Preparation method of alpha-olefin copolymer

文档序号：1947919 发布日期：2021-12-10 浏览：17次中文

阅读说明：本技术 一种α-烯烃共聚物的制备方法 (Preparation method of alpha-olefin copolymer ) 是由陈冠良张彦雨车传亮丁明强张鹏坤王磊于 2021-09-13 设计创作，主要内容包括：本发明公开了一种α-烯烃共聚物的制备方法,该方法包括以α-烯烃、乙烯为原料聚合生成α-烯烃共聚物的方法；所述α-烯烃是在含式Ⅰ所示活性组分催化剂体系的存在下以乙烯为原料制备得到的齐聚产物。本发明以所述α-烯烃(主要为1-辛烯)为原料制备POE共聚物,原料纯度高,杂质成分少,可以获得高聚合活性以及高的1-辛烯插入率,增强POE产品的弹性及其他性能。(The invention discloses a preparation method of alpha-olefin copolymer, which comprises a method for generating alpha-olefin copolymer by using alpha-olefin and ethylene as raw materials through polymerization; the alpha-olefin is an oligomerization product prepared by taking ethylene as a raw material in the presence of a catalyst system containing an active component shown in a formula I. The invention takes the alpha-olefin (mainly 1-octene) as the raw material to prepare the POE copolymer, has high purity of the raw material and less impurity components, can obtain high polymerization activity and high insertion rate of the 1-octene, and enhances the elasticity and other properties of the POE product.)

1. The preparation method of the alpha-olefin copolymer is characterized by comprising a method for generating the alpha-olefin copolymer by taking alpha-olefin and ethylene as raw materials through polymerization;

the alpha-olefin is an oligomerization product prepared by taking ethylene as a raw material in the presence of a catalyst system containing an active component shown in a formula I;

in the formula I, Z is selected from C₂–C₅₀Alkylene substituted amino, C₆–C₅₀Arylene-substituted amino group, C₁–C₅₀Alkyl-substituted amino, C₆–C₅₀Aryl substituted amino, wherein the N atom in the amino is respectively connected with two P atoms in the formula I;

R₁、R₂、R₃identical or different, each independently selected from C₁–C₅₀Hydrocarbyl and C₆–C₅₀An aryl group;

m is selected from metals of groups VIB-VIII;

rn represents a coordinating group for M selected from organic or inorganic anions capable of coordinating with cations, and the number of Rn groups is 3.

2. The process for producing an α -olefin copolymer according to claim 1, wherein in the formula I, Z is selected from the group consisting of C₂–C₆Alkylene substituted amino, C₆–C₁₀Arylene-substituted amino group, C₁–C₁₀Alkyl-substituted amino, C₆–C₁₀Aryl substituted amino;

R₁、R₂、R₃each independently selected from C₁–C₅₀A hydrocarbyl group;

m is chromium;

the Rn group is selected from halogens.

3. The method of claim 2, wherein the complex catalyst represented by formula i is selected from the group consisting of those represented by the following structural formulae:

4. the method of claim 1, wherein the catalyst system further comprises an aluminum-containing co-catalyst and optionally, a boron-containing co-catalyst;

preferably, the proportion of the complex catalyst shown in the formula I, the aluminum-containing cocatalyst and the boron-containing cocatalyst in the catalyst system is 1 (500-1000) to 1-1.2 by mol.

5. The method of claim 4, wherein the aluminum-containing cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, diethylaluminum monochloride, tributylaluminum, triisobutylaluminum, tripropylaluminum, trioctylaluminum, dimethylaluminum chloride, dimethylisobutylaluminum, dimethylethylaluminum, triphenylaluminum, triisopropylaluminum, tri-sec-butylaluminum, ethyldimethylaluminum, methyldiethylaluminum, methylaluminoxane and modified methylaluminoxane.

6. The method of claim 4, wherein the boron-containing cocatalyst is selected from one or more of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) boron, tributylaminotetrakis (p-trifluoromethylphenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylamine tetrakis (pentafluorophenyl) boron, triphenylcarbenium tetraphenylboron, triphenylcarbenium tetrakis (p-trifluoromethylphenyl) boron, and methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate.

7. The method for producing an α -olefin copolymer according to any one of claims 1 to 6, wherein the α -olefin has a 1-octene content of 99.2 to 99.6%, a peroxide content of 0.8 to 1.5ppm, a carbonyl compound (as acetaldehyde) content of 2 to 4ppm, a water content of 2 to 4ppm, and a chlorine content of 3 to 4 ppm.

8. The process for producing an α -olefin copolymer according to any one of claims 1 to 7, wherein the α -olefin is obtained by oligomerization in the presence of a catalyst system comprising an active component represented by the formula I, an aluminum-containing cocatalyst and a boron-containing cocatalyst;

the oligomerization reaction conditions are as follows: the reaction temperature is 0-100 ℃, preferably 45-55 ℃, the reaction pressure is 0.1-10 MPa, preferably 4.0-6.0 MPa, and the reaction time is 1-120 min, preferably 30-90 min;

in the oligomerization reaction, the addition amount of the catalyst system is 2.0-4.0 mu mol/ml based on the concentration of metal in the complex catalyst shown in the formula I.

9. The method for producing an α -olefin copolymer according to any one of claims 1 to 8, wherein the method for producing an α -olefin copolymer comprises:

heating the reaction kettle to 140-150 ℃, vacuumizing and drying for 30-60 min, replacing with nitrogen for three times, and cooling the reaction kettle to below 80 ℃; adding a solvent and the alpha-olefin into a reaction kettle, then adding a metallocene catalyst, an aluminum-containing cocatalyst and a boron-containing cocatalyst, heating to 140-200 ℃, preferably 140-160 ℃, introducing ethylene to a reaction pressure of 0.1-10 MPa, preferably 3.0-5.0 MPa, starting a polymerization reaction, preferably 5-10 min for 1-15 min, emptying the ethylene, putting the reaction solution into ethanol, and collecting precipitated solids to obtain the alpha-olefin copolymer.

10. The method for producing an α -olefin copolymer according to claim 9, wherein the metallocene catalyst is a CGC catalyst;

the aluminum-containing cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, diethyl aluminum monochloride, tributylaluminum, triisobutylaluminum, tripropylaluminum, trioctylaluminum, dimethylaluminum chloride, dimethylaluminum isobutylate, dimethylethylaluminum, triphenylaluminum, triisopropylaluminum, tri-sec-butylaluminum, ethyldimethylaluminum, methyldiethylaluminum, methylaluminoxane and modified methylaluminoxane, preferably modified methylaluminoxane;

the boron-containing cocatalyst is one or more selected from the group consisting of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) boron, tributylaminotetrakis (p-trifluoromethylphenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylamine tetrakis (pentafluorophenyl) boron, triphenylcarbenium tetraphenylboron, triphenylcarbenium tetrakis (p-trifluoromethylphenyl) boron, methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate, preferably methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate;

the amount of the aluminum-containing cocatalyst is 200-1000 times of the catalyst, preferably 200-500 times of the molar amount of the metal;

the amount of the boron-containing cocatalyst is 1.0-1.5 times of the catalyst, preferably 1.0-1.2 times of the catalyst in terms of metal molar weight.

Technical Field

The invention relates to a preparation method, in particular to a preparation method of an alpha-olefin copolymer.

Background

Polyolefin elastomers (POE) are random copolymers of ethylene and α -olefin catalyzed by metallocene, have excellent weatherability and chemical resistance, good compatibility with polyolefin, high elasticity of rubber and easy processability of plastic, and the obtained elasticity has lower cost, lighter weight, lower energy consumption and more environmental friendliness.

The alpha-olefin production technology as the important raw material of POE is a key factor for restricting the industrialization of POE of enterprises. At present, the production methods of alpha-olefin are divided into ethylene oligomerization methods and coal-to-olefin methods, wherein the coal-to-olefin methods often obtain multi-component alpha-olefin, and if the method is further applied to preparation of POE, not only a single component needs to be separated out through high energy consumption, but also the reaction activity and the monomer insertion rate are seriously affected due to excessive oxygen, sulfur and other miscellaneous elements in the product, so that the preparation of POE by using the coal-to-olefin as a comonomer is restricted. The preparation of alpha-olefin by ethylene oligomerization method is more prone to generate single linear alpha-olefin with specific carbon number, which is the main source of POE comonomer, but the technical bottleneck at present is that the product selectivity is low, and the content of linear alpha-olefin with specific carbon number is low, so that high energy consumption is still needed for product separation. For example, WO2004056479A1 of Sasol (Sasol corporation) discloses that a chromium compound with a nitrogen-phosphorus coordination framework is used as a catalyst to catalyze ethylene oligomerization at 45 ℃ and 4.5MPa to generate 16.6-32.7% of 1-hexene and 44-67% of 1-octene.

Phillips (Phillips company) EP0780353A1 takes a chromium compound with pyrrole as a ligand as a catalyst, and catalyzes ethylene trimerization at 115 ℃ and 10MPa to generate 1-hexene with the purity of 93 percent, but the method is only suitable for producing medium and low-end products, namely 1-hexene, and cannot prepare high-carbon-number alpha-olefins such as 1-octene, 1-decene and the like.

In conclusion, it is necessary to develop a high-selectivity, high-purity and high-carbon-number α -olefin that can be directly applied to the preparation of POE, so as to avoid the costly separation process and apparatus and ensure considerable copolymerization activity and monomer insertion rate.

Disclosure of Invention

The invention provides a preparation method of alpha-olefin copolymer, which directly uses high-purity alpha-olefin product (1-octene) obtained by ethylene oligomerization reaction in the presence of a specific catalyst as a comonomer for application, can meet the high standard requirement of POE copolymerization raw materials in the industry, and is beneficial to preparing POE elastomer with higher monomer insertion rate.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of alpha-olefin copolymer comprises a method for generating alpha-olefin copolymer by taking alpha-olefin and ethylene as raw materials through polymerization;

the alpha-olefin is an oligomerization product prepared by taking ethylene as a raw material in the presence of a catalyst system containing an active component shown in a formula I;

R₁、R₂、R₃identical or different, each independently selected from C₁–C₅₀Hydrocarbyl and C₆–C₅₀An aryl group;

m is selected from metals of groups VIB-VIII;

rn represents a coordinating group for M selected from organic or inorganic anions capable of coordinating with cations, and the number of Rn groups is 3.

In the present invention, as a preferred embodiment, in formula I, Z is selected from C₂–C₆Alkylene substituted amino, C₆–C₁₀Arylene-substituted amino group, C₁–C₁₀Alkyl-substituted amino, C₆–C₁₀Aryl substituted amino;

R₁、R₂、R₃each independently selected from C₁–C₅₀A hydrocarbyl group;

m is chromium;

the Rn group is selected from halogens.

In the present invention, as a preferred embodiment, the complex catalyst represented by formula i is selected from the group consisting of those represented by the following structural formulae:

preferably, the preparation method of the complex catalyst shown in the formula I comprises the following steps:

1) cooling the tetrahydrofuran solution of the Grignard reagent to 0-5 ℃, dropwise adding the tetrahydrofuran solution dissolved with alkyl ketone, stirring at room temperature for 15-24 h after dropwise adding, evaporating to remove the solvent, and drying at 60-65 ℃ for 6-8 h in vacuum to obtain a compound of formula II;

the molar ratio of the Grignard reagent to the alkyl ketone is 1 (1-1.2);

the volume usage (ml) of the tetrahydrofuran is 100-150 times of the molar usage of the raw materials;

preferably, the Grignard reagent is selected from one or more of n-butyl magnesium bromide, isopropyl magnesium bromide, phenyl magnesium bromide, n-butyl magnesium chloride, isopropyl magnesium chloride, and phenyl magnesium chloride;

preferably, the alkyl ketone is selected from one or more of 5-nonanone, 2, 4-dimethyl-3-pentanone, benzophenone and 2-methyl-3-heptanone.

2) Cooling thionyl chloride to 0-5 ℃, adding a compound of the formula II under stirring, heating to 50-55 ℃ after the addition, stirring for reacting for 6-8 h, concentrating to dryness, and drying at 60-65 ℃ in vacuum for 6-8 h to obtain a compound of the formula III;

the volume (ml) of the thionyl chloride is 1000-2000 times of the molar weight of the compound shown in the formula II;

3) dissolving 1, 4-dibromo-2-fluorobenzene in tetrahydrofuran, placing the tetrahydrofuran at-80 to-78 ℃, slowly dripping n-butyllithium within 2 to 3 hours, stirring and reacting for 2 to 3 hours after dripping is finished, slowly dripping a compound shown in the formula III at-80 to-78 ℃, slowly heating to room temperature and stirring for 2 to 3 hours after dripping is finished, adding deionized water and n-hexane for extraction, spin-drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane to obtain a compound shown in the formula IV;

the molar ratio of the compound shown in the formula III, 1, 4-dibromo-2-fluorobenzene and n-butyllithium is 1: 1.1-1.3: 1.1 to 1.5;

the volume consumption (ml) of the tetrahydrofuran is 30-50 times of the molar consumption of the 1, 4-dibromo-2-fluorobenzene;

the volume consumption (ml) of the deionized water and the volume consumption (ml) of the normal hexane are respectively 0.8-1 time of the volume consumption (ml) of the tetrahydrofuran;

4) cooling the ether solution of phosphorus trichloride to-80-78 ℃, slowly dropwise adding diethylamine, after dropwise adding, heating to room temperature within 2-3 h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂；

The molar ratio of the phosphorus trichloride to the diethylamine is 1: 2-2.4;

the volume usage (ml) of the diethyl ether is 10-30 times of the molar usage of the phosphorus trichloride;

5) dissolving n-butyllithium in tetrahydrofuran, placing at-78 to-80 ℃, dissolving a compound shown in the formula IV in the tetrahydrofuran, slowly dropwise adding the compound into the n-butyllithium within 2-3 h, stirring and reacting for 1-2 h after dropwise adding, and slowly dropwise adding a compound (Et) at-80 to-78 DEG₂N)PCl₂Heating the tetrahydrofuran solution to-10 ℃, stirring overnight, adding toluene, stirring for 1-2 h, spin-drying the solvent, adding toluene, filtering to remove precipitates, spin-drying the filtrate, adding phosphorus trichloride, performing reflux reaction for 2-3 h, removing the solvent at 80 ℃ in vacuum, adding n-hexane into the spin-dried solid, stirring, filtering, and spin-drying the filtrate to obtain a compound of formula V;

the compound of formula IV, n-butyllithium, (Et)₂N)PCl₂And PCl₃In a molar ratio of 1: 1-1.2: 0.5-0.8: 2.5 to 2.8;

the volume usage (ml) of the tetrahydrofuran is 10-40 times of the molar usage of the raw materials;

the volume consumption (ml) of the toluene and the n-hexane is 50-100 ml;

6) dissolving a compound shown in the formula V in dichloromethane, stirring at-5-0 ℃, adding triethylamine, slowly dropwise adding primary amine, after the dropwise addition of the primary amine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran for three times, and spin-drying the filtrate to obtain a compound shown in the formula VI;

the molar ratio of the primary amine to the compound of formula v is 1:2 to 2.5; the dosage of triethylamine is 2-2.8 times of the molar weight of primary amine;

the volume dosage (ml) of the dichloromethane is 10-50 times of the molar dosage of the compound of the formula V;

the volume consumption (ml) of the tetrahydrofuran is 10-50 ml;

the primary amine is selected from one or more of isopropylamine, tert-butylamine, (1,1,2, 2-tetramethylpropyl) amine hydrochloride, 2-amino-2, 3-dimethylbutane, aminomethyl trimethylsilane and cyclohexylamine;

7) heating and refluxing a metal compound and a compound shown in a formula V for 24-72 hours in toluene, wherein the heating temperature is 80-100 ℃, removing filtrate in vacuum, and performing vacuum drying on insoluble substances to obtain a complex catalyst shown in a formula I;

the metal compound is an organic chromium compound, preferably one or more selected from chromium acetylacetonate, chromium trichloride tris (tetrahydrofuran), chromium 2-ethylhexanoate, chromium benzoylacetonate, chromium tris (2,2,6, 6-tetramethyl-3, 5-pimelic acid), chromium hexafluoro-2, 4-glutarate and chromium acetate hydroxide;

the molar ratio of the metal compound to the compound of formula V is 1:1 to 1.2;

the volume dosage (ml) of the toluene is 10-50 times of the molar dosage of the compound of the formula V;

all the above synthesis experiments were performed under nitrogen atmosphere.

The above reaction steps can be represented by the following reaction process expression:

wherein X represents halogen, R' is selected from C₂–C₅₀Alkylene group, C₆–C₅₀Arylene radical, C₁–C₅₀Alkyl radical, C₆–C₅₀Radical of aryl, R₁、R₂、R₃Rn and M are as defined above for formula I.

In the present invention, as a preferred embodiment, the catalyst system further comprises an aluminum-containing promoter and, optionally, a boron-containing promoter;

In the present invention, as a preferred embodiment, the aluminum-containing cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, diethylaluminum monochloride, tributylaluminum, triisobutylaluminum, tripropylaluminum, trioctylaluminum, dimethylaluminum chloride, dimethylisobutylaluminum, dimethylethylaluminum, triphenylaluminum, triisopropylaluminum, tri-sec-butylaluminum, ethyldimethylaluminum, methyldiethylaluminum, methylaluminoxane and modified methylaluminoxane.

In the present invention, as a preferred embodiment, the boron-containing cocatalyst is selected from one or more of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) boron, N-dimethylaniliniumtetrakis (pentafluorophenyl) boron, tributylaminotetrakis (p-trifluoromethylphenyl) boron, N-diethylaniliniumtetraphenylboron, N-diethylaniliniumtetrakis (pentafluorophenyl) boron, diethylamine tetrakis (pentafluorophenyl) boron, triphenylcarbeniumtetraphenylboron, triphenylcarbeniumtetrakis (p-trifluoromethylphenyl) boron, methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate.

In the present invention, as a preferred embodiment, the α -olefin has a monoolefin content of 99.6 to 99.8%, a 1-octene content of 99.2 to 99.6%, a peroxide content of 0.8 to 1.5ppm, a carbonyl compound content (calculated as acetaldehyde) of 2 to 4ppm, a water content of 2 to 4ppm, and a chlorine content of 3 to 4 ppm.

In the present invention, as a preferred embodiment, the α -olefin is obtained by oligomerization in the presence of a catalyst system comprising an active component represented by formula i, an aluminum-containing cocatalyst and a boron-containing cocatalyst;

in the oligomerization reaction, the addition amount of the catalyst system is 2.0-4.0 mu mol/ml based on the concentration of metal in the complex catalyst shown in the formula I. Furthermore, the molar ratio of the complex catalyst shown in the formula I, the aluminum-containing cocatalyst and the boron-containing cocatalyst in the catalyst system is 1 (500-1000) to 1-1.2.

Specifically, in the ethylene oligomerization reaction, the adding mode of the catalyst system is not limited in the present invention, and the active component shown in formula i, the aluminum-containing cocatalyst and the boron-containing cocatalyst may be mixed in advance and then added together into the reactor, or may be added into the reactor separately to prepare the activated catalyst by mixing, so as to provide the catalytic activity for the oligomerization reaction.

As a preferred embodiment of the invention, before the reaction, the reaction kettle is heated to 120-150 ℃, vacuumized for 1-3 hours, replaced by nitrogen, replaced by ethylene for 3-5 times after being cooled to normal temperature, and the solvent is added into the reaction kettle, and then the catalyst system is added to carry out ethylene oligomerization reaction.

In a preferred embodiment of the invention, the oligomerization reaction is carried out in the presence of an organic solvent, wherein the organic solvent is one or more of aliphatic hydrocarbon and aromatic hydrocarbon; preferably, the aliphatic hydrocarbon is n-heptane, pentane, cyclohexane or methylcyclohexane, and the aromatic hydrocarbon is one or more of toluene, xylene, ethylbenzene, n-propylbenzene and diphenylmethane.

In the invention, the oligomerization reaction is an intermittent reaction, the catalyst activity is more than 800Kg/gM/h in the intermittent process, and M is active metal.

The alpha-olefin prepared by the scheme of the invention is in a liquid state, after the reaction is finished, the polymer generated by oligomerization is filtered and removed, and the selectivity of 1-octene in the filtrate is tested; then, the 1-octene product is refined by rectification, and the purity and the impurity content of the 1-octene in the product are tested. The rectification conditions were as follows: the pressure in the tower is 0.05-0.15 MPaG, the temperature of the tower kettle is 130-140 ℃, the temperature of the tower top is 118-125 ℃, the reflux ratio is 1.5-2.2, the height of the rectifying column is 1000mm, and the packing is a triangular spiral.

In the present invention, as a preferred embodiment, the method for preparing the α -olefin copolymer comprises:

Preferably, the metallocene catalyst is a silicon-bridged CGC catalyst, and the dosage of the catalyst in the reaction system is 1.2-2.5 mu mol relative to the volume of each liter of the reactor;

the aluminum-containing cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, diethylaluminum monochloride, tributylaluminum, triisobutylaluminum, tripropylaluminum, trioctylaluminum, dimethylaluminum chloride, dimethylaluminum isobutylate, dimethylethylaluminum, triphenylaluminum, triisopropylaluminum, tri-sec-butylaluminum, ethyldimethylaluminum, methyldiethylaluminum, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO), preferably Modified Methylaluminoxane (MMAO);

the amount of the aluminum-containing cocatalyst is 200-1000 times of the catalyst, preferably 200-500 times of the molar amount of the metal;

the amount of the boron-containing cocatalyst is 1.0-1.5 times of the catalyst, preferably 1.0-1.2 times of the catalyst in terms of metal molar weight.

The invention takes the alpha-olefin (mainly 1-octene) as the raw material to prepare the POE copolymer, has higher raw material purity and less impurity components, can improve the insertion rate of the 1-octene in the product POE, and enhances the elasticity and other properties of the POE product.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.

The starting materials used in the examples are conventional in the art and the purity specifications used are either analytically or chemically pure.

The source information of the main raw materials in the following examples:

1, 4-dibromo-2-fluorobenzene: 97.0%, Bailingwei technologies, Beijing;

p-dibromobenzene: 99.0%, Shanghai Aladdin Biotechnology, Inc.;

sulfoxide chloride: 99.7%, Shanghai Aladdin Biotechnology, Inc.;

triethylamine: not less than 99.0%, Shanghai Allatin Biotechnology Ltd;

diethylamine: not less than 99.0%, Shanghai Allatin Biotechnology Ltd;

phosphorus trichloride: 95.5% or more, national drug group chemical reagent limited;

n-butyl lithium: 15.0% hexane solution (1.6mol), Shanghai Aladdin Biotech Ltd;

toluene: 99.5%, Shanghai Michelin Biotechnology, Inc.;

tetrahydrofuran: 99.0%, Shanghai Aladdin Biotechnology, Inc.;

dichloromethane: 99.8%, Shanghai Aladdin Biotechnology, Inc.;

chromium trichloride tris (tetrahydrofuran): 98%, Bailingwei technologies, Beijing;

triisobutylaluminum: 99.0%, saren chemical technology (shanghai) ltd;

n-butyl magnesium bromide: 98.5%, Wuhanxin Yangyui and chemical technology, Inc.;

isopropyl magnesium bromide: tetrahydrofuran solution (1.0mol), Beijing Bailingwei science and technology Co., Ltd;

phenyl magnesium bromide: tetrahydrofuran solution (1.0mol), sahn chemical technology (shanghai) ltd;

isopropylamine: 99.0%, chemical reagents of national drug group, ltd;

tert-butylamine: not less than 99.5%, national drug group chemical reagent limited;

cyclohexane: not less than 99.0%, chemical reagents of national drug group limited;

(1,1,2, 2-tetramethylpropyl) amine hydrochloride: 95.0 percent, Jiangsu Aikang biological medicine research and development Limited company;

2-amino-2, 3-dimethylbutane: 95.0 percent, Jiangsu Aikang biological medicine research and development Limited company;

aminomethyl trimethylsilane: 98.0%, Shanghai Aladdin Biotechnology, Inc.;

5-nonanone: 98.0%, Shanghai Michelin Biotechnology, Inc.;

2, 4-dimethyl-3-pentanone: 98.0%, Shanghai Michelin Biotechnology, Inc.;

benzophenone: 99.0%, Shanghai Aladdin Biotechnology, Inc.;

iPr-PNP: 98.0%, Jiangsu Xinnuo catalyst Co., Ltd;

MMAO: modified methylaluminoxane, 7% n-heptane solution, Nouryon;

tetrakis (pentafluorophenyl) borate-methyldi- (octadecyl) ammonium salt: : AR, Shanghai Aladdin Biotechnology GmbH;

dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) titanium dichloride (CGC): 98.5%, Jiangsu Xinnoco catalyst Co.

In each embodiment of the invention, the reaction raw materials participating in polymerization are used after being refined by sodium wire reflux.

Secondly, the following test method is adopted in each example of the invention:

the liquid phase products are characterized by gas chromatography, so that the mass of each liquid phase product is obtained, and the solid products are separated, dried and weighed;

analysis conditions for gas chromatography: the temperature of a sample injection product is 250 ℃; the temperature of the column box is 35 ℃;

temperature rising procedure: firstly keeping the temperature at 35 ℃ for 10 minutes, then increasing the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping the temperature at 250 ℃ for 10 minutes, and then beginning to cool until the room temperature;

detector temperature: 250 ℃; carrier: 1.0 Mpa; air: 0.03 MPa; hydrogen gas: 0.03 MPa;

the characterization of the product is carried out by taking nonane as an internal standard substance and the calculation method is as follows:

in the formula, m1 represents the mass of a certain substance, m is the mass of nonane, a1 is the peak area of the substance measured in a GC, and a is the peak area of the nonane measured in the GC. k is a correction coefficient.

The compounds of the examples were characterized by means of nuclear magnetic resonance spectroscopy (Brucker ARX-400).

The molecular weight and molecular weight distribution of the polymer obtained in the example of ethylene/1-octene polymerization were measured by PL-GPC220 at 150 ℃ using three PLgel 10 μm MIXED-B separation columns in series, 1,2, 4-trichlorobenzene as solvent.

The melting points of the polymers were measured by a conventional DSC (Q2000) method, and the polymerization activities of the polymers were calculated according to the following formulas: polymerization activity is the polymer mass/(metal content in catalyst polymerization time).

Reference is made to the method for calculating the insertion rate of 1-octene (Macromolecules 1999, 32, 3817). The polymer high-temperature nuclear magnetism is obtained by using deuterated 1,1,2, 2-tetrachloroethane as a solvent and adopting Bruker DMX300MHz test at the temperature of 120 ℃.

[ example 1 ] preparation of Complex catalyst Cat1

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling a tetrahydrofuran (200ml) solution of n-butyl magnesium bromide (2.0mol) to 0 ℃, dropwise adding the tetrahydrofuran (200ml) solution dissolved with 5-nonanone (2.0mol), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ for 6h in vacuum to obtain a compound II.

2) Cooling 1600ml of thionyl chloride to 0 ℃, adding the compound II (1.6mol) under stirring, heating to 50 ℃ after the addition is finished, stirring for reacting for 6h, concentrating to dryness, and drying at 60 ℃ in vacuum for 6h to obtain a compound III.

3) Dissolving 1, 4-dibromo-2-fluorobenzene (2.2mol) in tetrahydrofuran (66ml), placing at-80 ℃ for 2h, slowly dropwise adding n-butyllithium (2.2mol) within 2h, stirring for reacting for 2h after dropwise adding, slowly dropwise adding a compound III (2.0mol) at-80 ℃, slowly heating to room temperature after dropwise adding, stirring for 2h, adding deionized water (52ml) and n-hexane (52ml) for extraction, spin-drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane, and obtaining a compound IV.

4) Cooling the solution of phosphorus trichloride (3.0mol) in diethyl ether (30ml) to-80 deg.C, slowly adding diethylamine (6.0mol) dropwise, heating to room temperature within 2h, filtering, and spin drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) in tetrahydrofuran (6ml) at-10 deg.CStirring overnight, adding toluene (50ml), stirring for 1h, spin-drying the solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying the filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at the temperature of minus 5 ℃, adding triethylamine (2.0mol), slowly dropwise adding isopropylamine (1.0mol), after the dropwise adding of the isopropylamine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.28-7.18(m，12H)，3.00-2.97(m，1H)，1.54(s，24H)，1.31-1.29(d，24H)，1.10-1.07(d，6H)，0.90(s，36H)

7) heating and refluxing 0.8mol of chromium trichloride tris (tetrahydrofuran) and 0.8mol of compound VI in 8ml of toluene for 24h, wherein the heating temperature is 80 ℃, removing the filtrate in vacuum, and performing vacuum pumping on insoluble substances to obtain the complex Cat1 shown in the following formula.

[ example 2 ] preparation of Complex catalyst Cat2

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling the solution of isopropyl magnesium bromide (2.0mol) in tetrahydrofuran (220ml) to 1 ℃, dropwise adding the solution of 2, 4-dimethyl-3-pentanone (2.2mol) in tetrahydrofuran (220ml), stirring at room temperature for 20h after dropwise adding, evaporating to remove the solvent, and drying at the vacuum temperature of 62 ℃ for 7h to obtain a compound II.

2) 1760ml of thionyl chloride is cooled to 1 ℃, and the compound II (1.6mol) is added under stirring, after the addition, the temperature is raised to 52 ℃, the reaction is stirred for 7 hours, the mixture is concentrated to be dry, and the mixture is dried for 7 hours under vacuum at 62 ℃, so that the compound III is obtained.

3) Dissolving 1, 4-dibromo-2-fluorobenzene (2.4mol) in tetrahydrofuran (84ml), placing at-79 ℃ for 3h, slowly dropwise adding n-butyllithium (2.4mol) within 3h, stirring for reacting for 3h after dropwise adding, slowly dropwise adding a compound III (2.0mol) at-79 ℃, slowly heating to room temperature after dropwise adding, stirring for 3h, adding deionized water (75ml) and n-hexane (75ml) for extraction, spin-drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane, and obtaining a compound IV.

4) Cooling the solution of phosphorus trichloride (3.0mol) in diethyl ether (45ml) to-79 ℃, slowly adding diethylamine (6.3mol) dropwise, after the dropwise addition is finished, heating the solution in the reactor 3 to room temperature, filtering, and spin-drying the filtrate to obtain the product compound (Et₂N)PCl₂。

5) Dissolving n-butyllithium (1.3mol) in tetrahydrofuran (26ml), placing at-79 ℃, dissolving a compound IV (1.2mol) in tetrahydrofuran (24ml), slowly dropwise adding into the n-butyllithium within 3h, stirring for reacting for 2h after the dropwise adding is finished, and slowly dropwise adding a compound (Et) at-78-80 DEG₂N)PCl₂(0.7mol) tetrahydrofuran (14ml), heating to-10 deg.C, stirring overnight, adding toluene (60ml), stirring for 2h, spin-drying solvent, adding toluene (60ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.1mol) refluxing for 3h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (60ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.2mol) in dichloromethane (44ml), stirring at the temperature of minus 1 ℃, adding triethylamine (2.2mol), slowly dropwise adding isopropylamine (1.0mol), after the dropwise adding of the isopropylamine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (20ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.28-7.18(m，12H)，3.00-2.97(m，1H)，2.25-2.20(m，12H)，1.10-1.07(d，6H)，0.88(s，72H)

7) heating and refluxing 0.80mol of chromium trichloride tris (tetrahydrofuran) and 0.88mol of compound VI in 17ml of toluene for 36h, wherein the heating temperature is 90 ℃, removing the filtrate in vacuum, and performing vacuum pumping on insoluble substances to obtain the complex Cat 2.

[ example 3 ] preparation of Complex Cat3

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling the tetrahydrofuran (240ml) solution of phenylmagnesium bromide (2.0mol) to 2 ℃, dropwise adding the tetrahydrofuran (288ml) solution of benzophenone (2.4mol), stirring at room temperature for 24h after dropwise adding, evaporating to remove the solvent, and drying at 65 ℃ for 8h in vacuum to obtain the compound II.

2) 2400ml of thionyl chloride is cooled to 2 ℃, and compound II (1.6mol) is added under stirring, after the addition, the temperature is raised to 53 ℃, the reaction is stirred for 8 hours, the reaction solution is concentrated to be dry, and the reaction solution is dried for 8 hours under vacuum at 63 ℃ to obtain compound III.

3) Dissolving 1, 4-dibromo-2-fluorobenzene (2.6mol) in tetrahydrofuran (105ml), placing at-78 ℃ for 2.5h, slowly dropwise adding n-butyllithium (2.8mol) within 2.5h, stirring for reacting for 2.5h after dropwise adding, slowly dropwise adding a compound III (2.0mol) at-78 ℃, slowly heating to room temperature after dropwise adding, stirring for 2.5h, adding deionized water (105ml) and n-hexane (105ml) for extracting, spin drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane, and obtaining a compound IV.

4) Cooling the diethyl ether (60ml) solution of phosphorus trichloride (3.0mol) to-78 ℃, slowly adding diethylamine (6.6mol) dropwise, after the dropwise addition is finished, heating to room temperature within 2.5h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.4mol) in tetrahydrofuran (42ml), standing at-78 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (36ml), slowly adding dropwise into n-butyllithium within 2.5h, stirring to react for 1.5h, and slowly adding dropwise compound (Et) at-78 deg.C₂N)PCl₂(0.8mol) tetrahydrofuran (24ml), heating to-10 deg.C, stirring overnight, adding toluene (80ml), stirring for 1.5h, spin-drying solvent, adding toluene (80ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.2mol) refluxing for 2.5h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (80ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.4mol) in dichloromethane (72ml), stirring at the temperature of minus 3 ℃, adding triethylamine (2.4mol), slowly dropwise adding isopropylamine (1.0mol), after the dropwise adding of the isopropylamine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (30ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.33-7.24(m，40H)，7.11-7.00(m，28H)，6.95-6.88(m，8H)，3.00-2.97(m，1H)，1.10-1.07(d，6H)

7) heating and refluxing 0.8mol of chromium trichloride tris (tetrahydrofuran) and 1.0mol of compound VI in toluene (30ml) for 72h, wherein the heating temperature is 100 ℃, removing the filtrate in vacuum, and obtaining the complex Cat3 after insoluble substances are dried in vacuum.

[ example 4 ] preparation of Complex 4

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling a tetrahydrofuran (300ml) solution of n-butyl magnesium bromide (2.0mol) to 3 ℃, dropwise adding a tetrahydrofuran (300ml) solution dissolved with 2, 4-dimethyl-3-pentanone (2.0mol), stirring at room temperature for 24h after dropwise adding is finished, evaporating to remove the solvent, and drying at 65 ℃ for 8h in vacuum to obtain a compound II.

2) 3200ml of thionyl chloride is cooled to 3 ℃, and a compound II (1.6mol) is added under stirring, after the addition, the temperature is raised to 55 ℃, the stirring reaction is carried out for 8 hours, the mixture is concentrated to be dry, and the mixture is dried for 8 hours under the vacuum condition at 65 ℃ to obtain a compound III.

3) Dissolving 1, 4-dibromo-2-fluorobenzene (2.4mol) in tetrahydrofuran (120ml), placing at-78 ℃ for 3h, slowly dropwise adding n-butyllithium (3.0mol) within 3h, stirring for reacting for 3h after dropwise adding, slowly dropwise adding a compound III (2.0mol) at-78 ℃, slowly heating to room temperature after dropwise adding, stirring for 3h, adding deionized water (120ml) and n-hexane (120ml) for extraction, spin drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane, and obtaining a compound IV.

4) Cooling the diethyl ether (90ml) solution of phosphorus trichloride (3.0mol) to-78 ℃, slowly dropwise adding diethylamine (7.2mol), after dropwise adding, heating to room temperature within 3h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.4mol) in tetrahydrofuran (56ml), standing at-78 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (48ml), slowly adding dropwise into n-butyllithium within 3h, stirring to react for 2h, and slowly adding dropwise compound (Et) at-78 deg.C₂N)PCl₂(1.0mol) in tetrahydrofuran (40ml), the temperature was raised to-10 ℃, stirring overnight, toluene (50ml) was added and stirred for 2h, the solvent was dried, toluene (100ml) was added, the precipitate was removed by filtration, the filtrate was dried, PCl was added₃(3.3mol) refluxing for 3h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (100ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.5mol) in dichloromethane (125ml), stirring at 0 ℃, adding triethylamine (2.8mol), slowly dropwise adding isopropylamine (1.0mol), after the dropwise adding of the isopropylamine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (50ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.28-7.18(m，12H)，3.00-2.97(m，1H)，2.25-2.20(m，8H)，1.54(s，8H)，1.31-1.29(m，16H)，1.09-1.06(d，6H)，0.88(s，60H)

7) heating and refluxing 0.8mol of chromium trichloride tris (tetrahydrofuran) and 1.0mol of compound VI in 50ml of toluene for 72h, wherein the heating temperature is 100 ℃, removing the filtrate in vacuum, and obtaining the complex Cat4 after insoluble substances are dried in vacuum.

[ example 5 ] preparation of Complex 5

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling the tetrahydrofuran (225ml) solution of phenylmagnesium bromide (2.0mol) to 0 ℃, dropwise adding the tetrahydrofuran (215ml) solution dissolved with 5-nonanone (2.0mol), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ for 6h in vacuum to obtain the compound II.

2) Cooling 1600ml of thionyl chloride to 5 ℃, adding the compound II (1.6mol) under stirring, heating to 50 ℃ after the addition is finished, stirring for reacting for 6h, concentrating to dryness, and drying at 60 ℃ in vacuum for 6h to obtain a compound III.

3) Dissolving 1, 4-dibromo-2-fluorobenzene (2.2mol) in tetrahydrofuran (66ml), placing at-80 ℃ for 2h, slowly dropwise adding n-butyllithium (2.2mol) within 2h, stirring for reacting for 2h after dropwise adding, slowly dropwise adding a compound III (2.0mol) at-80 ℃, slowly heating to room temperature after dropwise adding, stirring for 2h, adding deionized water (60ml) and n-hexane (60ml) for extraction, spin-drying an organic phase, purifying by adopting a silica gel column chromatography method, wherein a mobile phase is n-hexane, and obtaining a compound IV.

4) Cooling the diethyl ether (30ml) solution of phosphorus trichloride (3.0mol) to-80 ℃, slowly adding diethylamine (6.0mol) dropwise, after the dropwise addition is finished, heating to room temperature within 3h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.37-7.28(m，24H)，7.07-7.02(m，8H)，3.00-2.97(m，1H)，1.87(s，12H)，1.31-1.29(m，32H)，1.10-1.06(d，6H)，0.89(s，24H)

[ example 6 ] preparation of Complex 6

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling a tetrahydrofuran (200ml) solution of phenylmagnesium bromide (2.0mol) to 5 ℃, dropwise adding a tetrahydrofuran (200ml) solution dissolved with 2-methyl-3-heptanone (2.0mol), stirring at room temperature for 15h after dropwise adding is finished, evaporating to remove the solvent, and drying at 60 ℃ in vacuum for 6h to obtain a compound II.

4) Cooling the diethyl ether (30ml) solution of phosphorus trichloride (3.0mol) to-80 ℃, slowly adding diethylamine (6.0mol) dropwise, after the dropwise addition is finished, heating to room temperature within 2.5h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.35-7.26(m，24H)，7.09-7.04(m，8H)，3.02-2.99(m，1H)，2.55(m，1H)，1.87(s，8H)，1.35-1.27(m，8H)，1.12-1.08(d，6H)，0.91(s，36H)

[ example 7 ] preparation of Complex Cat7

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling a tetrahydrofuran (200ml) solution of n-butyl magnesium bromide (2.0mol) to 5 ℃, dropwise adding the tetrahydrofuran (200ml) solution dissolved with benzophenone (2.0mol), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ in vacuum for 6h to obtain a compound II.

2) Cooling 1600ml of thionyl chloride to 3 ℃, adding the compound II (1.6mol) under stirring, heating to 50 ℃ after the addition is finished, stirring for reacting for 6h, concentrating to dryness, and drying at 60 ℃ in vacuum for 6h to obtain a compound III.

4) Cooling the solution of phosphorus trichloride (3.0mol) in diethyl ether (30ml) to-80 ℃, slowly adding diethylamine (6.0mol) dropwise, after the dropwise addition is finished, heating to room temperature within 2h, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.40-7.28(m，44H)，7.20-7.07(m，8H)，3.00-2.96(m，1H)，2.53-2.50(m，8H)，1.31-1.25(m，16H)，1.10-1.06(d，6H)，0.93(s，12H)

[ example 8 ] preparation of Complex Cat8

All synthetic experiments were performed under nitrogen atmosphere.

1) Cooling a tetrahydrofuran (200ml) solution of phenylmagnesium bromide (2.0mol) to 5 ℃, dropwise adding a tetrahydrofuran (200ml) solution dissolved with 2, 4-dimethyl-3-pentanone (2.0mol), stirring at room temperature for 15h after dropwise adding is finished, evaporating to remove the solvent, and drying at 60 ℃ for 6h in vacuum to obtain a compound II.

4) A solution of phosphorus trichloride (3.0mol) in diethyl ether (30ml) was cooled to-80Slowly dropwise adding diethylamine (6.0mol), heating to room temperature within 3h after dropwise adding, filtering, and spin-drying the filtrate to obtain the product compound (Et)₂N)PCl₂。

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.42-7.30(m，44H)，7.22-7.10(m，8H)，3.00-2.96(m，1H)，2.62-2.59(m，8H)，1.10-1.06(d，6H)，0.89(s，48H)

[ example 9 ] preparation of Complex Cat9

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling the solution of isopropyl magnesium bromide (2.0mol) in tetrahydrofuran (200ml) to 0 ℃, dropwise adding the solution of 5-nonanone (2.0mol) in tetrahydrofuran (200ml), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ for 6h under vacuum to obtain the compound II.

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.26-7.16(m，12H)，3.05-2.97(m，1H)，2.20-2.15(m，4H)，1.56(s，16H)，1.35-1.30(m，32H)，1.15-1.10(d，6H)，0.89(s，48H)

[ example 10 ] preparation of Complex Cat10

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling the solution of isopropyl magnesium bromide (2.0mol) in tetrahydrofuran (200ml) to 3 ℃, dropwise adding the solution of benzophenone (2.0mol) in tetrahydrofuran (200ml), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ in vacuum for 6h to obtain the compound II.

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.42-7.30(m，44H)，7.22-7.10(m，8H)，2.30-2.95(m，5H),1.20-1.15(d，6H)，0.85(s，24H)

[ example 11 ] preparation of Complex Cat11

All synthetic experiments were performed under nitrogen atmosphere:

1) cooling a tetrahydrofuran (200ml) solution of n-butyl magnesium bromide (2.0mol) to 5 ℃, dropwise adding the tetrahydrofuran (200ml) solution dissolved with 5-nonanone (2.0mol), stirring at room temperature for 15h after dropwise adding, evaporating to remove the solvent, and drying at 60 ℃ for 6h in vacuum to obtain a compound II.

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at the temperature of minus 5 ℃, adding triethylamine (2.0mol), slowly dropwise adding tert-butylamine (1.0mol), after the dropwise adding of the tert-butylamine is finished, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.30-7.22(m，12H)，1.50(s，24H)，1.31-1.25(m，57H)，0.90(s，36H)

[ example 12 ] preparation of Complex Cat12

All synthetic experiments were performed under nitrogen atmosphere:

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 ℃, dissolving a compound IV (1.2mol) in tetrahydrofuran (12ml), slowly dropwise adding the mixture into the n-butyllithium within 2h, stirring for reacting for 1h after the dropwise addition is finished, and slowly dropwise adding a compound containing N-butyllithium at-80 DEGOrganic compound (Et)₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at the temperature of minus 5 ℃, adding triethylamine (2.0mol), slowly dropwise adding (1,1,2, 2-tetramethylpropyl) amine hydrochloride (1.0mol), after the dropwise adding of the (1,1,2, 2-tetramethylpropyl) amine hydrochloride is finished, heating to room temperature for overnight stirring, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.30-7.22(m，12H)，1.55(s，24H)，1.29-1.26(m，54H)，0.94(s，45H)

7) heating and refluxing 0.8mol of chromium trichloride tris (tetrahydrofuran) and 0.8mol of a compound VI in a formula under the condition of toluene (8ml) for 24 hours at the heating temperature of 80 ℃, removing filtrate in vacuum, and performing vacuum pumping on insoluble substances to obtain the complex Cat 12.

[ example 13 ] preparation of Complex Cat13

All synthetic experiments were performed under nitrogen atmosphere:

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at the temperature of minus 5 ℃, adding triethylamine (2.0mol), slowly dropwise adding 2-amino-2, 3-dimethylbutane (1.0mol), after the dropwise adding of the 2-amino-2, 3-dimethylbutane is finished, heating to room temperature for overnight stirring, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.32-7.25(m，12H)，2.08-2.05(m，1H)，1.58(s，24H)，1.30-1.28(m，54H)，0.88(s，42H)

[ example 14 ] preparation of Complex Cat14

All synthetic experiments were performed under nitrogen atmosphere:

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) in tetrahydrofuran (6ml), the temperature was raised to-10 ℃, stirred overnight, toluene (50ml) was added and stirred for 1h, the solution was spun dryAdding toluene (50ml), filtering to remove precipitate, spin drying the filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at-5 ℃, adding triethylamine (2.0mol), slowly dropwise adding aminomethyl trimethylsilane (1.0mol), after the dropwise adding of the aminomethyl trimethylsilane is finished, heating to room temperature for overnight stirring, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.26-7.22(m，12H)，1.98(s，2H)1.52(s，24H)，1.31-1.25(m，48H)，0.92(s，42H)，0.08(s，9H)

[ example 15 ] preparation of Complex Cat15

All synthetic experiments were performed under nitrogen atmosphere:

5) Dissolving n-butyllithium (1.2mol) in tetrahydrofuran (12ml), standing at-80 deg.C, dissolving compound IV (1.2mol) in tetrahydrofuran (12ml), slowly adding dropwise into n-butyllithium within 2h, stirring to react for 1h, slowly adding dropwise compound (Et) at-80 deg.C₂N)PCl₂(0.6mol) tetrahydrofuran (6ml), heating to-10 deg.C, stirring overnight, adding toluene (50ml), stirring for 1h, spin-drying solvent, adding toluene (50ml), filtering to remove precipitate, spin-drying filtrate, adding PCl₃(3.0mol) refluxing for 2h, removing the solvent at 80 ℃ in vacuum, adding n-hexane (50ml) into the dried solid, stirring, filtering, and drying the filtrate to obtain the compound V.

6) Dissolving a compound V (2.0mol) in dichloromethane (20ml), stirring at the temperature of minus 5 ℃, adding triethylamine (2.0mol), slowly dropwise adding cyclohexylamine (1.0mol), after the cyclohexylamine is dropwise added, heating to room temperature, stirring overnight, filtering, leaching a filter cake with tetrahydrofuran (10ml) for three times, and spin-drying the filtrate to obtain a compound VI.

Compound vi has a hydrogen spectrum as follows:

¹H NMR(400MHz，CDCl₃)：7.26-7.22(m，12H)，2.57-2.52(m，1H)，1.74-1.69(m，4H)，1.54-1.49(m，30H)，1.31-1.15(m，30H)，0.91(s，42H)

Comparative example 1 preparation of Complex MET1

The complex catalyst MET1 was prepared according to the method in example 1, with the only difference that: replacing the raw material 1, 4-dibromo-2-fluorobenzene in the step 3 with p-dibromobenzene.

The ligand structure of compound vi prepared in this comparative example is as follows:

the hydrogen spectrum of the ligand is as follows:

¹H NMR(400MHz，CDCl₃)：7.28-7.18(m，8H)，7.10-7.07(m，8H)，3.00-2.97(m，1H)，1.54(s，24H)，1.31-1.29(d，24H)，1.10-1.07(d，6H)，0.90(s，36H)

comparative example 2 preparation of Complex MET2

Using commercial iPr-PNP (shown in formula A) as a ligand, heating and refluxing tris (tetrahydrofuran) chromium trichloride (0.8mol) and the ligand (0.8mol) for 24h under toluene (8ml), wherein the heating temperature is 80 ℃, removing the filtrate in vacuum, and obtaining the complex MET2 after insoluble substances are dried in vacuum.

Ethylene oligomerization reactions were carried out on the complexes Cat 1-15 prepared in examples 1-15 and the complexes MET 1-2 prepared in comparative examples 1-2, respectively, and the data of product selectivity, product index and the like measured are shown in Table 1.

The ethylene oligomerization reaction is carried out by adopting a 500ml high-pressure reaction kettle, the temperature of the reaction kettle is heated to 120 ℃, the reaction kettle is vacuumized for 3h, after nitrogen displacement is carried out for a plurality of times, ethylene is filled into the reaction kettle and is reduced to room temperature, 200ml of methylcyclohexane is added into the reaction kettle, then the complex, triisobutylaluminum and N, N-dimethylanilinium tetrakis (pentafluorophenyl) boron are sequentially added, and the ethylene oligomerization reaction is carried out under the conditions of 50 ℃ and 4.5 MPa. Wherein the molar concentration of the complex in the system is 1 mu mol/ml (calculated by chromium), the dosage of triisobutylaluminum is shown in Table 1 (calculated by Al/Cr molar ratio), and the dosage of N, N-dimethylanilinium tetrakis (pentafluorophenyl) boron is 1:1 calculated by B/Cr molar ratio. After the reaction is finished, filtering to obtain filtrate, and testing the selectivity of 1-octene as shown in table 1; then sending the filtrate into a rectifying tower for refining, wherein the rectifying conditions are as follows: 0.05MPaG, the temperature of a tower kettle is 135 ℃, the temperature of a tower top is 121 ℃, the reflux ratio is 1.5, the height of a rectifying column is 1000mm, and the filler is a triangular ring spiral filler.

The product purity and the impurity content of the product extracted from the tower top were measured and are shown in table 1, respectively.

TABLE 1 oligomerization selectivity and product testing

[ examples 16 to 30 ]

The 1-octene products prepared in each example 1-15 in table 1 were used as raw materials, and the following copolymerization reactions were performed:

the method comprises the steps of carrying out ethylene/1-octene copolymerization reaction by adopting a 2000ml high-pressure reaction kettle, heating the reaction kettle to 120 ℃, vacuumizing for 3h, replacing with nitrogen for several times, filling ethylene, cooling to room temperature, sequentially adding 0.8L of IsoparE, 0.2L of self-made 1-octene and 2.5 mu mol of CGC catalyst, adding MMAO (modified methylaluminoxane) according to the Al/Ti-200-500, adding tetra (pentafluorophenyl) boric acid-methyl di- (octadecyl) ammonium salt according to the B/Ti-1.0-1.2, heating to 180 ℃, then filling 3MPa ethylene to start polymerization reaction, and reacting for 10 min. The ethylene was then vented, the reaction solution was placed in ethanol, the precipitated solid was collected, dried to constant weight in a vacuum oven at 60 ℃ and weighed, and the sample analysis was performed with the test results shown in table 2.

[ COMPARATIVE EXAMPLES 3 to 4 ]

Copolymerization and sample analysis were carried out using the 1-octene products prepared in comparative examples 1 to 2 in Table 1 as raw materials, respectively, in accordance with the method in example 16, and the test results are shown in Table 2.

Comparative example 5

The copolymerization and the analysis of the samples were carried out according to the method of example 16, with the only difference that: the 1-octene product was replaced with the Ineos (Enlishi) commercial product 1-octene (98.5%). The test results are shown in table 2.

Comparative example 6

The copolymerization and the analysis of the samples were carried out according to the method of example 16, with the only difference that: the 1-octene product was replaced with Aladdin (Allatin) commercial product 1-octene (98%). The test results are shown in table 2.

TABLE 2 copolymerization product testing

Under the same polymerization conditions, 1-octene is prepared by using the catalyst of formula I, and the polymer obtained by copolymerizing the catalyst with ethylene has higher polymerization activity and monomer insertion rate compared with the polymer obtained by using the commercial 1-octene.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

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