CN114890987B - 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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CN114890987B
CN114890987B CN202210385192.7A CN202210385192A CN114890987B CN 114890987 B CN114890987 B CN 114890987B CN 202210385192 A CN202210385192 A CN 202210385192A CN 114890987 B CN114890987 B CN 114890987B
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lithium
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thiophenol
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CN114890987A (en
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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 follows,

Description

Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof
Technical field:
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.
The background technology is as follows:
olefin materials such as polyethylene and polypropylene are synthetic resin materials with the largest global use amount, and are widely applied to various fields of industrial production and daily life. With the development of polyolefin industry in China, the traditional bulk polyolefin products such as polypropylene, LDPE and the like are realized in domestic, but the high-end products such as polyolefin elastomer (POE), cycloolefin copolymer (COC), olefin Block Copolymer (OBC) and the like still depend on import seriously. The development of high-end polyolefin products with more excellent performance and more abundant profits is a market demand and a national safety strategic demand. To achieve the development of high-end polyolefin products, the development of high-efficiency olefin polymerization catalysts is a soul to achieve this goal.
The IVB group metallocene catalyst (Ti, zr and Hf) has definite structure and single active center, has more excellent performance in the aspects of polymerization activity, product structure control and the like, successfully opens up 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 the ligand structure and further regulating the space structure and central metal charge of the catalyst, the olefin such as ethylene, propylene, 1-octene, norbornene and the like can be coordinated and inserted in a specific angle and mode, and the polyolefin material with different compositions, sequence structures and stereospecifics can be obtained.
The double-metallocene catalyst constructed by bridged double-indenyl (structure a), bridged cyclopentadiene-fluorenyl (structure b) and other ligands has unique performance in catalyzing ethylene and alpha-olefin polymerization, especially propylene polymerization, and can prepare polypropylene materials with different tacticity with high activity; when the monocyclopentadiene catalyst (structures c and d) constructed by non-bridge Lian Maoji, phenol oxygen group and the like catalyzes ethylene, alpha-olefin and cycloolefin to be copolymerized, the large coordination space can realize high insertion rate of 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 material is prepared by copolymerization. Foreign companies such as DOW, exxon Mobil, mitsui, polyplastic and the like have developed a series of high-end polyolefin materials by means of metallocene catalysts, and great economic benefits are brought. However, both the double-metallocene catalyst and the constrained geometry catalyst have the phenomenon of too low insertion rate when catalyzing large steric hindrance monomers (such as cycloolefin). When the single metallocene catalyst constructed by non-bridge Lian Maoji and phenol oxygen groups is used for catalyzing ethylene, alpha-olefin and cycloolefin to be copolymerized, the insertion rate of the alpha-olefin and the cycloolefin is high, but the polymerization activity is low and the thermal stability of the catalyst is poor.
The invention comprises the following steps:
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 process for preparing the same and its use 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:
wherein the thiophenol ligand has thienyl L and substituent R, 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 R is 0-4, and the substitution positions are the rest positions of the thiophenyl and the thienyl L on the benzene ring.
Thienyl L on thiophenol ligand is structure shown in formula II, substituent R 1 、R 2 、R 3 、R 4 The same or different, are respectively selected from hydrogen, C1-C12 alkyl, C6-C12 aryl and trimethylsilyl, preferably hydrogen, methyl, ethyl, isopropyl, trimethylsilyl and phenyl;
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 type may be different.
The invention also provides a preparation method of the ligand, which comprises the following steps:
(a) Under the inert gas atmosphere, a halogen-containing thiophenol compound A is dissolved in an anhydrous solvent, mixed with an alkyl lithium compound at a low temperature, and then cooled to room temperature for reaction to generate a phase intermediate lithium salt B;
(b) Dispersing the lithium salt B in an anhydrous solvent in an inert gas atmosphere, mixing the solution with a ketone compound C containing thiophene at a low temperature, and then heating to react to generate a phase intermediate D;
(c) Intermediate D is reduced with active hydrogen to produce the ligand shown in formula I.
Preferably, in step (a), the molar ratio of alkyl lithium compound to halogen-containing thiophenol compound A is from 1.6 to 2.5:1, a step of;
preferably, in step (B), the molar ratio of thiophene-containing ketone compound C to lithium salt B is from 0.8 to 1.5:1, a step of;
preferably, in step (a), the low temperature is-78 ℃ to 0 ℃;
preferably, in step (b), the low temperature is-78 ℃ to 0 ℃;
preferably, in the step (b), the temperature is raised to room temperature to 75 ℃;
preferably, the halogenated thiophenol compound a has the structural formula:
wherein R, n definesY is halogen as defined above;
preferably, the structural formula of the thiophene-containing ketone compound C is as follows:
wherein R is 1 、R 2 、R 3 、R 4 The definition is the same as the definition 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 the step (c) may be selected from one or more of water, alcohols may be selected from methanol, ethanol, propanol, etc., and acid compounds may be selected from formic acid, acetic acid, or hydrochloric acid.
The reaction scheme of the ligand preparation method is shown as follows:
an olefin polymerization catalyst having the structural formula:
wherein M is a metal selected from IVB-group metals, preferably from titanium, zirconium, hafnium; substituent R, R 1 、R 2 、R 3 、R 4 The substitution number n represents the same meaning as the 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:
the invention also provides a preparation method of the olefin polymerization catalyst, which comprises the following steps: under the inert gas atmosphere, the ligand of the invention is dissolved in an anhydrous solvent, mixed with a catalyst I under the low temperature condition, then cooled to room temperature for reaction to generate a phase intermediate, the phase intermediate is washed by a poor solvent, and then the intermediate is subjected to complex reaction with a salt of metal M, so that an olefin polymerization catalyst is prepared;
preferably, the molar ratio of the ligand to the catalyst one 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, and the like;
preferably, the molar ratio of the intermediate to the salt of metal M is 1:0.8 to 1.2;
preferably, the mixing temperature of the ligand and the catalyst one is-90 to-20 ℃;
preferably, the poor solvent is selected from the group consisting of n-hexane, n-pentane, n-heptane, cyclohexane.
The reaction route of the method is as follows:
in addition, the catalyst can also be prepared by directly complexing intermediate D and metal M salts during ligand synthesis. The method comprises the following steps: dispersing the intermediate D of the ligand in an anhydrous solvent in an inert gas atmosphere, mixing with alkyl lithium at a low temperature, and adding salt of metal M for complex reaction to prepare a complex;
preferably, the molar ratio of intermediate D to alkyl lithium 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 intermediate D to the salt of metal M is 1:0.8 to 1.2;
preferably, the mixing temperature of the ligand and the catalyst is from-90 to-20 ℃;
preferably, the poor solvent is selected from the group consisting of n-hexane, n-pentane, n-heptane, cyclohexane.
The reaction route of the method is as follows:
the invention also provides a method for catalyzing olefin polymerization reaction by using the catalyst, which takes the catalyst as a main catalyst and takes one or more of alkyl aluminum, methyl Aluminoxane (MAO), modified aluminoxane (MMAO), alkyl aluminum chloride and boron reagent as a cocatalyst, and the main catalyst and the cocatalyst are combined according to a certain proportion for further catalyzing olefin polymerization.
Further, the cocatalysts used were MAO, MMAO, triisobutylaluminum, triphenylcarbon tetrapentafiuorophenylboron.
Further, the olefins catalytically polymerized are: one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, norbornene, etc.
Further, the molar ratio 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 catalyst addition amount to the olefin addition amount was 1:1000 to 1000000 molar equivalents.
The invention provides a bridged thiophenol-thienyl double-effect ligand, and an olefin polymerization catalyst constructed by the ligand and used for olefin polymerization. Compared with the prior art, the invention has the following beneficial effects: in the catalytic polymerization of olefins, in particular the copolymerization of butenes, hexenes, octenes, norbornenes and ethylene, a high insertion of comonomers is ensured while maintaining a high activity. The catalyst of the invention can conveniently regulate and control the electron-withdrawing 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 thiophenol group benzene ring, 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 the polyolefin materials with controllable molecular weight, controllable structure and various performances.
The specific embodiment is as follows:
for a better understanding of the technical solution of the present invention, the following description will further explain the content of the present invention in conjunction with the following specific examples, but the content of the present invention is not limited to the following examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
The concentrations in the examples below are molar concentrations unless otherwise specified.
The starting materials used in the examples were all conventional in the art and the purity specifications used were either analytically pure or chemically pure.
Raw material source information in the examples:
2-Bromothiophenol (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%, ala-dine
2-chloro-4-methylaniline (2-Cl-4-Me-C) 6 H 3 NH 2 ): 98%, ala-dine
2-chloro-3-methoxyaniline (2-Cl-3-MeO-C) 6 H 3 NH 2 ): 98%, ala-dine
2-chloro-4-methoxyaniline (2-Cl-4-MeO-C) 6 H 3 NH 2 ): 98%, ala-dine
2-chloro-4-cyanoaniline (2-Cl-4-CN-C) 6 H 3 NH 2 )：98％，Innochem
3-Chlorophenylthiophenol (3-Cl-C) 6 H 4 SH)：98％，Adamas
3- (3-thienyl) propionic acid: 95%, carbofuran science and technology
Sodium nitrite (NaNO) 2 )：Alirich
Potassium ethylxanthate (potassium O-ethyldithiocarbonate): 95%, TCI
Hydrochloric acid: 37%, innochem
N-butyllithium (n-BuLi): 1.6M hexane solution, carbofuran technology
Test method
The structures of the compounds and polymers synthesized in the invention are measured by Brucker ARX-400 nuclear magnetic resonance apparatus and are prepared by deuterated chloroform (CDCl) 3 ) With deuterated benzene (C) 6 D 6 ) Deuterated 1, 2-tetrachloroethane (C) 2 D 2 Cl 4 ) Is solvent, measured at room temperature or 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 the solvent. The activity of the catalyst for preparing the polymer by catalysis is calculated according to the following formula:
ligand synthesis examples
EXAMPLE 1 Synthesis of ligand L-1
(a) Synthesis of thiophene-containing ketone C1
N, N-dimethylformamide (2.0 mL) and 3- (3-thienyl) propionic acid (512 mmol) were dissolved in chloroform (400 mL) under nitrogen atmosphere, and thionyl chloride (1024 mmol) was added dropwise after mixing uniformly. And (5) heating and refluxing for 2 hours after the dripping is finished, cooling, and concentrating in vacuum to obtain an intermediate. The intermediate was dissolved in 1, 2-dichloroethane (600 ml), aluminum trichloride (512 mmol) was added and stirred overnight at 25℃and then heated to reflux for 2 hours, cooled and added to an aqueous hydrochloric acid (5%). Extraction with dichloromethane, drying over anhydrous sodium sulfate, and rotary evaporation to remove the solvent. Purification by column chromatography (dichloromethane) and spin-drying gave a thiophene-containing ketone 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 lithium 2-bromophenyl thiophenate
2-Bromobenzylthiophenol (80 mmol) was dissolved in 200ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (138 mmol) was added dropwise at 0℃and gradually warmed to room temperature, stirred overnight at room temperature, 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 (60 mmol) was dispersed in 60ml of anhydrous toluene under nitrogen atmosphere and cooled to-35 ℃. Thiophene-containing ketone C1 (64 mmol) was dissolved in 40ml of anhydrous toluene and cooled to-35℃and added dropwise to a lithium salt of thiophenol, stirred overnight, followed by heating to 70℃for reaction for 4h. After cooling to room temperature, a saturated solution of 40ml of ammonium chloride was added and quenched. 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
(a) Synthesis of 2-chloro-6-methylbenzothiool
Sodium nitrite (293 mmol) was dissolved in water (100 mL) at-10deg.C and then added dropwise to a solution of 2-chloro-6-methylaniline (245 mmol) in hydrochloric acid (3 mol/L,200 mL) and after the addition was completed, the reaction was continued at-10deg.C for 1 hour. Subsequently, the reaction solution was heated to 80℃and an aqueous potassium ethylxanthate solution (414 mmol, 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 in portions to KOH solution (1220 mmol, dissolved in 52mL water and 280mL ethanol) and heated at reflux for 21 hours. The reaction solution was cooled to 0 ℃, diluted with ice water (500 mL), pH was adjusted to 2 with hydrochloric acid, extracted with ethyl acetate, the organic phase was collected, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and the solvent was removed by spin-drying to obtain 2-chloro-6-methylbenzothioate (80%).
(b) Synthesis of lithium salt of 2-chloro-6-methylbenzothioate
2-chloro-6-methylphenylsulfiol (50 mmol) was dissolved in 100ml of anhydrous THF under nitrogen atmosphere, 100mmol of n-butyllithium was added dropwise at-45 ℃ and gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give a lithium salt of thiophenol (yield: 89%).
(c) Synthesis of ligand L-2
The resulting lithium salt (33 mmol) was dissolved in 60ml of anhydrous toluene under nitrogen atmosphere and cooled to-35 ℃. Thiophene-containing ketone C1 (30 mmol) obtained in example 1 was dissolved in 40ml of anhydrous toluene, cooled to-35℃and added dropwise to a lithium salt of thiophenol, stirred overnight, followed by heating to 70℃for reaction for 4h. After cooling, a saturated solution of 60ml of ammonium chloride was added and quenched. 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
(a) Preparation of 2-chloro-4-methylbenzothiool
Sodium nitrite (293 mmol) was dissolved in water (100 mL) at-10deg.C and then added dropwise to a solution of 2-chloro-4-methylaniline (245 mmol) in hydrochloric acid (3 mol/L,200 mL) and after the addition was completed, the reaction was continued at-10deg.C for 1 hour. Subsequently, the reaction solution was heated to 80℃and an aqueous potassium ethylxanthate solution (414 mmol, 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 in portions to KOH solution (1220 mmol, dissolved in 52mL water and 280mL ethanol) and heated at reflux for 21 hours. The reaction solution was cooled to 0 ℃, diluted with ice water (500 mL), pH was adjusted to 2 with hydrochloric acid, extracted with ethyl acetate, the organic phase was collected, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and the solvent was removed by spin-drying to obtain 2-chloro-4-methylbenzothioate (78%).
(b) Preparation of lithium salt of 2-chloro-4-methylbenzothioate
2-chloro-4-methylphenylsulfiol (60 mmol) was dissolved in 150ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (120 mmol) was added dropwise at-78deg.C, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give lithium salt of thiophenol (yield: 92%).
(c) Synthesis of ligand L-3
The resulting lithium salt (30 mmol) was dissolved in 180ml of anhydrous toluene under nitrogen atmosphere and cooled to-35 ℃. Thiophene-containing ketone C1 (45 mmol) obtained in example 1 was dissolved in 120ml of anhydrous toluene, cooled to-35℃and added dropwise to a lithium salt of thiophenol, stirred overnight, followed by heating to 70℃for reaction for 4h. After cooling, a saturated solution of 60ml of ammonium chloride was added and quenched. 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)。
Examples 4 to 8 Synthesis of ligands L-4 to 8
In examples 4-8, thiophene-containing ketone C1 was prepared according to the method of example 1, and the halothiophenol precursor was synthesized in exactly the same manner and in exactly the same proportions as the synthesis of 2-chloro-6-methylphenylsulfol in example 2, except that the precursor was used. The ligand L-4-8 in examples 4-8 was synthesized by the same method and raw material ratio as the ligand L-2 in example 2, except that the halothiophenol precursor or thiophene-containing ketone compound was used, and the specific type of the compound was as shown in Table 1.
TABLE 1 Synthesis of ligands 4-8
Catalyst synthesis examples
Example 9 preparation of catalyst Cat l
(a) Ligand L-1 (20 mmol) prepared in example 1 was dissolved in 50ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (50 mmol) was added at-78deg.C, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give lithium salt of ligand L-1 (yield: 96%).
(b) The lithium salt (15 mmol) obtained in step (a) and titanium tetrachloride (16 mmol) 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 obtain catalyst Cat 1 in 81% yield.
The catalyst Cat 1 is subjected to nuclear magnetic characterization, and the result is 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
(a) The ligand L-2 (20 mmol) prepared in example 2 was dissolved in 50ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (50 mmol) was added at-78deg.C, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give lithium salt of ligand L-2 (yield: 96%).
(b) The lithium salt (15 mmol) obtained in step (a) and titanium tetrachloride (15 mmol) 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 obtain 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
(a) The ligand L-3 (20 mmol) prepared in example 3 was dissolved in 50ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (50 mmol) was added at-78deg.C, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give lithium salt of ligand L-2 (yield: 95%).
(b) The lithium salt (15 mmol) obtained in step (a) and titanium tetrachloride (15 mmol) 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
Examples 12-17 catalysts were prepared in exactly the same manner and proportions as example 10, except that the ligand used was different from the halide of metal M; see table 2 for specific alternatives.
TABLE 2 preparation of catalysts C3-C6, C8-C14
Examples Catalyst Ligand Metal salts Yield is good
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
Catalyst Cat 1 was prepared by the same method as in example 9, and the prepared catalyst Cat 1 (20 mmol) was dissolved in 50ml of anhydrous toluene under nitrogen atmosphere, methyl magnesium bromide (20 mmol) was added at-78℃and gradually warmed to room temperature, stirred overnight at room temperature, magnesium salt was removed by filtration, toluene solvent was removed by filtration under reduced pressure, and washed three times with n-hexane to obtain catalyst Cat 8 (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
The main difference between this example and example 18 is 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
The main difference between this example and example 18 is 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)。
Polymerization of olefins
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. 4. Mu. Mol Cat 1 were added, then again evacuated and replaced 3 times with ethylene. 100ml of toluene was injected with a syringe and 3.4ml of methylaluminoxane (MAO, 1.46M in toluene) was added thereto, so that Al/M=1250. The reaction was stirred vigorously for 0min at 130℃with an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 2126kg & 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 dried continuously at 130℃for 6 hours, evacuated while hot and replaced 3 times with nitrogen, and 5. Mu. Mol Cat 2 was added. Ethylene-propylene was reacted at 1:2 are mixed in a mixing tank, and then the reaction kettle is replaced by an ethylene-propylene mixed gas for 3 times. 100ml of toluene was injected by syringe and 3.4ml of methylaluminoxane (MAO, 1.46M in toluene) was added thereto, so that Al/M=1000. At 40 ℃, the mixed gas pressure of 4atm is maintained, and the reaction is vigorously stirredAnd 10min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 675kg mol-1 (M) h -1 Polymer weight average molecular weight: 75kg & mol-1, mw/Mn=2.9, propylene insertion rate 53mol%.
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 was added, then again evacuated and replaced 3 times 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=500. The reaction was vigorously stirred at 170℃for 10min while maintaining a butene pressure of 8 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 651kg & mol-1 (M) & h-1. Polymer weight average molecular weight: 78kg 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 with nitrogen for 3 times. The kettle temperature was reduced to 50 ℃,1 μmol Cat 4 was added, 400ml toluene was injected with a syringe, and 3.4ml methylaluminoxane (MAO, 1.46M in toluene) was added to make Al/m=5000. 240ml of octene was then added and the reaction was stirred vigorously for 10min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 195kg mol-1 (M) h -1 . Polymer weight average molecular weight: 65kg 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 kettle temperature was reduced to 50 ℃, 5 μmol Cat 5 was added, 100ml toluene was injected with a syringe, and 10ml modified methylaluminoxane (MMAO, 1.50M in toluene) was added to make Al/m=3000. Subsequently 20ml of octene was added and vigorously stirredThe reaction was carried out for 10min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 395kg mol-1 (M) h -1 . Polymer weight average molecular weight: 75kg 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 with nitrogen 3 times. 1. Mu. Mol Cat 7 was added, then again evacuated and replaced 3 times with ethylene. 100ml of toluene was injected by syringe and 3.3ml of modified methylaluminoxane (MAO, 1.50M in toluene) was added thereto so that Al/M=5000. The reaction was vigorously stirred at 150℃for 30min while maintaining an ethylene pressure of 20 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, and vacuum drying to constant weight. Polymerization activity: 3790kg mol-1 (M) h -1 Polymer weight average molecular weight: 195kg 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, then again evacuated and replaced 3 times with ethylene. 100ml of a 2mol/L norbornene-toluene solution was injected by syringe. 1.7ml of methylaluminoxane (MAO, 1.46M in toluene) was added again, making Al/M=500. The reaction was vigorously stirred at 90℃for 10min while maintaining an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, 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=2.3, norbornene insertion rate 54mol%.
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 with nitrogen 3 times. 100ml of toluene, 0.2mmol of triisobutylaluminum were injected by syringe, and 5. Mu. Mol of Cat 7 and 10. Mu.m were further addedmol of triphenylcarbon tetrapentafluorophenyl boron Ph 3 CB(C 6 F 5 ) 4 Mixing and adding. The reaction was vigorously stirred at 150℃for 5min while maintaining an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 4460kg & mol-1 (M) & h -1 . Polymer weight average molecular weight: 142kg 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 with nitrogen 3 times. Then again, vacuum was pulled and replaced 3 times with ethylene. 100ml of a 2mol/L norbornene-toluene solution was injected using a syringe, and 1.5ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E) was further added. Then, 5. Mu. Mol Cat 9 was added thereto, and the reaction was vigorously stirred at 50℃for 2 minutes while maintaining an ethylene pressure of 5 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, 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=2.7, norbornene insertion rate 53mol%.
Example 30 Cat 10 catalyzed ethylene/norbornene polymerization
A250 ml stainless steel autoclave equipped with a magnetic stirrer was dried continuously at 130℃for 6 hours, evacuated and replaced 3 times with nitrogen while hot, and then evacuated and replaced 3 times with ethylene. 100ml of a 5mol/L norbornene-toluene solution was injected by syringe, followed by 6ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E). At 90℃5. Mu. Mol Cat 12 was injected and the ethylene pressure of 5atm was maintained, and the reaction was vigorously stirred for 3min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 8550kg & mol-1 (M) & h -1 . Polymer weight average molecular weight: 148kg mol -1 Mw/Mn=2.6, norbornene insertion rate 66mol%.
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 and replaced 3 times with nitrogen while hot, and then evacuated and replaced 3 times with ethylene. 100ml of a 2mol/L norbornene-toluene solution was injected using a syringe, and 4ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E) was added. At 90℃5. Mu. Mol Cat 11 was injected and the ethylene pressure of 5atm was maintained, and the reaction was vigorously stirred for 5 minutes. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 6480kg mol-1 (M) h -1 . Polymer weight average molecular weight: 173kg mol -1 Mw/Mn=2.5, norbornene insertion rate 57mol%.
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, 90ml of 1-hexene were injected by syringe, the temperature in the kettle 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 maintained under vigorous stirring for 10min at an ethylene pressure of 20 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 7580kg mol-1 (M) h -1 . Polymer weight average molecular weight: 1750kg & mol -1 Mw/Mn= 2.5,1-hexene insertion 19mol%.
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. 150ml of toluene, 90ml of 1-hexene were injected by syringe, the temperature in the kettle was heated to 90℃and 3.4ml of methylaluminoxane (MAO, 1.46M in toluene) was added. 5. Mu. Mol Cat 1 was added thereto and the reaction was vigorously stirred for 10 minutes while maintaining an ethylene pressure of 30 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, washing with water for several times, and vacuum drying to constant weightAnd (5) weighing. Polymerization activity: 14580kg & mol-1 (M) & h -1 . Polymer weight average molecular weight: 2500kg mol -1 Mw/Mn= 2.5,1-hexene insertion 18mol%.
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 with nitrogen 3 times. Then again, vacuum was pulled and replaced 3 times with ethylene. 100ml of 5mol/L norbornene-toluene solution, 6.8ml methylaluminoxane (MAO, 1.46M in toluene) was injected using a syringe. At 70℃2. Mu. Mol Cat 11 was added and the reaction was vigorously stirred for 10min while maintaining an ethylene pressure of 4 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 14600kg & mol-1 (M) & h -1 . Polymer weight average molecular weight: 75kg mol -1 Mw/Mn=2.3, norbornene insertion rate 66mol%.
Example 35 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 with nitrogen 3 times. Then again, vacuum was pulled and replaced 3 times with ethylene. 100ml of 5mol/L norbornene-toluene solution, 6.8ml methylaluminoxane (MAO, 1.46M in toluene) was injected using a syringe. At 130℃2. Mu. Mol Cat 11 was added and the reaction was vigorously stirred for 10min while maintaining an ethylene pressure of 6 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization activity: 44600kg & mol-1 (M) & h -1 . Polymer weight average molecular weight: 65kg mol -1 Mw/Mn=2.5, norbornene insertion rate 64mol%.
Comparative example
In addition, the invention also adopts reported metallocene catalyst for polymerization comparison to illustrate the characteristics of the catalyst. The catalyst information used in the comparative example is as follows:
catalyst a (rac-vinyl bis indenyl zirconium dichloride): sigma Aldrich, 98% purity;
catalyst b (isopropyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride): enoKai Co., purity 95%;
catalyst c (pentamethylcyclopentadienyl-2, 6-diisopropylphenyl titanium dichloride) is self-synthesized by the following steps:
a) 12mmol of 2, 6-diisopropylphenol (enokie, 98%) is dissolved in 50ml of anhydrous THF, 12mmol of n-butyllithium is slowly added dropwise at-78 ℃, gradually warmed to room temperature after the addition, stirred overnight at room temperature, filtered and the precipitated lithium salt is collected.
b) 12mmol of pentamethylcyclopentadiene (Sigma Aldrich, 95%) was diluted with 50ml of anhydrous n-hexane in a glove box, 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) 5mmol of titanium tetrachloride, 5mmol of pentamethyl cyclopentadienyl lithium and 50ml of anhydrous toluene were weighed in a glove box and reacted at room temperature for 4 hours. Then, 2, 6-diisopropylphenol sodium (5 mmol) was added thereto, and after 30 minutes of reaction, the mixture was 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)。
Comparative examples 1 to 3
Comparative examples 1-3 were identical to example 35 except that the catalysts used were different.
Comparative examples 4 to 6
Comparative examples 4-6 were identical to example 32 except that the catalysts used were different.
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Claims (32)

1. A thiophenol-thiophene ligand, characterized by the following structure:
wherein the thiophenol ligand has thienyl L and substituent R, and the number n of the substituent R is 0-4;
thienyl L on thiophenol ligand is structure shown in formula II, substituent R 1 、R 2 、R 3 、R 4 The same or different, are respectively selected from hydrogen, C1-C12 alkyl, C6-C12 aryl and trimethylsilyl,
the substituent R of the thiophenol ligand is selected from C1-C12 alkyl, C6-C12 aryl, alkoxy and cyano.
2. The ligand of claim 1, wherein the substituents R 1 、R 2 、R 3 、R 4 Is selected from hydrogen, methyl, ethyl, isopropyl, trimethylsilyl and phenyl.
3. A method of preparing a ligand according to claim 1, comprising the steps of:
(a) Under the inert gas atmosphere, a halogen-containing thiophenol compound A is dissolved in an anhydrous solvent, mixed with an alkyl lithium compound at a low temperature, and then cooled to room temperature for reaction to generate a phase intermediate lithium salt B;
(b) Dispersing the lithium salt B in an anhydrous solvent in an inert gas atmosphere, mixing the solution with a ketone compound C containing thiophene at a low temperature, and then heating to react to generate a phase intermediate D;
(c) Intermediate D is reduced with active hydrogen to produce the ligand shown in formula I.
4. A process for the preparation of a ligand according to claim 3, wherein in step (a), the molar ratio of alkyl lithium compound to halogen-containing thiophenol compound a is from 1.6 to 2.5:1.
5. a process for the preparation of a ligand according to claim 3, wherein in step (B) the molar ratio of thiophene-containing ketone compound C to lithium salt B is from 0.8 to 1.5:1.
6. a process for preparing a ligand according to claim 3, wherein in step (a), the low temperature is-78 ℃ to 0 ℃.
7. A process for preparing a ligand according to claim 3, wherein in step (b), the low temperature is-78 ℃ to 0 ℃.
8. A process for preparing a ligand according to claim 3, wherein in step (b), the temperature is raised to a temperature of from room temperature to 75 ℃.
9. A method of preparing a ligand according to claim 3, wherein the halogenated thiophenol compound a has the structural formula:
wherein R, n is as defined in claim 1 and Y is halogen.
10. A method for preparing a ligand according to claim 3, wherein the thiophene-containing ketone compound C has the structural formula:
wherein R is 1 、R 2 、R 3 、R 4 The definition is the same as that of claim 1.
11. A method of preparing a ligand according to claim 3, wherein the alkyl lithium compound is selected from one or more of methyl lithium, ethyl lithium, n-butyl lithium, hexyl lithium.
12. A method for preparing a ligand according to claim 3, wherein the active hydrogen for reduction in step (c) is selected from one or more of water, alcohols and acid compounds.
13. An olefin polymerization catalyst characterized by the structural formula:
wherein M is a metal selected from IVB-group metals, substituent R, R 1 、R 2 、R 3 、R 4 Representing the same meaning as the ligand of claim 1; the X group is selected from halogen, hydrogen or alkane with 1-10 carbon atoms.
14. The catalyst of claim 13 wherein M is selected from titanium, zirconium, hafnium.
15. The catalyst of claim 14 wherein the olefin polymerization catalyst is selected from the group consisting of the following structures:
16. a process for preparing the olefin polymerization catalyst of claim 13, comprising the steps of: dissolving the ligand in any one of claims 1-2 in anhydrous solvent under inert gas atmosphere, mixing with the catalyst I under low temperature condition, then raising to room temperature for reaction to generate phase intermediate, washing with poor solvent, and then carrying out complexation reaction on the intermediate and salt of metal M, thus obtaining the olefin polymerization catalyst.
17. The method of claim 16, wherein the molar ratio of ligand to catalyst one is 1:1.6-2.5.
18. The process of claim 16, wherein the catalyst one is an alkyl lithium or an alkali metal hydride selected from methyl lithium, ethyl lithium, butyl lithium or hexyl lithium.
19. The process of claim 16, wherein the molar ratio of intermediate to metal M salt is 1:0.8 to 1.2.
20. The process of claim 16 wherein the ligand and catalyst one are mixed at a temperature of from-90 to-20 ℃.
21. The method of claim 16, wherein the poor solvent is selected from the group consisting of n-hexane, n-pentane, n-heptane, cyclohexane.
22. A process for preparing the olefin polymerization catalyst of claim 13, comprising the steps of: a process for the direct complexation of intermediate D synthesized by the method of claim 3 with a salt of metal M.
23. The preparation method according to claim 22, comprising the steps of: dispersing the intermediate D in an anhydrous solvent under the inert gas atmosphere, mixing with alkyl lithium at a low temperature, and adding a salt of metal M for complexation reaction to prepare the complex.
24. The process according to claim 23, wherein the molar ratio of intermediate D to alkyl lithium is 1:0.8-1.2.
25. The method according to claim 23, wherein the alkyl lithium is one or more selected from methyl lithium, ethyl lithium, butyl lithium, and hexyl lithium.
26. The process according to claim 22, wherein the molar ratio of intermediate D to the salt of metal M is 1:0.8 to 1.2.
27. The preparation method according to claim 23, wherein the mixing temperature of the ligand and the alkyl lithium is-90 to-20 ℃.
28. A method for olefin polymerization, characterized in that the catalyst prepared by the method of any one of claims 13-15 or 16-27 is used as a main catalyst, and one or more of alkyl aluminum, methylaluminoxane, 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 so as to catalyze olefin polymerization.
29. The process for the polymerization of olefins according to claim 28, wherein the cocatalyst used is MAO, MMAO, triisobutylaluminum, triphenylcarbon tetrapentafiuorophenylboron.
30. The process for the polymerization of olefins according to claim 28, wherein the olefin catalyzed polymerization is: one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, norbornene.
31. The process for the polymerization of olefins according to claim 28, wherein the molar ratio of cocatalyst to procatalyst center metal is from 40 to 20000:1, the polymerization temperature is 0-170 ℃ and the polymerization pressure is 0.1-10 MPa.
32. The process for the polymerization of olefins according to claim 28 wherein the molar equivalent ratio of catalyst loading to olefin loading is 1:1000 to 1000000 molar equivalents.
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