CN114890987A - Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof - Google Patents

Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof Download PDF

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CN114890987A
CN114890987A CN202210385192.7A CN202210385192A CN114890987A CN 114890987 A CN114890987 A CN 114890987A CN 202210385192 A CN202210385192 A CN 202210385192A CN 114890987 A CN114890987 A CN 114890987A
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lithium
thiophenol
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邓明
郭华
李小冬
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses a thiophenol-thiophene ligand and a preparation method thereof, an olefin polymerization catalyst and a preparation method and application thereof, wherein the ligand has a structure shown as the following,

Description

Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof
The technical field is as follows:
the invention relates to the field of olefin polymerization, in particular to a thiophenol-thiophene ligand and a preparation method thereof, an olefin polymerization catalyst and a preparation method thereof, and application of the catalyst in catalyzing olefin polymerization.
Background art:
olefin materials such as polyethylene and polypropylene are synthetic resin materials which are used in the largest amount in the world, and are widely used in various fields of industrial production and daily life. With the development of the polyolefin industry in China, the traditional bulk polyolefin products such as polypropylene, LDPE and the like are made into China, but the high-end products such as polyolefin elastomer (POE), Cyclic Olefin Copolymer (COC), Olefin Block Copolymer (OBC) and the like still depend on import. The polyolefin is developed to a high-end polyolefin product with more excellent performance and more abundant profit, and is a market demand and a national security strategy demand. In order to realize the development of high-end polyolefin products, the research and development of high-efficiency olefin polymerization catalysts are the soul for realizing the aim.
The IVB group metallocene catalyst (Ti, Zr and Hf) has a definite structure and a single active center, has more excellent performances in polymerization activity, product structure control and the like, successfully opens the era of metallocene polyolefin materials, and is also a way for generating high-end products such as POE, COC, OBC and the like. By designing a ligand structure, the space structure and the central metal charge of the catalyst are further regulated and controlled, so that olefins such as ethylene, propylene, 1-octene, norbornene and the like are coordinately inserted in a specific angle and mode, and the polyolefin material with different compositions, sequence structures and stereo structures can be obtained.
Figure BDA0003593347940000021
The double metallocene catalyst constructed by the ligands of bridging bisindenyl (structure a), bridging cyclopentadiene-fluorenyl (structure b) and the like has unique performance in catalyzing the polymerization of ethylene and alpha-olefin, particularly propylene, and can prepare polypropylene materials with different tactics at high activity; when the single metallocene catalyst (structures c and d) constructed by non-bridged cyclopentadienyl, phenoxy and the like is used for catalyzing the copolymerization of ethylene, alpha-olefin and cycloolefin, the large coordination space of the single metallocene catalyst can realize the high insertion rate of a comonomer; the constrained geometry catalyst (structure e) constructed by taking the bridged amino-cyclopentadienyl ligand as a representative has the characteristic of high activity when ethylene and alpha-olefin are polymerized, especially when POE materials are prepared by copolymerization. Foreign companies such as DOW, Exxon Mobil, Mitsui, Polyplastic, etc. have developed a series of high-end polyolefin materials with metallocene catalysts, resulting in great economic benefits. However, the insertion rate of the metallocene catalyst and the constrained geometry catalyst is too low when the metallocene catalyst and the constrained geometry catalyst catalyze large steric hindrance monomers (such as cycloolefins). When the single metallocene catalyst constructed by the non-bridged cyclopentadienyl and the phenoxy is used for catalyzing the copolymerization of ethylene, alpha-olefin and cycloolefin, the alpha-olefin and the cycloolefin have high insertion rates, but the phenomena of low polymerization activity and poor thermal stability of the catalyst exist.
The invention content is as follows:
the invention aims to provide a thiophenol-thiophene ligand and a preparation method thereof, wherein the ligand can be used as an olefin polymerization catalyst ligand to form a complex with metal for olefin polymerization reaction.
Another object of the present invention is to provide an olefin polymerization catalyst, a method for preparing the same, and use thereof in olefin polymerization.
The catalyst has the characteristics of high catalytic activity, good thermal stability and high comonomer insertion rate, is suitable for ethylene homopolymerization, ethylene/1-octene, ethylene/norbornene and other copolymerization, and can be used for efficiently preparing polyolefin materials such as polyethylene, polyolefin elastomer, cycloolefin copolymer and the like.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a thiophenol-thiophene ligand having the structure:
Figure BDA0003593347940000031
wherein the thiophenol ligand has thienyl L and substituent R, and the substitution position of the thienyl L is any position of ortho-position, meta-position and para-position on the benzene ring; the number n of the substituent groups R is 0-4, and the substitution positions are the rest positions except for the thiophenyl and the thienyl L on the benzene ring.
The thienyl L on the thiophenol ligand is a structure shown as a formula II, and the substituent R 1 、R 2 、R 3 、R 4 The same or different, respectively selected from hydrogen, C1-C12 alkyl, C6-C12 aryl, trimethylsilyl, preferably hydrogen, methyl, ethyl, isopropyl, trimethylsilyl, phenyl;
Figure BDA0003593347940000032
the substituent R of the thiophenol ligand is selected from C1-C12 alkyl, C6-C12 aryl, alkoxy and cyano;
when n is 2 or more, the substituent R may be different in type.
The invention also provides a preparation method of the ligand, which comprises the following steps:
(a) dissolving a halogen-containing thiophenol compound A in an anhydrous solvent under the inert gas atmosphere, mixing the halogen-containing thiophenol compound A with an alkyl lithium compound at a low temperature, and then heating to room temperature for reaction to generate a phase intermediate lithium salt B;
(b) dispersing the lithium salt B in an anhydrous solvent under the atmosphere of inert gas, mixing the lithium salt B with a ketone compound C containing thiophene at a low temperature, and then heating to react to generate a phase intermediate D;
(c) the intermediate D is reduced by active hydrogen to generate the ligand shown in the formula I.
Preferably, in step (a), the molar ratio of the alkyllithium compound to the halogen-containing thiophenol compound a is 1.6 to 2.5: 1;
preferably, in the step (B), the molar ratio of the thiophene-containing ketone compound C to the lithium salt B is 0.8-1.5: 1;
preferably, in step (a), the cryogenic temperature is-78 ℃ to 0 ℃;
preferably, in step (b), the cryogenic temperature is-78 ℃ to 0 ℃;
preferably, in the step (b), the temperature is increased to room temperature to 75 ℃;
preferably, the structural formula of the halogenated thiophenol compound A is as follows:
Figure BDA0003593347940000041
wherein R, n has the same definition as above and Y is halogen;
preferably, the thiophene-containing ketone compound C has the structural formula:
Figure BDA0003593347940000042
wherein R is 1 、R 2 、R 3 、R 4 The definitions are the same as above.
Preferably, the alkyl lithium compound is selected from methyl lithium, ethyl lithium, n-butyl lithium, hexyl lithium, and the like;
preferably, the active hydrogen for reduction in step (c) is selected from one or more of water, alcohols selected from methanol, ethanol or propanol, and acid compounds selected from formic acid, acetic acid or hydrochloric acid.
The reaction scheme of the preparation method of the ligand is shown as follows:
Figure BDA0003593347940000051
an olefin polymerization catalyst having the formula:
Figure BDA0003593347940000052
wherein M is a metal selected from group IVB metals, preferably from titanium, zirconium, hafnium; substituent R, R 1 、R 2 、R 3 、R 4 The number of substitutions n represents the same meaning as that of the above ligand; the X group is selected from halogen, hydrogen or alkane with 1-10 carbon atoms.
Further, the olefin polymerization catalyst of the present invention is selected from the following structures:
Figure BDA0003593347940000053
the invention also provides a preparation method of the olefin polymerization catalyst, which comprises the following steps: dissolving the ligand in an anhydrous solvent under an inert gas atmosphere, mixing the ligand with the catalyst I under a low temperature condition, heating to room temperature for reaction to generate a phase intermediate, washing with a poor solvent, and carrying out a complex reaction on the intermediate and a salt of a metal M to prepare the olefin polymerization catalyst;
preferably, the molar ratio of the ligand to the first catalyst is 1: 1.6-2.5;
preferably, the catalyst one is alkyl lithium or alkali metal hydride, such as methyl lithium, ethyl lithium, butyl lithium, hexyl lithium, etc.;
preferably, the molar ratio of the intermediate to the salt of the metal M is 1: 0.8 to 1.2;
preferably, the mixing temperature of the ligand and the first catalyst is-90 to-20 ℃;
preferably, the poor solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane.
The reaction route of the method is as follows:
Figure BDA0003593347940000061
in addition, the catalyst can also be prepared by directly complexing an intermediate D during ligand synthesis with a salt of the metal M. The method comprises the following steps: dispersing an intermediate D of the ligand in an anhydrous solvent under an inert gas atmosphere, mixing the intermediate D with alkyl lithium under a low-temperature condition, and adding a salt of a metal M to perform a complex reaction to prepare a complex;
preferably, the molar ratio of intermediate D to alkyllithium is 1: 0.8-1.2;
preferably, the alkyl lithium is selected from methyl lithium, ethyl lithium, butyl lithium, hexyl lithium, and the like;
preferably, the molar ratio of the intermediate D to the salt of the metal M is 1: 0.8 to 1.2;
preferably, the mixing temperature of the ligand and the catalyst is-90 to-20 ℃;
preferably, the poor solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane.
The reaction scheme of the method is as follows:
Figure BDA0003593347940000071
the invention also provides a method for catalyzing olefin polymerization reaction by using the catalyst, which takes the catalyst as a main catalyst and one or more of alkyl aluminum, Methyl Aluminoxane (MAO), modified aluminoxane (MMAO), alkyl aluminum chloride and boron reagents as a cocatalyst, and combines the main catalyst and the cocatalyst according to a certain proportion for use, thereby catalyzing olefin polymerization.
Further, the cocatalyst used is MAO, MMAO, triisobutylaluminum, triphenylcarbeniumtetrapentafluorophenyl boron.
Further, the olefins catalytically polymerized are: one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, norbornene, and the like.
Further, the molar ratio of the central metal of the cocatalyst to the central metal of the main catalyst is 40-20000: 1, the polymerization temperature is 0-170 ℃, and the polymerization pressure is 0.1-10 MPa.
Further, the molar equivalent ratio of the added amount of the catalyst to the added amount of the olefin is 1: 1000 to 1000000 molar equivalents.
The invention provides a bridged thiophenol-thienyl double-effect ligand, and an olefin polymerization catalyst constructed by the bridged thiophenol-thienyl double-effect ligand and used for olefin polymerization. Compared with the prior art, the invention has the following beneficial effects: when catalyzing olefin polymerization, particularly butene, hexene, octene, norbornene and ethylene copolymerization, high activity can be maintained, and high insertion of a comonomer can be ensured. The catalyst of the invention can conveniently regulate and control the electronic effect of the catalyst by controlling the electron supply and extraction capability of the substituent group on the thiophenol group, and can conveniently regulate and control the three-dimensional effect of the catalyst by controlling the substitution position on the benzene ring of the thiophenol group, thereby realizing the regulation and control of the olefin polymerization performance of olefin monomers, realizing the high insertion rate of comonomer while keeping high activity, and obtaining polyolefin materials with controllable molecular weight, controllable structure and various performances.
The specific implementation mode is as follows:
in order to better understand the technical solution of the present invention, the following specific examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The concentrations in the following examples are molar concentrations unless otherwise specified.
The raw materials used in the examples are conventional in the art, and the purity specifications used are either analytically or chemically pure.
Raw material source information in examples:
2-bromophenylthiophenol (2-Br-C) 6 H 4 SH)：98％,TCI
2-chloro-6-methylaniline (2-Cl-6-Me-C) 6 H 3 NH 2 )：98％，TCI
2-chloro-5-methylaniline (2-Cl-5-Me-C) 6 H 3 NH 2 ): 98% of Aladdin
2-chloro-4-methylaniline (2-Cl-4-Me-C) 6 H 3 NH 2 ): 98% of Aladdin
2-chloro-3-methoxyaniline (2-Cl-3-MeO-C) 6 H 3 NH 2 ): 98% of Aladdin
2-chloro-4-methoxyaniline (2-Cl-4-MeO-C) 6 H 3 NH 2 ): 98% of Aladdin
2-chloro-4-cyanoaniline (2-Cl-4-CN-C) 6 H 3 NH 2 )：98％，Innochem
3-Chlorobenzene thiol (3-Cl-C) 6 H 4 SH)：98％，Adamas
3- (3-thienyl) propionic acid: 95% Bailingwei science and technology
Sodium nitrite (NaNO) 2 )：Alirich
Potassium ethyl xanthate (O-ethyl dithio potassium carbonate): 95% TCI
Hydrochloric acid: 37% Innochem
N-butyl lithium (n-BuLi): 1.6M Hexane solution, Bailingwei science
Test method
The structures of the synthesized compound and the polymer are measured by a Brucker ARX-400 nuclear magnetic resonance spectrometer and deuterated chloroform (CDCl) 3 ) With deuterated benzene (C) 6 D 6 ) Deuterated 1,1,2, 2-tetrachloroethane (C) 2 D 2 Cl 4 ) As solvent, at room temperature or at 90 ℃.
The molecular weight and molecular weight distribution of the polymer synthesized in the present invention were measured by PL-GPC220 at 150 ℃ using three PLgel 10 μm MIXED-B separation columns in series, 1,2, 4-trichlorobenzene as a solvent. The activity of the catalyst for preparing polymers is calculated according to the following formula:
Figure BDA0003593347940000091
ligand Synthesis example
Example 1 Synthesis of ligand L-1
Figure BDA0003593347940000092
(a) Synthesis of thiophene-containing ketone compound C1
Figure BDA0003593347940000101
Under a nitrogen atmosphere, N-dimethylformamide (2.0mL) and 3- (3-thienyl) propionic acid (512mmol) were dissolved in chloroform (400mL), and after mixing well, thionyl chloride (1024mmol) was added dropwise. After the dropwise addition, the mixture is heated and refluxed for 2 hours, cooled and concentrated in vacuum to obtain an intermediate. The intermediate was dissolved in 1, 2-dichloroethane (600ml), aluminum trichloride (512mmol) was added and stirred at 25 ℃ overnight, then heated under reflux for 2 hours, cooled and added to an aqueous solution of hydrochloric acid (5%). The mixture is extracted by dichloromethane, dried by anhydrous sodium sulfate and evaporated to remove the solvent. Purification by column chromatography (dichloromethane) and spin-drying gave thiophene-containing keto compound C1 as a white powder (yield: 80%).
1 H-NMR(C6D6):7.27-7.23ppm(1H),7.08-7.06ppm(1H),2.67-2.63ppm(2H),2.59-2.55ppm(2H)。
(b) Synthesis of 2-bromophenylthiophenol lithium salt
2-bromophenylthiol (80mmol) was dissolved in 200ml of anhydrous THF under a nitrogen atmosphere, n-butyllithium (138mmol) was added dropwise at 0 ℃ and gradually warmed to room temperature, stirred at room temperature overnight, filtered, and washed three times with anhydrous n-hexane to give a lithium salt of thiophenol (yield: 79%).
(c) Synthesis of ligand L-1
The resulting lithium salt (60mmol) was dispersed in 60ml of anhydrous toluene under a nitrogen atmosphere and cooled to-35 ℃. Thiophene-containing ketone compound C1(64mmol) was dissolved in 40ml of anhydrous toluene, cooled to-35 ℃, added dropwise to a lithium salt of thiophenol, stirred overnight, and then heated to 70 ℃ for reaction for 4 h. After cooling to room temperature, the mixture was quenched by addition of a saturated solution of 40ml ammonium chloride. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and further purified by column chromatography to give ligand L-1 (yield 52%).
1 H-NMR(CDCl 3 ):7.55-7.51ppm(1H),7.41-7.32ppm(2H),7.21-7.12ppm(3H),6.96-6.92ppm(1H),6.39-6.35ppm(1H),3.82-3.78ppm(1H),3.58-3.56ppm(1H)。
Example 2 Synthesis of ligand L-2
Figure BDA0003593347940000111
(a) Synthesis of 2-chloro-6-methylthiophenol
Sodium nitrite (293mmol) was dissolved in water (100mL) at low temperature of-10 ℃ and then added dropwise to a solution of 2-chloro-6-methylaniline (245mmol) in hydrochloric acid (3mol/L,200mL) and, after completion of the addition, the reaction was continued at-10 ℃ for 1 hour. The reaction solution was then heated to 80 ℃ and an aqueous solution of potassium ethylxanthate (414mmol, dissolved in 120mL of water) was added dropwise to the reaction solution. After 1h of reaction, it was cooled to room temperature, and the organic layer was washed with saturated aqueous sodium bicarbonate solution and water. The organic phase was then added portionwise to KOH solution (1220mmol, dissolved in 52mL of water and 280mL of ethanol) and heated at reflux for 21 h. The reaction was cooled to 0 ℃, diluted with ice water (500mL), adjusted to pH 2 with hydrochloric acid, extracted with ethyl acetate, the organic phase collected, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and the solvent removed by spin-drying to give 2-chloro-6-methylphenylthiophenol (80%).
(b) Synthesis of 2-chloro-6-methylthiophenol lithium salt
2-chloro-6-methylphenylthiophenol (50mmol) was dissolved in 100ml of anhydrous THF under a nitrogen atmosphere, 100mmol of n-butyllithium was added dropwise at-45 ℃ gradually to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to obtain a lithium salt of thiophenol (yield: 89%).
(c) Synthesis of ligand L-2
The resulting lithium salt (33mmol) was dissolved in 60ml of anhydrous toluene under a nitrogen atmosphere and cooled to-35 ℃. The thiophene-containing ketone compound C1(30mmol) obtained in example 1 was dissolved in 40ml of anhydrous toluene, cooled to-35 ℃, added dropwise to a lithium salt of thiophenol, stirred overnight, and then heated to 70 ℃ to react for 4 h. After cooling, the mixture was quenched with 60ml of a saturated solution of ammonium chloride. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and further purified by column chromatography to give ligand L-2 (yield 82%).
1H-NMR(CDCl 3 ):7.54-7.51ppm(1H),7.28-7.22ppm(1H),7.13-7.10ppm(1H),7.01-6.91ppm(2H),6.37-6.34ppm(1H),3.85-3.82ppm(1H)，3.02ppm(1H)，2.31-2.29ppm(3H)。
Example 3 Synthesis of ligand L-3
Figure BDA0003593347940000121
(a) Preparation of 2-chloro-4-methylthiophenol
Sodium nitrite (293mmol) was dissolved in water (100mL) at low temperature of-10 ℃ and then added dropwise to a solution of 2-chloro-4-methylaniline (245mmol) in hydrochloric acid (3mol/L,200mL) and, after completion of the addition, the reaction was continued at-10 ℃ for 1 hour. The reaction solution was then heated to 80 ℃ and an aqueous solution of potassium ethylxanthate (414mmol, dissolved in 120mL of water) was added dropwise to the reaction solution. After 1h of reaction, cool to room temperature and wash the organic layer with saturated aqueous sodium bicarbonate and water. The organic phase was then added portionwise to KOH solution (1220mmol, dissolved in 52mL of water and 280mL of ethanol) and heated at reflux for 21 h. The reaction was cooled to 0 ℃, diluted with ice water (500mL), adjusted to pH 2 with hydrochloric acid, extracted with ethyl acetate, the organic phase collected, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and the solvent removed by spin-drying to give 2-chloro-4-methylphenylthiophenol (78%).
(b) Preparation of lithium 2-chloro-4-methylthiophenol salt
2-chloro-4-methylphenylthiophenol (60mmol) was dissolved in 150ml of anhydrous THF under a nitrogen atmosphere, n-butyllithium (120mmol) was added dropwise at-78 deg.C, gradually warmed to room temperature, stirred at room temperature overnight, filtered, and washed three times with anhydrous n-hexane to obtain a lithium salt of thiophenol (yield: 92%).
(c) Synthesis of ligand L-3
The resulting lithium salt (30mmol) was dissolved in 180ml of anhydrous toluene under a nitrogen atmosphere and cooled to-35 ℃. The thiophene-containing ketone compound C1(45mmol) obtained in example 1 was dissolved in 120ml of anhydrous toluene, cooled to-35 deg.C, added dropwise to a lithium salt of thiophenol, stirred overnight, and then heated to 70 deg.C to react for 4 h. After cooling, the mixture was quenched with 60ml of a saturated solution of ammonium chloride. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and further purified by column chromatography to give ligand L-2 (yield 54%). 1H-NMR (CDCl) 3 ):7.75-7.71ppm(1H),7.55-7.51ppm(1H),7.13-6.94ppm(3H),6.39-6.37ppm(1H),3.84-3.81ppm(1H)，3.56ppm(1H)，2.31-2.29ppm(3H)。
Example 4-8 Synthesis of ligands L-4 to 8
In examples 4 to 8, the thiophene-containing ketone compound C1 was prepared according to the method of example 1, and the halogenated thiol precursor was prepared by exactly the same method and ratio as those for the synthesis of 2-chloro-6-methylphenylthiophenol in example 2, except that the precursor was used. The synthesis of the ligand L-4-8 in the embodiment 4-8 adopts the same preparation method and raw material ratio as the ligand L-2 in the embodiment 2, and the difference is that the adopted halogenated thiophenol precursors or thiophene-containing ketone compounds are different, and the specific selection type is shown in Table 1.
TABLE 1 Synthesis of ligands 4-8
Figure BDA0003593347940000141
Catalyst Synthesis example
Example 9 preparation of catalyst Cat l
Figure BDA0003593347940000142
(a) Ligand L-1(20mmol) prepared in example 1 was dissolved in 50ml of anhydrous THF under a nitrogen atmosphere, n-butyllithium (50mmol) was added thereto at-78 deg.C, gradually warmed to room temperature, stirred at room temperature overnight, filtered, and washed three times with anhydrous n-hexane to give a lithium salt of ligand L-1 (yield: 96%).
(b) The lithium salt (15mmol) from step (a) and titanium tetrachloride (16mmol) were added to 50ml of anhydrous toluene at-45 ℃ and then slowly returned to room temperature and stirred for 12 hours. Lithium chloride was removed by filtration. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give catalyst Cat 1 in 81% yield.
The catalyst Cat 1 is subjected to nuclear magnetic characterization, and the results are as follows: 1 H-NMR(C 6 D 6 ):7.58ppm(1H),7.36-7.27ppm(3H),7.08-6.98ppm(2H),6.31-6.23ppm(2H)。
example 10 preparation of catalyst Cat 2
Figure BDA0003593347940000151
(a) Ligand L-2(20mmol) prepared in example 2 was dissolved in 50ml of anhydrous THF under a nitrogen atmosphere, n-butyllithium (50mmol) was added at-78 deg.C, gradually warmed to room temperature, stirred at room temperature overnight, filtered, and washed three times with anhydrous n-hexane to give a lithium salt of ligand L-2 (yield: 96%).
(b) The lithium salt (15mmol) from step (a) and titanium tetrachloride (15mmol) were added to 50ml of anhydrous toluene at-45 ℃ and then slowly returned to room temperature and stirred for 12 hours. Lithium chloride was removed by filtration. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give catalyst Cat 2 in 83% yield. 1 H-NMR(C 6 D 6 ):7.54-7.49ppm(2H),7.28-7.18ppm(2H),7.01-6.98ppm(H),
6.31-6.23ppm(2H),2.34-2.30ppm(3H)。
Example 11 preparation of catalyst Cat 3
Figure BDA0003593347940000152
(a) Ligand L-3(20mmol) prepared in example 3 was dissolved in 50ml of anhydrous THF under a nitrogen atmosphere, n-butyllithium (50mmol) was added thereto at-78 deg.C, gradually warmed to room temperature, stirred at room temperature overnight, filtered, and washed three times with anhydrous n-hexane to give a lithium salt of ligand L-2 (yield: 95%).
(b) The lithium salt (15mmol) from step (a) and titanium tetrachloride (15mmol) were added to 50ml of anhydrous toluene at-45 ℃ and then slowly returned to room temperature and stirred for 12 hours. Lithium chloride was removed by filtration. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give catalyst Cat 3 in 80% yield. 1 H-NMR(C 6 D 6 ):7.65-7.61ppm(1H),7.33-7.29ppm(1H),7.19ppm(1H),7.03-6.98ppm(2H),6.31-6.23ppm(2H)。
Examples 12 to 17, preparation of catalysts Cat 4 to 7, Cat 11 to 12
Figure BDA0003593347940000161
Examples 12-17 catalysts were prepared using exactly the same procedure and formulation as in example 10, except that the ligand used was different from the halide of metal M; see table 2 for specific selection.
TABLE 2 preparation of catalysts C3-C6, C8-C14
Examples Catalyst and process for preparing same Ligands Metal salt Yield of
12 Cat 4 L-4 TiCl4 84％
13 Cat 5 L-5 TiCl4 82％
14 Cat 6 L-6 TiCl4 79％
15 Cat 7 L-7 TiCl4 89％
16 Cat 11 L-8 TiCl4 66％
17 Cat 12 L-8 ZrCl4 78％
Example 18 preparation of catalyst Cat 8
Figure BDA0003593347940000162
Catalyst Cat 1 was prepared in the same manner as in example 9, and catalyst Cat 8 was obtained by dissolving prepared catalyst Cat 1(20mmol) in 50ml of anhydrous toluene under a nitrogen atmosphere, adding methylmagnesium bromide (20mmol) at-78 ℃, gradually raising the temperature to room temperature, stirring overnight at room temperature, filtering to remove magnesium salts, removing the toluene solvent under reduced pressure, and washing three times with n-hexane (yield: 96%). 1 H-NMR(C 6 D 6 ):7.56ppm(1H),7.36-7.27ppm(3H),7.08-6.98ppm(2H),6.33-6.25ppm(2H),0.32ppm(6H)。
Example 19 preparation of catalyst Cat 9
Figure BDA0003593347940000171
This example differs from example 18 mainly in that catalyst Cat 1 was replaced with catalyst Cat 2 prepared by the same method as in example 10.
Cat 9: 1 H-NMR(C 6 D 6 ):7.54-7.49ppm(2H),7.26-7.18ppm(2H),7.08-6.98ppm(1H),6.31-6.23ppm(2H),2.34ppm(3H),0.29ppm(6H)。
Example 20 preparation of catalyst Cat 10
Figure BDA0003593347940000172
This example differs from example 18 mainly in that catalyst Cat 1 was replaced with catalyst Cat 6 prepared by the same method as in example 14.
Cat 10: 1 H-NMR(C 6 D 6 ):7.58ppm(1H),7.36ppm(1H),7.20ppm(1H),7.08-6.98ppm(2H),6.33-6.25ppm(2H),3.90ppm(3H),0.27ppm(6H)。
Olefin polymerization
Example 21 Cat 1 catalyzed ethylene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. Mu. mol of Cat 1 were added, followed by additional vacuum and 3 replacements with ethylene. 100ml of toluene was injected by syringe, and 3.4ml of methylaluminoxane (MAO,1.46M in toluene) was added thereto so that Al/M became 1250. The reaction was stirred vigorously at 130 ℃ for l0min, maintaining an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 2126 kg. mol-1 (M). h-1, polymer weight average molecular weight: 752kg mol -1 ,Mw/Mn＝2.7。
Example 22 Cat 2 catalyzed ethylene-propylene polymerization
A250 ml stainless steel autoclave equipped with stirring was continuously dried at 130 ℃ for 6 hoursVacuum was applied while hot and replaced with nitrogen 3 times, and 5. mu. mol of Cat 2 was added. Ethylene-propylene was mixed at a ratio of 1: 2 in a gas mixing tank, and then replacing the reaction kettle for 3 times by using ethylene-propylene mixed gas. 100ml of toluene was injected into the flask by means of a syringe, and 3.4ml of methylaluminoxane (MAO,1.46M in toluene) was further added to the flask so that Al/M was 1000. The reaction was vigorously stirred at 40 ℃ for 10min while maintaining the mixed gas pressure of 4 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 675 kg. mol-1 (M). h -1 Polymer weight average molecular weight: 75 kg. mol-1, Mw/Mn 2.9, propylene insertion 53 mol%.
Example 23 Cat 3 catalyzed butene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. 5. mu. mol Cat 3 were added, followed by additional vacuum and 3-fold replacement with butene. 100ml of toluene was injected by syringe, and 1.7ml of methylaluminoxane (MAO,1.46M in toluene) was added thereto so that Al/M became 500. The reaction was stirred vigorously at 170 ℃ for 10min while maintaining a butene pressure of 8 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 651 kg. mol-1 (M). h-1. Polymer weight average molecular weight: 78 kg. mol-1, Mw/Mn 2.4.
Example 24 Cat 4 catalyzed octene polymerization
A1000 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. The kettle temperature was lowered to 50 ℃ and 1. mu. mol Cat 4 was added, 400ml of toluene was injected using a syringe, and 3.4ml of methylaluminoxane (MAO,1.46M in toluene) was added to make Al/M5000. 240ml of octene were then added and the reaction stirred vigorously for 10 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 195 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 65 kg. mol-1, Mw/Mn 2.3.
Example 25 Cat 5 catalyzed octene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. The pot temperature was lowered to 50 ℃ and 5. mu. mol Cat 5 was added, 100ml of toluene was injected with a syringe, and 10ml of modified methylaluminoxane (MMAO,1.50M in toluene) was added to make Al/M3000. Then 20ml of octene was added and the reaction stirred vigorously for 10 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 395kg mol-1 (M). h -1 . Polymer weight average molecular weight: 75 kg. mol-1, Mw/Mn 2.6.
Example 26 Cat 7 catalyzed ethylene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. Mu. mol of Cat 7 were added, followed by additional vacuum and 3 replacements with ethylene. 100ml of toluene was injected by syringe, and 3.3ml of modified methylaluminoxane (MAO,1.50M in toluene) was added to make Al/M5000. The reaction was vigorously stirred at 150 ℃ for 30min while maintaining an ethylene pressure of 20 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, and vacuum drying to constant weight. Polymerization Activity: 3790 kg. mol-1 (M). h -1 Polymer weight average molecular weight: 195 kg. mol-1, Mw/Mn 3.1.
Example 27 Cat 8 catalyzed ethylene/norbornene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. 5. mu. mol Cat 8 were added, followed by additional vacuum and 3 replacements with ethylene. 100ml of a 2mol/L norbornene-toluene solution were injected by means of a syringe. 1.7ml of methylaluminoxane (MAO,1.46M in toluene) was added thereto so that Al/M became 500. The reaction was stirred vigorously at 90 ℃ for 10min while maintaining an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 9710 kg. mol-1 (M). h-1. Polymer weight average molecular weight: 175kg mol -1 Mw/Mn of 2.3, lowerThe insertion rate of the bornylene is 54 mol%.
Example 28 Cat 8 catalyzed ethylene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. 100ml of toluene and 0.2mmol of triisobutylaluminum were injected by syringe, and 5. mu. mol of Cat 7 and 10. mu. mmol of triphenylcarbeniumtetrakispentafluorophenylboron Ph were added 3 CB(C 6 F 5 ) 4 Mixing and adding. The reaction was stirred vigorously at 150 ℃ for 5min while maintaining ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 4460 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 142 kg. mol-1, Mw/Mn 3.1.
Example 29 Cat 9 catalyzed ethylene/norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. Then, vacuum was applied and ethylene was substituted 3 times. 100ml of a 2mol/L norbornene-toluene solution was injected by a syringe, and 1.5ml of modified methylaluminoxane (MMAO,1.98M solution of IsoPar-E) was added thereto. Then 5. mu. mol Cat 9 was added thereto, and the mixture was reacted at 50 ℃ under an ethylene pressure of 5atm with vigorous stirring for 2 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 6550 kg. mol-1 (M). h-1. Polymer weight average molecular weight: 98kg mol -1 Mw/Mn was 2.7, and the norbornene insertion rate was 53 mol%.
Example 30 Cat 10 catalysis of ethylene/norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen, and then further evacuated and replaced 3 times with ethylene. 100ml of a 5mol/L norbornene-toluene solution was injected by a syringe, and 6ml of modified methylaluminoxane (MMAO,1.98M solution of IsoPar-E) was added thereto. 5 μmol of Cat 12 was injected at 90 ℃ and the ethylene pressure was maintained at 5atm, and the reaction was vigorously stirred for 3 min. Acidifying with 5% hydrochloric acidNeutralizing the reaction solution with ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 8550 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 148kg mol -1 Mw/Mn was 2.6 and the norbornene insertion rate was 66 mol%.
Example 31 Cat 11 catalyzed ethylene/norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen, and then further evacuated and replaced 3 times with ethylene. 100ml of a 2mol/L norbornene-toluene solution was injected by syringe, and 4ml of modified methylaluminoxane (MMAO,1.98M solution of IsoPar-E) was added thereto. At 90 ℃, 5 μmol of Cat 11 was injected, ethylene pressure of 5atm was maintained, and the reaction was vigorously stirred for 5 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 6480 kg/mol-1 (M). h -1 . Polymer weight average molecular weight: 173kg mol -1 Mw/Mn was 2.5, and the norbornene insertion rate was 57 mol%.
Example 32 Cat 12 catalyzed ethylene/1-hexene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen and 3 times with ethylene. 150ml of toluene and 90ml of 1-hexene were injected by syringe, the temperature in the vessel was heated to 90 ℃ and 3.4ml of methylaluminoxane (MAO,1.46M in toluene) was added. 5. mu. mol Cat 12 was added and the reaction was stirred vigorously for 10min while maintaining ethylene pressure at 20 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 7580 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 1750kg mol -1 Mw/Mn is 2.5, and the insertion rate of 1-hexene is 19 mol%.
Example 33 Cat 1 catalyzed ethylene/1-hexene polymerization
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen and 3 times with ethylene. By usingA syringe was charged with 150ml of toluene, 90ml of 1-hexene, the internal temperature was heated to 90 ℃ and 3.4ml of methylaluminoxane (MAO,1.46M in toluene) was added. 5. mu. mol Cat 1 was added, and the reaction was stirred vigorously for 10min while maintaining the ethylene pressure at 30 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 14580kg mol-1 (M). h -1 . Polymer weight average molecular weight: 2500kg mol -1 Mw/Mn is 2.5, and the insertion rate of 1-hexene is 18 mol%.
Example 34 Cat 1 catalyzed ethylene norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. Then, vacuum was applied and ethylene was substituted 3 times. 100ml of a 5mol/L norbornene-toluene solution and 6.8ml of methylaluminoxane (MAO,1.46M in toluene) were introduced by means of a syringe. At 70 deg.C, 2. mu. mol Cat 11 was added, and the reaction was vigorously stirred for 10min while maintaining ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 14600 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 75kg mol -1 Mw/Mn was 2.3, and the norbornene insertion rate was 66 mol%.
Example 35 Cat 1 catalysis of ethylene-norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced 3 times with nitrogen. Then, vacuum was applied and ethylene was substituted 3 times. 100ml of a 5mol/L norbornene-toluene solution and 6.8ml of methylaluminoxane (MAO,1.46M in toluene) were introduced by means of a syringe. 2. mu. mol Cat 11 was added at 130 ℃ and the reaction was vigorously stirred for 10min while maintaining the ethylene pressure of 6 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity: 44600 kg. mol-1 (M). h -1 . Polymer weight average molecular weight: 65 kg. mol -1 Mw/Mn was 2.5, and the norbornene insertion rate was 64 mol%.
Comparative example
In addition, the invention also adopts reported metallocene catalyst to carry out polymerization comparison so as to illustrate the characteristics of the catalyst. The information of the catalyst used in the comparative example is as follows:
catalyst a (rac-vinylbisindenyl zirconium dichloride): sigma Aldrich, 98% purity;
catalyst b (isopropyl (cyclopentadiene-9-fluorenyl) zirconium dichloride): enokay corporation, 95% pure;
the catalyst c (pentamethylcyclopentadienyl-2, 6-diisopropylphenol titanium dichloride) is synthesized by self, and the synthesis process is as follows:
a) 12mmol of 2, 6-diisopropylphenol (Inokay, 98%) was dissolved in 50ml of anhydrous THF, 12mmol of n-butyllithium was slowly added dropwise at-78 ℃ and gradually warmed to room temperature after the addition was completed, and the mixture was stirred at room temperature overnight, filtered, and the precipitated lithium salt was collected.
b) In a glove box, 12mmol of pentamethylcyclopentadiene (Sigma Aldrich, 95%) was diluted with 50ml of anhydrous n-hexane, 12mmol of n-butyllithium was added dropwise to the pentamethylcyclopentadiene solution, reacted overnight at room temperature, filtered, and the precipitated lithium salt was collected.
c) In a glove box, 5mmol of titanium tetrachloride and 5mmol of pentamethylcyclopentadienyl lithium were weighed, 50ml of anhydrous toluene was added, and the reaction was carried out at room temperature for 4 hours. Then, 2, 6-diisopropylsodium phenolate (5mmol) was added thereto, reacted for 30 minutes, returned to room temperature, and stirred for 24 hours. Lithium chloride was removed by filtration. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give catalyst c in 77% yield. 1 H-NMR(C 6 D 6 ):7.12-7.04ppm(3H),3.01ppm(2H),2.48ppm(15H),1.27ppm(12H)。
Figure BDA0003593347940000241
Comparative examples 1 to 3
Comparative examples 1-3, consistent with the conditions of example 35, with the difference that the catalyst used was different.
Figure BDA0003593347940000242
Comparative examples 4 to 6
Comparative examples 4 to 6, which are identical to the conditions of example 32, differ in the catalyst used.
Figure BDA0003593347940000251

Claims (9)

1. A thiophenol-thiophene ligand characterized by the structure:
Figure FDA0003593347930000011
wherein the thiophenol ligand has thienyl L and substituent R, and the number n of the substituent R is 0-4;
the thienyl L on the thiophenol ligand is a structure shown as a formula II, and the substituent R 1 、R 2 、R 3 、R 4 The same or different, respectively selected from hydrogen, C1-C12 alkyl, C6-C12 aryl, trimethylsilyl, preferably hydrogen, methyl, ethyl, isopropyl, trimethylsilyl, phenyl;
Figure FDA0003593347930000012
the substituent R of the thiophenol ligand is selected from C1-C12 alkyl, C6-C12 aryl, alkoxy and cyano.
2. A process for the preparation of a ligand according to claim 1, characterized in that it comprises the following steps:
(a) dissolving a halogen-containing thiophenol compound A in an anhydrous solvent under the inert gas atmosphere, mixing the halogen-containing thiophenol compound A with an alkyl lithium compound at a low temperature, and then heating to room temperature for reaction to generate a phase intermediate lithium salt B;
(b) dispersing the lithium salt B in an anhydrous solvent under the atmosphere of inert gas, mixing the lithium salt B with a ketone compound C containing thiophene at a low temperature, and then heating to react to generate a phase intermediate D;
(c) the intermediate D is reduced by active hydrogen to generate the ligand shown in the formula I.
3. The method for preparing the ligand according to claim 2, wherein in the step (a), the molar ratio of the alkyl lithium compound to the halogen-containing thiophenol compound A is 1.6-2.5: 1;
preferably, in the step (B), the molar ratio of the thiophene-containing ketone compound C to the lithium salt B is 0.8-1.5: 1;
preferably, in step (a), the cryogenic temperature is-78 ℃ to 0 ℃;
preferably, in step (b), the cryogenic temperature is-78 ℃ to 0 ℃;
preferably, in step (b), the temperature is increased to room temperature to 75 ℃.
4. The method for preparing the ligand according to claim 2 or 3, wherein the structural formula of the halogenated thiophenol compound A is as follows:
Figure FDA0003593347930000021
wherein R, n has the same definition as above, and Y is halogen;
preferably, the thiophene-containing ketone compound C has the structural formula:
Figure FDA0003593347930000022
wherein R is 1 、R 2 、R 3 、R 4 The definitions are the same as above.
5. A process for the preparation of a ligand according to any one of claims 2 to 4, wherein the alkyllithium compound is selected from one or more of methyllithium, ethyllithium, n-butyllithium, hexyllithium;
preferably, the active hydrogen for reduction in step (c) is selected from one or more of water, alcohols, and acids.
6. An olefin polymerization catalyst characterized by the structural formula:
Figure FDA0003593347930000023
wherein M is a metal selected from group IVB metals, preferably from titanium, zirconium, hafnium; substituent R, R 1 、R 2 、R 3 、R 4 Represents the same meaning as the above ligand; the X group is selected from halogen, hydrogen or alkane with 1-10 carbon atoms;
further, the olefin polymerization catalyst is selected from the following structures:
Figure FDA0003593347930000031
7. a process for preparing the olefin polymerization catalyst according to claim 6, comprising the steps of: dissolving the ligand of any one of claims 1-5 in an anhydrous solvent under an inert gas atmosphere, mixing with the catalyst under a low temperature condition, raising the temperature to room temperature for reaction to generate an intermediate, washing with a poor solvent, and then carrying out a complex reaction of the intermediate and a salt of the metal M to prepare the olefin polymerization catalyst;
preferably, the molar ratio of the ligand to the first catalyst is 1: 1.6-2.5;
preferably, the catalyst one is an alkyl lithium or alkali metal hydride, such as methyl lithium, ethyl lithium, butyl lithium or hexyl lithium;
preferably, the molar ratio of the intermediate to the salt of the metal M is 1: 0.8 to 1.2;
preferably, the mixing temperature of the ligand and the first catalyst is-90 to-20 ℃;
preferably, the poor solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane.
8. A process for preparing the olefin polymerization catalyst according to claim 6, comprising the steps of: directly complexing the intermediate D synthesized by the method of claim 2 with a salt of a metal M; preferably, the preparation method comprises the following steps: dispersing the intermediate D in an anhydrous solvent under an inert gas atmosphere, mixing the intermediate D with alkyl lithium at a low temperature, and adding a salt of a metal M to perform a complex reaction to prepare a complex;
preferably, the molar ratio of intermediate D to alkyllithium is 1: 0.8-1.2;
preferably, the alkyl lithium is selected from one or more of methyl lithium, ethyl lithium, butyl lithium, hexyl lithium;
preferably, the molar ratio of the intermediate D to the salt of the metal M is 1: 0.8 to 1.2;
preferably, the mixing temperature of the ligand and the catalyst is-90 to-20 ℃;
preferably, the poor solvent is selected from n-hexane, n-pentane, n-heptane or cyclohexane.
9. A method for olefin polymerization reaction is characterized in that the catalyst of claim 6 or the catalyst prepared by the method of claim 7 or 8 is used as a main catalyst, one or more of alkyl aluminum, methyl aluminoxane, modified aluminoxane, alkyl aluminum chloride and boron reagent are used as a cocatalyst, and the main catalyst and the cocatalyst are combined according to a certain proportion for use, so as to catalyze olefin polymerization;
further, the cocatalyst is MAO, MMAO, triisobutylaluminum, triphenyl carbenium tetrapentafluorophenyl boron;
further, the olefins catalytically polymerized are: one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene and norbornene;
further, the molar ratio of the central metal of the cocatalyst to the central metal of the main catalyst is 40-20000: 1, the polymerization temperature is 0-170 ℃, and the polymerization pressure is 0.1-10 MPa;
further, the molar equivalent ratio of the added amount of the catalyst to the added amount of the olefin is 1: 1000 to 1000000 molar equivalents.
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