CN114105814B - Ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof - Google Patents

Ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof Download PDF

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CN114105814B
CN114105814B CN202111429548.4A CN202111429548A CN114105814B CN 114105814 B CN114105814 B CN 114105814B CN 202111429548 A CN202111429548 A CN 202111429548A CN 114105814 B CN114105814 B CN 114105814B
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ligand
catalyst
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reaction
polymerization
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CN114105814A (en
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邓明
郭华
石正喜
吕英东
贾礼洋
高原
黄明路
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses a ligand and a preparation method thereof, an olefin polymerization catalyst and a preparation method thereof, wherein the ligand has a structure shown in a formula I,

Description

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 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:
polyolefin materials are the fastest growing synthetic resins with the largest yield, have become important props for modern scientific technology and social development, and are widely applied in various fields of industrial production and daily life. Under the drive of the market for novel polyolefin materials, high-end polyolefin materials such as polyolefin elastomer (POE), polyolefin block copolymer (OBC), cycloolefin copolymer (COC) and the like are developed and applied. In the development process of the polyolefin materials, the development and industrialization of olefin polymerization catalysts are important thrusters for promoting the development of the polyolefin industry. The development of olefin polymerization catalysts has become a focus of attention in both academia and industry.
Compared with the traditional Ziegler-Natta catalyst, the IV-group metallocene catalyst (Ti, zr, hf) has the characteristics of definite structure, single active center, designable catalyst structure and the like, so that the catalyst has more excellent performance in the aspects of polymerization activity, product structure control and the like, and becomes a catalytic system for industrial development. The ligand is modified, so that the space structure and the central metal charge of the metallocene catalyst are regulated, and the olefins such as ethylene, propylene, 1-octene, norbornene and the like are coordinated and inserted in a specific angle and mode, so that polyolefin materials with different compositions, sequence structures and stereoscopy can be obtained.
The metallocene catalyst constructed by ligands such as bridged bisindenyl (structure a) and bridged cyclopentadienyl-fluorenyl (structure b) has unique performance in catalyzing ethylene and alpha-olefin polymerization, especially propylene polymerization, and can prepare polypropylene materials with different tacticity with high activity; the constrained geometry catalyst (structure c) 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 of these catalysts have a phenomenon that the insertion rate is too low for a large steric hindrance olefin monomer such as cycloolefin or the like. When the metallocene catalyst (structure d) constructed by non-bridge Lian Maoji and phenol oxygen groups is used for catalyzing ethylene, alpha-olefin and cycloolefin to be copolymerized, the alpha-olefin and cycloolefin have high insertion rate, but have the phenomena of low polymerization activity and poor thermal stability of the catalyst.
Disclosure of Invention
The invention aims to provide a ligand and a preparation method thereof, wherein the ligand can be used as an olefin polymerization catalyst ligand, and forms a complex with metal for olefin polymerization reaction.
It is another object of the present invention to provide a process for preparing an olefin polymerization catalyst 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 ligand having the structure:
wherein the substituents S of indenyl groups 1 、S 2 、S 3 、S 4 、S 5 、S 6 The same or different, selected from hydrogen, C1-C12 alkyl, C6-C12 aryl, trimethylsilyl, etc., preferably hydrogen, methyl, ethyl, isopropyl, trimethylsilyl, phenyl, etc.; substituent R 2 Selected from hydrogen, C1-C12 alkyl, C6-C12 aryl, etc., preferably methyl, ethyl, isopropyl, t-butyl, phenyl, substituted phenyl, etc.; substituent R 1 Selected from hydrogen, C1-C12 alkyl, C6-C12 aryl, etc., preferably from hydrogen, methyl, isopropyl, phenyl, etc.
The invention also provides a preparation method of the ligand, which comprises the following steps:
(a) Under the inert gas atmosphere, the indene compound is dissolved in an anhydrous solvent, mixed with alkyl lithium or sodium hydride at a low temperature, and then heated to room temperature for reaction to generate a phase intermediate lithium or sodium salt B, and the phase intermediate lithium or sodium salt B is washed by a poor solvent.
(b) Dispersing the lithium or sodium salt B in an anhydrous solvent under the inert gas atmosphere, mixing with halogenated ketone compounds at a low temperature, and then, heating to room temperature for reaction to generate a phase intermediate C.
(c) And mixing the intermediate C with an ammonium chloride aqueous solution, and heating for reaction to generate the ligand shown in the formula I.
Preferably, the alkyl lithium is selected from methyl lithium, ethyl lithium, butyl lithium, hexyl lithium, and the like;
preferably, in step (a), the molar ratio of alkyl lithium compound or sodium hydride to indenyl compound 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 molar ratio of halogenated ketone compound to lithium or sodium salt B is between 0.8 and 1.5:1, a step of;
preferably, in step (b), the low temperature is-78 ℃ to 0 ℃;
preferably, the halogenated ketone compound has the structural formula:
wherein R is 1 、R 2 Y is halogen, and the definition is the same as the definition; preferably, the anhydrous solvent is selected from one or more of toluene, tetrahydrofuran, hexane, cyclohexane, methylcyclohexane, diethyl ether, etc.;
preferably, in step (C), the molar ratio of ammonium chloride to intermediate C is between 0.8 and 1.5:1, a step of;
preferably, in step (c), the heating temperature is selected from 40 ℃ to 80 ℃.
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 to titanium, zirconium, hafnium; substituent S 1 、S 2 、S 3 、S 4 、S 5 、S 6 And R is 1 、R 2 The meaning of the representation is the same as that of 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 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 under the low temperature condition, then heated 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 the salt of metal M, so as to prepare a complex;
preferably, the molar ratio of ligand to catalyst is 1:1.6-2.5;
preferably, the catalyst is an alkyl lithium or alkali metal hydride, such as methyl lithium, ethyl lithium, butyl lithium, hexyl lithium, sodium hydride, 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 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 another preparation method of the catalyst: under the inert gas atmosphere, the ligand of the invention is dissolved in an anhydrous solvent to carry out complexation reaction with an alkyl metal compound, thereby preparing the complex.
Preferably, the molar ratio of the ligand to the metal alkyl compound is 0.8 to 1.2; the anhydrous solvent is selected from one or more of benzene, toluene, xylene, tetrahydrofuran, diethyl ether and dichloromethane;
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.
Compared with the prior art, the invention has the following beneficial effects: in catalyzing olefin polymerization, especially butene, hexene, octene, norbornene and ethylene copolymerization, high activity is maintained while high insertion of comonomer is ensured. The ligand structure of the invention not only contains a cyclopentadienyl structure, but also has an imino group, the electron-donating ability of substituents on the cyclopentadienyl and imino groups can be controlled conveniently to regulate and control the electron effect of the catalyst, the steric effect of the catalyst can be controlled conveniently by controlling the steric hindrance of the substituents of the cyclopentadienyl, imino and bridging groups, thereby realizing the regulation and control of the olefin polymerization performance of olefin monomers, realizing the high insertion rate of comonomers while keeping high activity, and obtaining the polyolefin materials with controllable molecular weight, controllable structure and different 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:
indend: 99%, sigma-Aldrich
2-methylindene MeInd:98%, saen chemical technology (Shanghai) Co., ltd
1- (bromoacetyl) pyrene BrCH 2 (Pry) c=o: 97%, carbofuran science and technology
1-bromo-3, 3-dimethyl-2-butanone Br 2 CH(t-Bu)C＝O：97％，TCI
1-Phenylpropanothien-3-yl-2-bromoethyl-1-one Br 2 CH(Thio) c=o: 97%, carbofuran science and technology
2-Bromoacetophenone Br 2 CH(Ph)C＝O：98％，Alfa Aesar
2-bromo-4-methoxyacetophenone Br 2 CH(MeOPh) c=o, 98%, carbofuran technology
2-bromo-4, 4-dimethyl-3-pentanone Br (Me) CH (t-Bu) c=o, 98%, TCI
2-bromo-1-tetronic ketoneNaphthalene Br 2 CH(NAP) c=o, 97%, saen chemical technology (Shanghai) limited
2-Bromocyclopentanone Br 2 CH(CP) c=o, 97%, south Beijing Kang Manlin
N-butyllithium n-BuLi:1.6M hexane solution, carbofuran technology
Calcium hydride CaH 2 :93%, carbofuran technology
Sodium hydride NaH:60%, 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:
example l ligands 2 IndCHSynthesis of (t-Bu) c=nh (ligand 1)
(a) Indene (200 mmol) was dissolved in 500ml anhydrous THF under nitrogen atmosphere, n-butyllithium (300 mmol) was added dropwise at-45 ℃, 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 indene: indLi.
(b) Under nitrogen, the lithium salt IndLi (125 mmol) of indene is added to 500ml of anhydrous THF, and 1-bromo-3, 3-dimethyl-2-butanone Br is added dropwise at-45 ℃ 2 CH(t-Bu)C＝O (100 mmol), gradually warmed to room temperature after the completion of the dropwise addition, and reacted for 2 hours, filtered, the solvent was removed under reduced pressure, and purified by column chromatography to give an intermediate.
(c) The intermediate (50 mmol) was dissolved in tetrahydrofuran (200 ml), and ammonium chloride (60 mmol) and water (100 ml) were added to the system with stirring. The temperature of the system was raised to 60℃and reacted for 2h. The system was returned to room temperature, sodium bicarbonate was added until no more bubbles were generated, and filtered. A large amount of methylene chloride was added for extraction, the solvent was removed under reduced pressure, and purification by column chromatography was performed to obtain ligand 1. 1 H-NMR(CDCl 3 ):7.25-7.56(4H),6.44-6.73(2H),3.86-3.89ppm(1H),2.82-2.99ppm(2H)，1.17ppm(9H)。
Example 2 ligands 3 2 CHIndCHSynthesis of (t-Bu) c=nh (ligand 2)
(a) Methylindene (200 mmol) was dissolved in 50ml of anhydrous THF under nitrogen, n-butyllithium (200 mmol) 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 lithium salt of methylindene: CH (CH) 3 IndLi。
(b) Lithium salt CH of methylindene under nitrogen atmosphere 3 IndLi (110 mmol) was added to 50ml anhydrous THF and 1-bromo-3, 3-dimethyl-2-butanone Br was added dropwise at-45 ℃ 2 CH(t-Bu) c=o (100 mmol), gradually warmed to room temperature after completion of the dropwise addition, stirred at room temperature for 2h, filtered, the solvent was removed under reduced pressure, and purified by column chromatography to give an intermediate.
(c) The intermediate (50 mmol) was dissolved in tetrahydrofuran (200 ml), and ammonium chloride (75 mmol) and water (100 ml) were added to the system with stirring. The temperature of the system was raised to 60℃and reacted for 2h. The system was returned to room temperature, sodium bicarbonate was added until no more bubbles were generated, and filtered. A large amount of methylene chloride was added for extraction, the solvent was removed under reduced pressure, and the resultant was purified by column chromatography to obtain ligand 2. 1 H-NMR(CDCl 3 ):7.35-7.66(4H),6.50-6.52(1H),3.86-3.89ppm(1H),2.82-2.99ppm(2H),1.74ppm(3H),1.17ppm(9H)。
Example 3 ligandsInd(Me)CHSynthesis of (t-Bu) c=nh (ligand 3)
(a) Indene (200 mmol) was dissolved in 50ml of anhydrous THF under nitrogen atmosphere, n-butyllithium (160 mmol) was added dropwise at-45 ℃, 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 indene: indLi.
(b) The lithium salt of indene IndLi (100 mmol) was added to 500ml of anhydrous THF under nitrogen atmosphere, 2-bromo-4, 4-dimethyl-3-pentanone Br (Me) CH (t-Bu) C=O (150 mmol) was added dropwise at-45℃and gradually warmed to room temperature after the completion of the addition, stirred at room temperature for 2 hours, filtered, the solvent was removed under reduced pressure, and the intermediate was obtained by purification with column chromatography.
(c) The intermediate (50 mmol) was dissolved in tetrahydrofuran (200 ml), and ammonium chloride (40 mmol) and water (100 ml) were added to the system with stirring. The temperature of the system was raised to 60℃and reacted for 2h. The system was returned to room temperature, sodium bicarbonate was added until no more bubbles were generated, and filtered. A large amount of methylene chloride was added for extraction, the solvent was removed under reduced pressure, and the resultant was purified by column chromatography to give ligand 3. 1 H-NMR(CDCl 3 ):7.25-7.56(4H),6.44-6.73(2H),3.86-3.89ppm(1H),3.10-3.16ppm(1H),1.27ppm(3H),1.17ppm(9H)。
Examples 4 to 12
EXAMPLES 4 to 12 ligands were prepared by exactly the same methods and proportions as in example 2, except that indene compounds or keto halides were used, the specific alternatives are shown in Table 1
TABLE 1 Synthesis of ligands 4-12
Preparation of the catalyst:
example 13 preparation of catalyst C1
(a) Ligand 1:IndCH prepared in example 1 under nitrogen atmosphere 2 (t-Bu) c=nh (10 mmol) in 50ml anhydrous THF, sodium hydride (25 mmol) was added at-78 ℃, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give sodium salt: naIndCH 2 (t-Bu) c=nna (yield: 78%).
(b) The sodium salt (5 mmol) obtained in step (a) and titanium tetrachloride (6 mmol) were added to 50ml of anhydrous toluene at-45℃and then slowly returned to room temperature and stirred for 12 hours. Sodium chloride was removed by filtration. The toluene solvent was removed under reduced pressure, and washed three times with n-hexane to give catalyst Cl in 83% yield. 1 H-NMR(C 6 D 6 ):7.27-7.58(4H),6.04-6.08(2H),3.86-3.89ppm(1H),2.82-2.99ppm(2H),1.19ppm(9H)。
EXAMPLE 14 preparation of catalyst C2
(a) Ligand 2 was prepared in the same manner as in example 2, and ligand 2:CH was reacted under nitrogen atmosphere 3 IndCH 2 (t-Bu) c=nh (25 mmol) in 50ml anhydrous THF, n-butyllithium (40 mmol) was added at-78 ℃, gradually warmed to room temperature, stirred overnight at room temperature, filtered, and washed three times with anhydrous n-hexane to give a lithium salt: liCH (LiCH) 3 IndCH 2 t BuC =nli (yield: 58%).
(b) Solid lithium salt (6 mmol) and titanium tetrachloride (5 mmol) were added to 50ml of anhydrous toluene at-45℃and then slowly returned to room temperature and stirred for 12 hours. Sodium chloride was removed by filtration. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give a C2 catalyst in 83% yield. 1 H-NMR(C 6 D 6 ):7.38-7.69(4H),6.54-6.56(1H),3.89-3.92ppm(1H),2.84-2.99ppm(2H),1.76ppm(3H),1.15ppm(9H)。
EXAMPLE 15 preparation of catalyst C7
(a) Titanium tetrachloride (15 mmol) was added to 50ml of anhydrous THF under nitrogen atmosphere, methyl magnesium bromide (60 mmol) was added at-78℃and gradually warmed to room temperature, stirred overnight at room temperature, filtered, the filtrate was drained off and washed three times with anhydrous n-hexane to give tetramethyl titanium (yield: 92%).
(b) Tetramethyl titanium (10 mmol) was dissolved in anhydrous toluene at room temperature and ligand 1IndCH was added 2 (t-Bu) c=nh (10 mmol), and stirred for 4 hours. The toluene solvent was removed under reduced pressure and washed three times with n-hexane to give a C7 catalyst in 73% yield. 1 H-NMR(C 6 D 6 ):7.29-7.54(4H),6.04-6.08(2H),3.86-3.89ppm(1H),2.82-2.99ppm(2H),1.19ppm(9H),-0.23ppm(6H)。
Examples 16 to 26
Examples 16-19, examples 21-26 catalysts were prepared using exactly the same procedure and proportions as in example 14, except that the ligand used was different from the halide of metal M; example 20a catalyst was prepared in exactly the same manner and proportions as in example 15, 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
Catalyst Ligand MX 4 Yield is good
16 C3 IndCH 2 (Ph)C＝NH TiCl 4 84％
17 C4 MeIndCH 2 (t-Bu)C＝NH TiCl 4 82％
18 C5 Ind(Me)CH(CH 3 )C＝NH TiCl 4 79％
19 C6 IndCH 2 (CH 3 )C＝NH TiCl 4 89％
20 C8 MeIndCH 2 (t-Bu)C＝NH TiMe 4 86％
21 C9 IndCH 2 (t-Bu)C＝NH ZrCl 4 84％
22 C10 IndCH 2 (Pry)C＝NH TiCl 4 79％
23 C11 IndCH 2 (Thio)C＝NH TiCl 4 75％
24 C12 IndCH 2 (MeOPh)C＝NH TiCl 4 84％
25 C13 IndCH 2 (NAP)C＝NH TiCl 4 92％
26 C14 IndCH 2 (t-Bu)C＝NH HfCl 4 86％
Polymerization of olefins
Example 27, C1 catalytic 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 N2 gas. 4. Mu. Mol of C1 are added, then a further vacuum is applied 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 to make Al/Ti=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: 1526 kg.mol-1 (Ti). H-1. The polymer molecular weight was 982kg & mol-1, mw/Mn=2.5.
EXAMPLE 28C 2 catalyzed 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 N2 gas. 5. Mu. Mol of C2 are added. Then again, vacuum was pulled and replaced 3 times with propylene. 100ml of toluene was injected by syringe and 3.4ml of methylaluminoxane (MAO, 1.46M in toluene) was added thereto so that Al/Ti=1000. The reaction was vigorously stirred at 120℃for 10min while maintaining a propylene 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: 675kg & mol-1 (Ti) & h-1. The polymer mw=320 kg·mol-1, mw/mn=3.1.
Example 29, C3 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 N2 gas. 5. Mu. Mol of C3 are added, then a further vacuum is applied and replaced 3 times with ethylene. 100ml of toluene was injected by syringe and 1.7ml of methylaluminoxane (MAO, 1.46M in toluene) was added thereto so that Al/Ti=500. The reaction was vigorously stirred at 170℃for 10min while maintaining an ethylene 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 (Ti) & h-1. Polymer mw=5680 kg & mol-1, mw/mn=2.4.
Example 30C 4 catalyzed polymerization of 1-butene
A250 ml stainless steel autoclave equipped with stirring was dried continuously at 130℃for 6 hours, evacuated while hot and replaced 3 times with N2 gas. 5. Mu. Mol of C4 are added, then a further vacuum is applied and replaced 3 times with butene. 200ml of toluene was injected by syringe and 3.4ml of methylaluminoxane (MAO, 1.46M in toluene) was added thereto so that Al/Ti=1000. The butene pressure of l atm was maintained at 0℃and the reaction was vigorously stirred for 5min. 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: 153kg mol-1 (Ti). H-1. Polymer mw=1750 kg·mol-1, mw/mn=2.9.
Example 31C 5 catalytic 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 N2 gas. The kettle temperature was reduced to 50 ℃, 5 μmol of C5 was added, 100ml of toluene was injected with a syringe, and 17ml of methylaluminoxane (MAO, 1.46M in toluene) was added to make Al/ti=5000. 20ml 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 (Ti). H-1. The polymer mw=65 kg·mol-1, mw/mn=2.3.
EXAMPLE 32 Cl-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 N2 gas 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 of Cl was added and the reaction was maintained under ethylene pressure of 30atm with vigorous stirring 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: 13580 kg.mol-1 (Ti). H-1. The polymer Mw=2050 kg.mol-1 and Mw/Mn= 2.4,1-hexene insertion 23mol%.
Example 33C 8 catalytic 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 N2 gas. 5. Mu. Mol of C8 are 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/Ti=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: 10610kg & mol-1 (Ti) & h-1. The polymer Mw=95 kg·mol-1, mw/Mn=2.3, norbornene insertion rate 52mol%.
Example 34C 11 catalytic 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 N2 gas. 5. Mu. Mol of C11, then again evacuated and replaced 3 times with ethylene. 100ml of toluene was injected with a syringe and 1.5ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E) was added thereto so that Al/Ti=500. The reaction was vigorously stirred at 50℃for 2min 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: 4550kg & mol-1 (Ti) & h-1. The polymer molecular weight Mw=78 kg & mol-1, mw/Mn=2.7, norbornene insertion rate 53mol%.
Example 35C 12 catalytic 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 N2 gas. 5. Mu. Mol of C12, then again evacuated and replaced 3 times with ethylene. 100ml of toluene was injected with a syringe and 6ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E) was added thereto, so that Al/Ti=200. The reaction was vigorously stirred at 90℃for 3min 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: 7550 kg.mol-1 (Ti). H-1. The polymer molecular weight Mw=108 kg·mol-1, mw/Mn=2.7, norbornene insertion rate 56mol%.
Example 36C 13 catalytic 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 N2 gas. 5. Mu. Mol of C13, then again evacuated and replaced 3 times with ethylene. 100ml of toluene was injected with a syringe and 4ml of modified methylaluminoxane (MMAO, 1.98M solution in IsoPar-E) was added to make Al/Ti=1600. The reaction was vigorously stirred at 90℃for 5min 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: 6480 kg.mol-1 (Ti). H-1. The polymer molecular weight Mw=152 kg & mol-1, mw/Mn=2.4, norbornene insertion rate 54mol%.
Example 37, C7 catalytic 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 N2 gas. 100ml of toluene and 0.2mmol of triisobutylaluminum were injected by syringe, and 5. Mu. Mol of C7 and 10. Mu. Mmol of triphenylcarbon tetrapentafluorophenylboron Ph were further introduced 3 CB(C 6 F 5 ) 4 Mixing and adding. The reaction was vigorously stirred at 50℃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: 2460 kg.mol-1 (Ti). H-1. The polymer molecular weight mw=122 kg·mol-1, mw/mn=2.7.
Example 38, C9 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 N2 gas. 1. Mu. Mol of C9 was added, followed by additional evacuation and displacement with ethylene 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/Ti=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, vacuum drying to constant weight, and weighing. Polymerization activity: 2790 kg.mol-1 (Ti). H-1. The polymer molecular weight mw=155 kg·mol-1, mw/mn=3.2.
Example 39, C14 catalytic polymerization of l-octene
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 N2 gas. The kettle temperature was reduced to 50℃and 100ml of toluene, 0.2mmol of triisobutylaluminum, 20ml of 1-octene were injected with a syringe, followed by 5. Mu. Mol of C14 and 10. Mu. Mmol of triphenylcarbon tetrapentapentafluorophenyl boron Ph 3 CB(C 6 F 5 ) 4 Mixing and adding. The reaction was stirred vigorously for 5min. 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: 1380kg & mol-1 (Ti) & h-1. The polymer molecular weight mw=110 kg·mol-1, mw/mn=2.3.
EXAMPLE 40C 10 catalytic ethylene/l-octene 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 N2 gas and 3 times with ethylene. The kettle temperature was reduced to 50℃and 100ml of toluene, 0.2mmol of triisobutylaluminum, 20ml of 1-octene were injected with a syringe, followed by 5. Mu. Mol of C10 and 10. Mu. Mmol of triphenylcarbon tetrapentapentafluorophenyl boron Ph 3 CB(C 6 F 5 ) 4 Mixing and adding. Ethylene pressure was maintained at 7atm and the reaction was vigorously stirred for 5min. 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: 780kg mol-1 (Ti). H-1. Polymer molecular weight mw=130kg.mol-1, mw/mn=2.3, octene insertion 24mol%.
EXAMPLE 41 Cl-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 N2 gas. 2. Mu. Mol of C1 are added, then again evacuated and replaced 3 times with ethylene. 100ml of 5mol/L norbornene-toluene solution were injected via syringe. 6.8ml of methylaluminoxane (MAO, 1.46M in toluene) was added to make Al/Ti=5000. The reaction was vigorously stirred at 70℃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: 9610 kg.mol-1 (Ti). H-1. The polymer molecular weight Mw=55 kg & mol-1, mw/Mn=2.3, norbornene insertion rate 66mol%.
Example 42C 2 catalytic 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 N2 gas. 1. Mu. Mol of C2 was added, then again evacuated and replaced 3 times with ethylene. 100ml of 5mol/L norbornene-toluene solution were injected via syringe. 6.8ml of methylaluminoxane (MAO, 1.46M in toluene) was added to make Al/Ti=10000. The reaction was vigorously stirred at 70℃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: 3610 kg.mol-1 (Ti). H-1. The polymer molecular weight Mw=95 kg & mol-1, mw/Mn=2.3, norbornene insertion rate 66mol%.
EXAMPLE 43C 6 catalytic 1-hexene/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 N2 gas. 1. Mu. Mol of C6 was added, then again evacuated and replaced 3 times with ethylene. 50ml of 5mol/L norbornene-toluene solution, 30ml of toluene, 20ml of 1-hexene were injected by syringe. 1.7ml of methylaluminoxane (MAO, 1.46M in toluene) was added again, making Al/Ti=2500. The reaction was vigorously stirred at 70℃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: 3610 kg.mol-1 (Ti). H-1. The polymer molecular weight Mw=45 kg·mol-1, mw/Mn=2.3, norbornene insertion rate 48mol%.
EXAMPLE 44C 9 catalytic copolymerization of ethylene and 1-hexene
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 N2 gas. 5. Mu. Mol of C9 are added, then again evacuated and replaced 3 times with ethylene. 100ml of toluene, 20ml of 1-hexene were injected by syringe, and 3.4ml of methyloxane (MAO, 1.46M in toluene) was added thereto so that Al/Zr=1000. The reaction was stirred vigorously at 50℃for 10min while maintaining the pressure of latm in ethylene. 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: 115kg & mol-1 (Zr) & h-1. Polymer molecular weight=350 kg.mol-1, mw/Mn= 2.1,1-hexene insertion 35mol%.
In addition, the invention also adopts reported metallocene catalyst for polymerization comparison to illustrate the characteristics of the catalyst. The main structure of the metallocene catalyst is as follows:
comparative examples 1 to 4
Comparative examples 1-4 were identical to example 41 except that the catalysts used were different.
Comparative examples 5 to 8
Comparative examples 5 to 8 were identical to example 32 except that the catalysts used were different.
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Claims (25)

1. A ligand, characterized by the following structure:
wherein the substituents S of indenyl groups 1 、S 2 、S 3 、S 4 、S 5 、S 6 The same or different is selected from hydrogen, methyl, ethyl and isopropyl; substituent R 2 Selected from hydrogen, C1-C12 alkyl, C6-C12 aryl; substituent R 1 Selected from hydrogen, methyl, isopropyl.
2. The ligand of claim 1, wherein the substituents R 2 Selected from methyl, ethyl, isopropyl, tert-butyl, phenyl; substituent R 1 Selected from hydrogen, methyl, isopropyl.
3. A method of preparing a ligand according to claim 1, comprising the steps of:
(a) Under the inert gas atmosphere, dissolving indene compounds in an anhydrous solvent, mixing with alkyl lithium or sodium hydride at a low temperature, and then heating to room temperature for reaction to generate phase intermediate lithium or sodium salt B;
(b) Dispersing the lithium or sodium salt B in an anhydrous solvent in an inert gas atmosphere, mixing with halogenated ketone compounds at a low temperature, and then, heating to room temperature for reaction to generate a phase intermediate C;
(c) Mixing the intermediate C with an ammonium chloride aqueous solution, and heating for reaction to generate a ligand shown in a formula I;
the structural formula of the halogenated ketone compound is as follows:
wherein R is 1 、R 2 Y is halogen as defined in claim 1;
the structure of the intermediate lithium or sodium salt B is as follows:wherein S is 1 、S 2 、S 3 、S 4 、S 5 、S 6 The definition is the same as that of claim 1,
the structure of intermediate C is:wherein R is 1 、R 2 、S 1 、S 2 、S 3 、S 4 、S 5 、S 6 The definition is the same as that of claim 1.
4. A method of preparing a ligand according to claim 3, comprising the steps of:
in step (a), the molar ratio of alkyl lithium compound or sodium hydride to indenyl compound is 0.8-1.5:1.
5. a process for the preparation of a ligand according to claim 3, wherein in step (B) the molar ratio of halogenated ketone compound to lithium or sodium salt B is between 0.8 and 1.5:1.
6. a process for the preparation of a ligand according to claim 3, wherein in step (C) the molar ratio of ammonium chloride to intermediate C is from 0.8 to 1.5:1.
7. a process for the preparation of a ligand according to claim 3, wherein in step (c) the heating temperature is selected from 40 ℃ to 80 ℃.
8. An olefin polymerization catalyst characterized by the structural formula:
wherein M is selected from titanium, zirconium and hafnium; substituent S 1 、S 2 、S 3 、S 4 、S 5 、S 6 And R is 1 、R 2 Representing the same meaning as the ligand of claim 1; x is selected from halogen, hydrogen or alkane with 1-10 carbon atoms.
9. An olefin polymerization catalyst characterized by a structure selected from the group consisting of:
10. a process for preparing the olefin polymerization catalyst according to claim 8 or 9, characterized by comprising the steps of: dissolving the ligand according to claim 1 or 2 or the ligand prepared by the preparation method according to any one of claims 3 to 7 in an anhydrous solvent under an inert gas atmosphere, mixing with a catalyst at a low temperature, then reacting at room temperature to generate a phase intermediate, washing with a poor solvent, and then carrying out complexation reaction on the intermediate and a salt of metal M to prepare a complex;
the structure of the intermediate is as follows:substituent S 1 、S 2 、S 3 、S 4 、S 5 、S 6 And R is 1 、R 2 Representing the same meaning as the ligand of claim 1;
the catalyst is alkyl lithium or alkali metal hydride.
11. The method of claim 10, wherein the ligand to catalyst molar ratio is 1:1.6-2.5.
12. The method according to claim 10, wherein the catalyst is methyllithium, ethyllithium, butyllithium, hexyllithium, sodium hydride.
13. The process of claim 10, wherein the molar ratio of intermediate to metal M salt is 1:0.8 to 1.2.
14. The method of claim 10, wherein the ligand and catalyst are mixed at a temperature of-90 to-20 ℃.
15. The process according to claim 10, wherein the poor solvent is selected from the group consisting of n-hexane, n-pentane, n-heptane, cyclohexane.
16. The method for producing an olefin polymerization catalyst according to claim 8 or 9, wherein the ligand according to claim 1 or 2 or the ligand produced by the production method according to any one of claims 3 to 7 is dissolved in an anhydrous solvent under an inert gas atmosphere and subjected to a complexation reaction with an alkyl metal compound, thereby producing a complex.
17. The method of claim 16, wherein the molar ratio of the ligand to the metal alkyl is from 0.8 to 1.2.
18. The method of claim 16, wherein the anhydrous solvent is selected from one or more of benzene, toluene, xylene, tetrahydrofuran, diethyl ether, and methylene chloride.
19. Use of a catalyst according to claim 8 or 9 or a catalyst prepared according to any one of claims 10 to 18 in the polymerisation of olefins.
20. The use according to claim 19, wherein the catalyst according to claim 8 or 9 or the catalyst prepared by the process according to any one of claims 10 to 18 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 in a certain ratio to catalyze the olefin polymerization reaction.
21. The use according to claim 20, wherein the cocatalyst is MAO, MMAO, triisobutylaluminum, triphenylcarbon tetrafluoro phenyl boron.
22. Use according to claim 20, to catalyze the polymerization of olefins: one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, norbornene.
23. The use according to claim 20, wherein the molar ratio of promoter to central metal of the procatalyst is between 40 and 20000:1.
24. the use according to claim 20, wherein the polymerization temperature is 0-170 ℃ and the polymerization pressure is 0.1-10 MPa.
25. The use according to claim 20, wherein the molar equivalent ratio of catalyst to olefin added is 1:1000 to 1000000 molar equivalents.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890987B (en) * 2022-04-13 2023-12-19 万华化学集团股份有限公司 Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002308843A (en) * 2001-04-06 2002-10-23 Mitsubishi Rayon Co Ltd Catalyst for polymerization of olefins and method for producing olefin based polymer
KR20030012098A (en) * 2001-07-30 2003-02-12 삼성종합화학주식회사 Multi-nuclear Transition Metal Catalysts and Polymerization Process Using the Same
CN1578783A (en) * 2001-09-14 2005-02-09 住友化学工业株式会社 Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same
CN104418768A (en) * 2013-08-20 2015-03-18 中国科学院上海有机化学研究所 Double-metal olefin polymerization catalyst
CN106397263A (en) * 2015-07-31 2017-02-15 中国石油化工股份有限公司 Ligand compound and preparation thereof, and complex containing ligand compound
CN111484574A (en) * 2020-04-26 2020-08-04 万华化学集团股份有限公司 Olefin polymerization catalyst, olefin polymerization catalyst composition and method for preparing polyolefin
CN111943973A (en) * 2020-08-25 2020-11-17 万华化学集团股份有限公司 Bimetallic complex of phenoxy imine ligand skeleton, preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002308843A (en) * 2001-04-06 2002-10-23 Mitsubishi Rayon Co Ltd Catalyst for polymerization of olefins and method for producing olefin based polymer
KR20030012098A (en) * 2001-07-30 2003-02-12 삼성종합화학주식회사 Multi-nuclear Transition Metal Catalysts and Polymerization Process Using the Same
CN1578783A (en) * 2001-09-14 2005-02-09 住友化学工业株式会社 Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same
CN104418768A (en) * 2013-08-20 2015-03-18 中国科学院上海有机化学研究所 Double-metal olefin polymerization catalyst
CN106397263A (en) * 2015-07-31 2017-02-15 中国石油化工股份有限公司 Ligand compound and preparation thereof, and complex containing ligand compound
CN111484574A (en) * 2020-04-26 2020-08-04 万华化学集团股份有限公司 Olefin polymerization catalyst, olefin polymerization catalyst composition and method for preparing polyolefin
CN111943973A (en) * 2020-08-25 2020-11-17 万华化学集团股份有限公司 Bimetallic complex of phenoxy imine ligand skeleton, preparation method and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes;Chi-Tien Chen et al.;《Polyhedron》;第1-23页 *
Sanji Hagishita et al..Potent Inhibitors of Secretory Phospholipase A2: Synthesis and Inhibitory Activities of Indolizine and Indene Derivatives.1996,第39卷(第19期),第3636-3658页. *
乙烯和１－辛烯聚合催化体系的研究进展;陈志康 等;《厦门大学学报（自然科学版）》;第59卷(第5期);第679-701页 *
聚烯烃弹性体催化剂研究进展;王静 等;《分子催化》;第34卷(第6期);第579-591页 *

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