above in olefin polymerization reactions, for example as a catalyst for olefin polymerization reactions.

[0036] According to embodiments of the present invention, the olefin polymerization includes, but is not limited to, homopolymerization of ethylene, copolymerization of ethylene and α-olefins, and copolymerization of ethylene and cyclic olefins.

[0037] According to an embodiment of the present invention, the α-olefin is selected from one or more of 1-butene, 1-pentene, 1-hexene, 1-octene, etc.

[0038] According to an embodiment of the present invention, the compound of formula (1) is obtained by the above preparation method.

[0039] The present invention also provides an olefin polymerization catalytic system, comprising a main catalyst and a co-catalyst, wherein the main catalyst is a compound of formula (1) above, and the co-catalyst is a borate, such as triphenylmethyltetra(pentafluorophenyl)borate.

[0040] Beneficial effects

[0041] This invention provides a method for synthesizing compound of formula (1). By using stable compound of formula I (the raw materials used are in a stable environment and do not deteriorate or decrease in purity during long-term storage) as starting material, the target product is synthesized simply and efficiently, which effectively reduces the difficulty of synthesizing compound of formula (1).

[0042] The compound of formula (1) prepared by the method of the present invention can be used as a catalyst in the homopolymerization of ethylene, the copolymerization of ethylene and α-olefins and ethylene and cyclic olefins. Under the condition of the presence of a co-catalyst, it exhibits high polymerization activity and good comonomer insertion rate, and can be used for the production of polyolefin elastomers. Attached Figure Description

[0043] Figure 1 Here is the synthetic route diagram for the compound of formula (1);

[0044] Figure 2 The 1H NMR spectrum of compound II;

[0045] Figure 3 The 1H NMR spectrum of compound III;

[0046] Figure 4 The NMR spectrum of the compound of formula (1);

[0047] Figure 5 The NMR spectra of compound V of Comparative Example 1 under different conditions show the purity changes.

[0048] Figure 6 The initial NMR spectrum of compound V in Comparative Example 1 is shown. Detailed Implementation

[0049] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0050] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0051] Example 1

[0052]

[0053] N-(tert-butyl)-1-(3-(1-tetrahydropyrrolidinyl)-1H-indenyl)-1,1-dimethylsilylamine (compound II): Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 2.2 g (10 mmol) of 3-tetrahydropyrrolidinyl-1-(1H-indenyl) hydrochloride into the reaction flask and dissolve it in 40 mL of tetrahydrofuran. Then add 1 g of [the solution] to the reaction flask. Molecular sieves were used, and stirring was started. A solution of tetrahydropyrrole (0.7 g, 9.8 mmol) dissolved in tetrahydrofuran (10 mL) was slowly added dropwise to the reaction flask, and the reaction was allowed to proceed for 30 minutes. The reaction system was then filtered, and the filtrate was collected in another reaction flask. Butyllithium (4.4 mL, 10.5 mmol) was added dropwise to the reaction flask at -78 °C, and the system was stirred at room temperature for 4 hours. N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.7 g, 10 mmol) was weighed and dissolved in 10 mL of tetrahydrofuran, and added dropwise to the reaction system at -78 °C. After the addition was complete, the system was stirred at room temperature overnight. The system in the reaction flask was concentrated under reduced pressure to remove the solvent. The residue in the reaction flask was then extracted with 50 mL of n-hexane, filtered, and the filtrate was concentrated under reduced pressure to obtain a dark red oily product (2.6 g, yield 85%). Figure 2 As shown, 1 ¹H NMR (400MHz, CDCl₃, rt): σ -0.14(s, 3H), -0.02(s, 3H), 0.66(s, 1H), 1.21(s, 9H), 1.98(m, 4H), 3.38(m, 4H), 5.36(s, 1H), 7.16(t, J = 7.2Hz, 1H), 7.22(t, J = 7.6Hz, 1H), 7.50(d, J = 7.6Hz, 1H), 7.63(d, J = 7.6Hz, 1H). This confirms the presence of compound II.

[0054]

[0055] Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium (Formula III): Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 3.1 g (10 mmol) of N-(tert-butyl)-1-(3-(1-tetrahydropyrrolyl)-1H-indenyl)-1,1-dimethylsilane (Formula II compound) into the reaction flask and dissolve it in 50 mL of n-hexane. Add 10 mL (24 mmol) of n-butyllithium dropwise to the reaction flask at -20 °C. After stirring the system at room temperature for 4 h, filter the reaction suspension and add the filter cake to another dry and clean 250 mL reaction flask. Then add 50 mL of tetrahydrofuran and stir to dissolve. Weigh 3.7 g (10 mmol) of titanium trichloride tetrahydrofuran complex (1:3) into the system, stir for 1 h, then add lead chloride (2.1 g, 7.5 mmol), and react at room temperature for 20 h. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Extract the residue in the reaction flask with 30 mL of toluene, filter, collect the filtrate, and concentrate under reduced pressure to remove the toluene. Filter the residue in the reaction flask and wash with 50 mL of n-hexane to give a black-green solid product (2.5 g, yield 58%). Figure 3 As shown, 1 ¹H NMR (400MHz, CDCl₃, rt): σ 0.68 (s, 3H), 0.85 (s, 3H), 1.32 (s, 9H), 2.05 (m, 4H), 3.72 (m, 2H), 4.02 (m, 2H), 5.65 (s, 1H), 7.24 (t, J = 8.0 Hz, 1H), 7.32 (t, J = 8.8 Hz, 1H), 7.60 (d, J = 8.8 Hz, 1H), 7.90 (d, J = 8.8 Hz, 1H). This confirms the presence of compound III.

[0056]

[0057] Dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium (compound of formula (1)): Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 3.5 g (8 mmol) of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium into the reaction flask and dissolve it in 80 mL of diethyl ether. Add 5.9 mL (17.6 mmol) of methyl magnesium chloride dropwise to the reaction flask at -20 °C. After stirring the system at room temperature for 4 h, concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 50 mL of n-hexane to the residue in the reaction flask for extraction, filter, collect the filtrate, concentrate under reduced pressure to obtain a dark red viscous oily product (2.9 g, yield 93%), and store it at low temperature in a glove box. Figure 4 As shown, 1 ¹H NMR (400MHz, CDCl₃, rt): σ-0.48(s, 3H), 0.38(s, 3H), 0.41(s, 3H), 0.67(s, 3H), 1.44(s, 9H), 2.05(m, 4H), 3.64(m, 2H), 3.82(m, 2H), 5.35(s, 1H), 6.97(t, J = 7.2Hz, 1H), 7.13(t, J = 6.4Hz, 1H), 7.36(d, J = 8.8Hz, 1H), 7.88(d, J = 8.4Hz, 1H). This proves that compound (1) is obtained.

[0058] Example 2

[0059]

[0060] N-(tert-butyl)-1-(3-(1-tetrahydropyrrolidinyl)-1H-indenyl)-1,1-dimethylsilylamine: Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 4.4 g (20 mmol) of 3-tetrahydropyrrolidinyl-1-(1H-indenyl) hydrochloride into the reaction flask and dissolve it in 50 mL of tetrahydrofuran. Then add 2 g of [the solution] to the reaction flask. Molecular sieves were used, and stirring was started. A solution of tetrahydropyrrole (1.5 g, 19.6 mmol) dissolved in tetrahydrofuran (10 mL) was slowly added dropwise to the reaction flask, and the reaction was allowed to proceed for 30 minutes. The reaction system was then filtered, and the filtrate was collected in another reaction flask. Butyllithium (8.8 mL, 21 mmol) was added dropwise to the reaction flask at -78 °C, and the system was stirred at room temperature for 3 hours. N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (3.3 g, 20 mmol) was weighed and dissolved in 10 mL of tetrahydrofuran, and added dropwise to the reaction system at -78 °C. After the addition was complete, the system was stirred at room temperature overnight. The system in the reaction flask was concentrated under reduced pressure to remove the solvent. The residue in the reaction flask was then extracted with 50 mL of n-hexane, filtered, and the filtrate was concentrated under reduced pressure to obtain a dark red oily product (5.5 g, yield 87%).

[0061]

[0062] Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium: Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 6.3 g (20 mmol) of N-(tert-butyl)-1-(3-(1-tetrahydropyrrolyl)-1H-indenyl)-1,1-dimethylsilane into the reaction flask and dissolve it in 80 mL of n-hexane. Add 18.3 mL (44 mmol) of n-butyllithium dropwise to the reaction flask at -20 °C. After stirring the system at room temperature for 15 h, filter the reaction suspension and add the filter cake to another dry and clean 250 mL reaction flask. Then add 80 mL of tetrahydrofuran and stir to dissolve. A titanium trichloride tetrahydrofuran complex (1:3) (8.9 g, 24 mmol) was weighed and added to the system. After stirring for 2 h, lead chloride (6.6 g, 24 mmol) was added, and the reaction was carried out at room temperature for 20 h. The system in the reaction flask was concentrated under reduced pressure to remove the solvent. The residue in the reaction flask was then extracted with 50 mL of toluene, filtered, and the filtrate was concentrated under reduced pressure to remove the toluene. The residue in the reaction flask was filtered and washed with 50 mL of n-hexane to give a black-green solid product (6.9 g, 80% yield).

[0063]

[0064] Dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium: Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 0.16 g (0.4 mmol) of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium into the reaction flask and dissolve it in 15 mL of diethyl ether. Add 0.25 mL (0.8 mmol) of methyl magnesium chloride dropwise to the reaction flask at -20 °C. After stirring the system at room temperature for 4 h, concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 20 mL of n-hexane to the residue in the reaction flask for extraction, filter and collect the filtrate, concentrate under reduced pressure to obtain a dark red viscous oily product (0.12 g, yield 85%), which is the compound of formula (1), and store it at low temperature in a glove box.

[0065] Example 3

[0066]

[0067] N-(tert-butyl)-1-(3-(1-tetrahydropyrrolidinyl)-1H-indenyl)-1,1-dimethylsilane: Prepare a dry, clean 250 mL reaction flask and place it in a glove box. Weigh 8.9 g (40 mmol) of 3-tetrahydropyrrolidin-1-(1H-indenyl) hydrochloride into the reaction flask and dissolve it in 100 mL of tetrahydrofuran. Then add 4.4 g of [the solution] to the reaction flask. Molecular sieves were used, and stirring was started. A solution of tetrahydropyrrole (2.8 g, 39.2 mmol) dissolved in tetrahydrofuran (15 mL) was slowly added dropwise to the reaction flask, and the reaction was allowed to proceed for 30 minutes. The reaction system was then filtered, and the filtrate was collected in another reaction flask. Butyllithium (17.5 mL, 42 mmol) was added dropwise to the reaction flask at -78 °C, and the system was stirred at room temperature for 2 hours. N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (6.6 g, 40 mmol) was dissolved in 50 mL of tetrahydrofuran and added dropwise to the reaction system at -78 °C. After the addition was complete, the system was stirred at room temperature overnight. The system in the reaction flask was concentrated under reduced pressure to remove the solvent. The residue in the reaction flask was then extracted with 100 mL of n-hexane, filtered, and the filtrate was concentrated under reduced pressure to obtain a dark red oily product (11 g, yield 88%).

[0068]

[0069] Dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium: Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh N-(tert-butyl)-1-(3-(1-tetrahydropyrrolyl)-1H-indenyl)-1,1-dimethylsilane (28.5 g, 90.6 mmol) into the reaction flask and dissolve it in 300 mL of n-hexane. Add n-butyllithium (80 mL, 190.3 mmol) dropwise to the reaction flask at -20 °C. After the system is moved to room temperature and stirred for 2 h, filter the reaction suspension and add the filter cake to another dry and clean 250 mL reaction flask. Then add 50 mL of tetrahydrofuran and stir to dissolve. Weigh out 33.6 g (90.6 mmol) of titanium trichloride tetrahydrofuran complex (1:3) and add it to the system. After stirring for 1 h, add lead chloride (12.6 g, 45.3 mmol) and react at room temperature for 20 h. Concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 200 mL of toluene to the residue in the reaction flask for extraction, filter, collect the filtrate, and concentrate under reduced pressure to remove the toluene.

[0070] The residue in the reaction flask was filtered and washed with 200 mL of n-hexane to give a black-green solid product (31 g, yield 79%).

[0071]

[0072] Dimethyl(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium: Prepare a dry and clean 250 mL reaction flask and place it in a glove box. Weigh 0.86 g (2 mmol) of dichloro(N-(tert-butyl)-1,1-dimethylsilyl-1-((1,2,3,3a,7a-η)-3-(1-tetrahydropyrrolyl)-1H-indenyl)amino)titanium into the reaction flask and dissolve it in 20 mL of diethyl ether. Add 1.5 mL (4.4 mmol) of methyl magnesium chloride dropwise to the reaction flask at -20 °C. After stirring the system at room temperature for 4 h, concentrate the system in the reaction flask under reduced pressure to remove the solvent. Add 30 mL of n-hexane to the residue in the reaction flask for extraction, filter and collect the filtrate, concentrate under reduced pressure to obtain a blackish-red viscous oily product (0.71 g, yield 91%), which is the compound of formula (1), and store it at low temperature in a glove box.

[0073] Comparative Example 1

[0074] The existing technology (Dow Global Technologies, CN1495188A) uses compound V as the raw material to synthesize compound (1). The initial NMR spectrum of compound V is shown below. Figure 6 As shown, the change in NMR purity over time is shown in the figure. Figure 5The NMR spectrum of compound V stored in a glove box at low temperature for one day showed a purity of 98%. After one week of storage in a glove box at room temperature, the purity decreased to 90%. After one week of storage in a Schlenk bottle, the purity decreased by 10% (i.e., reached 88%). It can be seen that compound V has poor stability and is difficult to synthesize compound (1) from it.

[0075]

[0076] Example 4

[0077] Measure 355 mL of n-hexane, 62 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120 °C, and raise the ethylene pressure in the reactor to 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of the polymerization system 450 mL, 1-octene concentration 0.89 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure in the polymerization reactor at 3.5 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening it. Take out the polymer and terminate it using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed to obtain the product, which weighed 65.8g.

[0078] Example 5

[0079] Measure 355 mL of n-hexane, 62 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 140 °C, and raise the ethylene pressure in the reactor to 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of the polymerization system 450 mL, 1-octene concentration 0.89 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure in the polymerization reactor at 3.5 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening it. Take out the polymer and terminate it using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed to obtain the product, which was 34.0 g.

[0080] Example 6

[0081] Measure 355 mL of n-hexane, 62 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 160 °C, and raise the ethylene pressure in the reactor to 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of the polymerization system 450 mL, 1-octene concentration 0.89 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure in the polymerization reactor at 3.5 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening it. Take out the polymer and terminate it using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed to obtain the product, which was 16.2g.

[0082] Example 7

[0083] Measure 263 mL of n-hexane, 154 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120 °C, introduce hydrogen gas at a partial pressure of 0.04 MPa, and introduce ethylene gas at a partial pressure of 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of polymerization system 450 mL, 1-octene concentration 2.20 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure of the polymerization reactor at 3.54 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening the reactor. The polymer was removed and the reaction was terminated using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed, yielding the product, which weighed 69.3 g.

[0084] Example 8

[0085] Measure 263 mL of n-hexane, 154 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120 °C, introduce hydrogen gas at a partial pressure of 0.10 MPa, and introduce ethylene gas at a partial pressure of 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of polymerization system 450 mL, 1-octene concentration 2.20 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure of the polymerization reactor at 3.6 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening the reactor. The polymer was removed and the reaction was terminated using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed, yielding the product, which was 79.4 g.

[0086] Example 9

[0087] Measure 263 mL of n-hexane, 154 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120 °C, introduce hydrogen gas at a partial pressure of 0.20 MPa, and introduce ethylene gas at a partial pressure of 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of polymerization system 450 mL, 1-octene concentration 2.20 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure of the polymerization reactor at 3.7 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening the reactor. The polymer was removed and the reaction was terminated using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed, yielding 90.1 g of the product.

[0088] Example 10

[0089] Measure 263 mL of n-hexane, 154 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120°C, introduce hydrogen gas at a partial pressure of 0.25 MPa, and introduce ethylene gas at a partial pressure of 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of polymerization system 450 mL, 1-octene concentration 2.20 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure of the polymerization reactor at 3.75 MPa. Maintain the polymerization temperature at 120°C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening the reactor. The polymer was removed and the reaction was terminated using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed, yielding the product, which was 104.0 g.

[0090] Example 11

[0091] Measure 263 mL of n-hexane, 154 mL of 1-octene, and 3 mL of triisobutylaluminum (1 mol / L concentration) solution and introduce them into the polymerization reactor at room temperature. Heat the polymerization reactor to 120 °C, introduce hydrogen gas at a partial pressure of 0.42 MPa, and introduce ethylene gas at a partial pressure of 3.5 MPa. Dissolve 5 μmol of the compound of formula (1) prepared in Example 1 as a catalyst and 10 μmol of the co-catalyst triphenylmethyltetra(pentafluorophenyl)borate in 30 mL of toluene to form an activated catalyst solution (total volume of polymerization system 450 mL, 1-octene concentration 2.20 mol / L). Then, quickly inject the activated catalyst solution into the polymerization reactor to initiate polymerization, and keep the ethylene gas switch on to replenish ethylene as needed, thereby maintaining the pressure of the polymerization reactor at 3.92 MPa. Maintain the polymerization temperature at 120 °C. After 60 min, turn off the ethylene gas inlet switch and the reactor heating switch, cool down to room temperature, and then depressurize the polymerization reactor to atmospheric pressure before opening the reactor. The polymer was removed and the reaction was terminated using an acid-alcohol solution (ethanol:hydrochloric acid = 9:1). After filtration, the polymer was dried to constant weight and weighed to obtain the product, which was 95.5 g.

[0092] Table 1 shows the catalyst activity and the polymers obtained in Examples 4-11. It can be seen that the compound of formula (1) can be used as a catalyst for the copolymerization reaction of ethylene and α-olefins. Under the condition of co-catalyst, it exhibits high polymerization activity and good comonomer insertion rate, and polyolefin elastomers are obtained.

[0093] Table 1

[0094]

[0095] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Process for the preparation of a compound of formula (1) characterized in that, The method comprises the following steps: The first step is to dissolve the compound of formula I in a solvent, add molecular sieves to the solution, and obtain a mixture; add a tetrahydropyrrole solution to the mixture to perform a first reaction; filter the reaction system after the first reaction is completed; add an alkyl metal reagent to the filtrate to perform a second reaction; then add a silicon amine compound solution to the second reaction system to perform a third reaction, and obtain a compound of formula II; The silicon amine compound is selected from N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl) amine; The solvent is selected from one or more of tetrahydrofuran, n-hexane and toluene; The temperature of the first reaction is 15-40°C, and the reaction time is 10-60 minutes; The temperature of the second reaction is 15-40°C, and the reaction time is 2-6 hours; The temperature of the third reaction is 15-40°C, and the reaction time is 8-20 hours; The alkyl metal reagent and the silicon amine compound solution are added to the system at a low temperature of -70 to -80°C; Formula I Formula II The second step is to react the compound of formula II with titanium tetrachloride tetrahydrofuran complex (1:3) to obtain a compound of formula III; Formula III The third step is to react the compound of formula III with an alkyl magnesium chloride to obtain the compound of formula (1); （1）。 2. The production method according to claim 1, characterized by, The alkyl metal reagent is n-butyllithium.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the compound of formula I, the tetrahydropyrrole, the alkyl metal reagent and the silicon amine compound is 1:(0.8-1.2):(0.8-1.2):(0.8-1.2).

4. The preparation method according to claim 1, characterized in that, The first step further comprises the following steps: vacuum concentration to remove the solvent, extraction of the residue, collection of the extract, and continuous vacuum concentration and washing.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the compound of formula II, the alkyl metal reagent and titanium tetrachloride tetrahydrofuran complex (1:3) is 1:(1.8-3):(0.8-1.2). And / or, the molar ratio of the compound of formula II and lead chloride is 1:(0.3-0.6).

6. The method of claim 1, wherein, The second step comprises the following steps: dissolving the compound of formula II in n-hexane, adding an alkyl metal reagent to the solution to perform a first reaction, dissolving the reaction product in tetrahydrofuran, adding titanium tetrachloride tetrahydrofuran complex (1:3) and lead chloride to the solution to perform a second reaction, and obtaining the compound of formula III.

7. The production method according to claim 6, characterized by, The second step further comprises the following steps: vacuum concentration to remove the solvent, extraction of the residue, collection of the extract, and continuous vacuum concentration and washing.

8. The method of claim 1, wherein, The third step comprises the following steps: dissolving the compound of formula III in a solvent, adding an alkyl magnesium chloride to the solution to perform a reaction, and obtaining the compound of formula (1).

9. The method of claim 1, wherein, The molar ratio of the compound of formula III and the alkyl magnesium chloride is 1:(1.5-3).

10. The method of claim 1, wherein, The alkylmagnesium chloride is selected from C 1-6 alkylmagnesium chloride.

11. The preparation method according to claim 8, characterized in that, The solvent is diethyl ether.

12. The method of claim 8, wherein, The alkyl magnesium chloride is added to the solution of the compound of formula III in the form of a solution.

13. The preparation method according to claim 8, characterized in that, The temperature of the reaction is 15-40°C, and the reaction time is 1-8 hours.

14. The method of claim 1, wherein, The alkyl magnesium chloride is selected from methyl magnesium chloride or ethyl magnesium chloride.

Images