CN111747995A

CN111747995A - Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof

Info

Publication number: CN111747995A
Application number: CN202010749068.5A
Authority: CN
Inventors: 王原; 郭建双; 郑浩; 王新威; 李济祥; 徐绍魁; 赵志成
Original assignee: Shanghai Research Institute of Chemical Industry SRICI
Current assignee: Shanghai Research Institute of Chemical Industry SRICI
Priority date: 2020-07-30
Filing date: 2020-07-30
Publication date: 2020-10-09
Anticipated expiration: 2040-07-30
Also published as: CN111747995B

Abstract

The invention relates to a nitrogen-containing aryloxy cyclopentadienyl titanium compound, a preparation method and application thereof, wherein the preparation method comprises the following steps: the nitrogen-containing phenolic ligand compound and the titanium trichloride compound react in an organic solvent, and then the nitrogen-containing aryloxy titanocene compound is obtained through filtration, concentration and recrystallization, and the nitrogen-containing aryloxy titanocene compound is a high-efficiency olefin polymerization catalyst and can be used for polymerization reactions such as ethylene or alpha-olefin homopolymerization, ethylene and alpha-olefin copolymerization, olefin and polar monomer copolymerization and the like. Compared with the prior art, the nitrogen-containing aryloxy titanocene compound has the advantages that: the method has the advantages of easily obtained raw materials, simple synthesis route, high product yield, relatively stable property and higher catalytic activity, can obtain polyethylene with ultrahigh molecular weight, polypropylene, ethylene and alpha-olefin copolymer with high comonomer content and olefin and polar monomer copolymer, and can meet the requirements of industrial application.

Description

Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof

Technical Field

The invention belongs to the technical field of olefin polymerization, and relates to a nitrogen-containing aryloxy ligand cyclopentadienyl titanium compound, a preparation method thereof and application thereof in olefin polymerization.

Background

Polyolefin materials such as Polyethylene (PE) and polypropylene (PP) have the advantages of high strength, low density, strong chemical corrosion resistance, low manufacturing cost and the like, and can replace common materials such as paper, wood, glass, metal, concrete and the like to a certain extent, so that the polyolefin materials have wide application and become the most widely applied polymer materials in the world today. Depending on the polymerization process, the molecular weight and the polymer chain differences, there are classifications of High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP) and some high end polyolefin products. Essentially, the critical properties and the field of application of a polymer are determined mainly by its molecular structure, such as: molecular weight and its distribution, branching degree and short-chain branch distribution, crystallization and entanglement behavior of molecular chains, and the like, and the fundamental factor controlling the molecular chain structure is the catalyst. Therefore, designing and synthesizing a metal complex catalyst with a novel structure, and realizing the controllability of the olefin polymerization process and the polymer microstructure become the research core in the field.

Since the 90 s of the last century, scientists have been striving to find catalysts with superior catalytic performance and have made a series of important advances. Fujita et al, Mitsui, Japan, developed phenoxyimine titanium group metal complexes and found that they are useful for olefin polymerization. The ligand structure of the catalyst is easy to modify, the performance of the catalyst can be regulated and controlled by designing the framework structure of the catalyst, polyethylene and stereoregular polypropylene with different molecular weights are prepared, and the catalyst can also catalyze the copolymerization of ethylene and alpha-olefin, so that novel polyolefin materials (Catalysis today, 2011,164,2-8) with various varieties are developed. Researches show that the phenoxyl imine titanium compound has medium polymerization activity of catalyzing ethylene, the obtained polymer has narrow molecular weight distribution and active polymerization characteristic, and in addition, the catalyst can also effectively carry out propylene three-dimensional control polymerization. The phenoxyimine zirconium compound has extremely high polymerization activity for catalyzing ethylene, can prepare ultra-high molecular polyethylene, but has sensitive stability to temperature, can generate ligand dissociation at high temperature, and can inactivate the catalyst. The Brookhart group reports a nickel neutral salicylaldimine complex, which can realize the regulation and control of catalyst performance and polymer molecular weight by introducing different types of substituents on a ligand framework, introducing a steric hindrance anthracene group, a naphthyl group and other rigid groups on an aryloxy ring and imine respectively, and adjusting the space environment and electronic factors around a metal center, wherein the polymerization process can be carried out in a polar medium, but the catalyst preparation route is long and the synthesis cost is high (Journal of American Chemical Society,2018,140,6685 and 6689). The Sun group reports that quinoline imine ligand cyclopentadienyl titanium complex has high catalytic ethylene polymerization activity under the activation of Methylaluminoxane (MAO), and the ultrahigh molecular weight polyethylene with narrow molecular weight distribution is prepared; it also utilizes such titanium complexes to catalyze the copolymerization of ethylene and alpha-olefins to yield copolymers of ethylene and 1-hexene and ethylene and 1-octene with a certain short chain branch content (Journal of organometallic chemistry,2014,753, 34-41).

In summary, the research on olefin polymerization catalysts has made a major breakthrough, and the regulation and control of the catalyst activity, stability and polymer microstructure are achieved to some extent by the effective metal complex catalyst structure design. However, the metal complex catalyst reported at present is difficult to combine excellent catalytic activity and thermal stability, and the comonomer responsiveness is generally low. Therefore, there is a need to improve the framework structure of the metal complex, optimize the steric environment around the metal center and the electron density, and obtain a metal complex catalyst with stable catalytic performance and high comonomer responsiveness at high temperature.

Disclosure of Invention

One of the objects of the present invention is to provide a nitrogen-containing aryloxycarbonyl titanium compound.

The second purpose of the invention is to provide a preparation method of the nitrogen-containing aryloxy titanocene compound.

The invention also aims to provide an application of the nitrogen-containing aryloxy titanocene compound, which can be used as a catalyst to catalyze the polymerization of alpha-olefins such as ethylene, propylene and the like to obtain homopolymers of the alpha-olefins such as ethylene, propylene and the like; or catalyzing ethylene to be copolymerized with propylene, 1-hexene or 1-octene to obtain a copolymer of ethylene and propylene, 1-hexene or 1-octene; or catalyzing the olefin to be copolymerized with the polar monomer to obtain the copolymer of the olefin and the polar monomer.

The purpose of the invention can be realized by the following technical scheme:

a nitrogen-containing aryloxy titanocene compound has the following chemical structural formula:

in the formula (I), the compound is shown in the specification,

R¹～R⁴each independently selected from one of the following groups: hydrogen, C₁～C₁₀Alkyl of linear, branched or cyclic structure, C₇～C₂₀Mono-or poly-aryl substituted alkyl, phenyl, halogen;

R⁵～R¹³are independently selected respectivelyOne from the following groups: hydrogen, C₁～C₁₀Alkyl of linear, branched or cyclic structure, phenyl;

R¹⁴one selected from the following groups: cyclopentadienyl, indenyl, fluorenyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted cyclopentadienyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted indenyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted fluorenyl.

Preferably, in the formula (I),

R¹～R⁴each independently selected from one of the following groups: hydrogen, C₁～C₆Alkyl of linear, branched or cyclic structure, cumyl, phenyl, halogen;

R⁵～R¹³each independently selected from one of the following groups: hydrogen, C₁～C₆Alkyl of linear, branched or cyclic structure, phenyl;

The structural formula of a typical nitrogen-containing aryloxycarbonyl titanium compound is as follows:

a preparation method of nitrogen-containing aryloxy titanocene compound comprises the following steps: reacting a nitrogen-containing phenol ligand compound with a titanocene trichloride compound in an organic solvent, and then filtering, concentrating and recrystallizing to obtain the nitrogen-containing aryloxy titanocene compound;

the chemical structural formula of the nitrogen-containing phenolic ligand compound is as follows:

the titanocene trichloride compound is R¹⁴TiCl₃Preferably pentamethylcyclopentadienyltitanium trichloride or indenyl titanium trichloride.

The reaction formula is shown as follows:

in the nitrogen-containing phenol ligand compound and titanocene trichloride compound represented by the above reaction formula (II), the substituent R¹～R¹⁴Is consistent with the requirement of meeting all corresponding groups of the nitrogen-containing aryloxy titanocene compound.

Preferably, the organic solvent comprises one or two of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether or n-hexane.

Preferably, the molar ratio of the nitrogen-containing phenol ligand compound to the titanocene trichloride compound is 1 (1.0-2.0), the reaction temperature is-78-110 ℃, and the reaction time is 1-96 h.

Preferably, the reaction temperature is 0-70 ℃, and the reaction time is 1-24 h.

The application of the nitrogen-containing aryloxy titanocene compound is used as a catalyst for olefin polymerization reaction or copolymerization reaction of olefin and polar monomer.

Preferably, when used, the catalyst promoter and/or the carrier are also added, and the homopolymerization or copolymerization is carried out by adopting a solution polymerization mode, an emulsion polymerization mode, a gas phase polymerization mode or a slurry polymerization mode.

Preferably, the cocatalyst is alkylaluminoxane selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isopropylaluminoxane or a borofluoride compound selected from bis (pentafluorophenyl) borane, tris (pentafluorophenyl) borane or a tetrakis (pentafluorophenyl) boron salt;

the carrier is selected from one or two of porous silica gel, magnesium chloride, alumina, molecular sieve or clay;

the olefin is selected from alpha-olefin such as ethylene, propylene, 1-hexene or 1-octene;

the polar monomer is an olefin derivative containing a polar group, and the polar group is selected from carbonyl, hydroxyl, carboxyl, ester group, alkoxy, amino, amido or thioether group.

Preferably, when an olefin monomer is homopolymerized, the nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as a cocatalyst, so that the olefin monomer is homopolymerized at 0-150 ℃, and the molar ratio of the main catalyst to the cocatalyst is 1 (1-100000);

when olefin monomers are copolymerized, a nitrogen-containing aryloxy cyclopentadienyl titanium compound is used as a main catalyst, alkyl aluminoxane or a boron fluorine compound is used as an auxiliary catalyst, at least two olefin monomers are copolymerized at 0-150 ℃, the molar ratio of the main catalyst to the auxiliary catalyst is 1 (1-100000), the pressure of the olefin monomers is 0.1-10.0 MPa, and the molar ratio of the catalyst to the olefin monomers is 1 (1000-100000);

when olefin and polar monomer are copolymerized, a nitrogen-containing aryloxy cyclopentadienyl titanium compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as an auxiliary catalyst, the olefin monomer and the polar monomer are copolymerized at 0-150 ℃, the molar ratio of the main catalyst to the auxiliary catalyst is 1 (1-100000), the pressure of the olefin monomer is 0.1-10.0 MPa, the molar ratio of the polar monomer to the olefin monomer is 1 (1-1000), and the molar ratio of the catalyst to the olefin monomer is 1 (1000-100000).

The technical conception of the invention is as follows:

the research finds that the complex with large steric hindrance substituent on the ligand not only shows high catalytic activity, but also can obtain polymers with higher regularity, therefore, the increase of the steric hindrance of the metal center is beneficial to protecting the active center, and can improve the stereo and regioselectivity of the polymerization process⁶The coordination mode greatly improves the stability of the complex. The quinoline imine ligand titanocene compound catalyzes ethylene polymerization to show moderate activity, and possible reasons are analyzedThe method comprises the following steps: 1) the cyclopentadienyl electron-donating effect of the cyclopentadienyl ligand part is weak, and the electron density around the metal center cannot be effectively adjusted; 2) the quinoline imine ligand has larger steric hindrance and stronger structural rigidity, and the coordination atoms are close to each other in space, so that the space around the active center of the catalyst is crowded, and the two factors are not beneficial to the coordination insertion of the monomer. Therefore, the invention considers the regulation of the ligand framework, and changes the coordination environment and the charge density around the metal center by introducing the phenol-pyridine-aromatic imine ligand with dispersed coordination atoms and the cyclopentadiene structural group with strong electron supply characteristic so as to realize the synthesis of the catalyst with high activity, thermal stability and high comonomer responsiveness.

Compared with the prior art, the nitrogen-containing aryloxy titanocene compound can be used as a high-efficiency olefin polymerization catalyst for polymerization reactions such as ethylene or alpha-olefin homopolymerization, ethylene and alpha-olefin copolymerization, olefin and polar monomer copolymerization and the like. The nitrogen-containing aryloxy titanocene compound has the following obvious advantages: the catalyst has the advantages of easily obtained raw materials, simple synthetic route, convenient preparation, high product yield, relatively stable property and higher catalytic activity, can obtain polyethylene and polypropylene with ultrahigh molecular weight and narrow molecular weight distribution, can obtain ethylene and alpha-olefin copolymer with high comonomer content and olefin and polar monomer copolymer, and can meet the requirements of industrial application.

Detailed Description

The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

Example 1:

synthesis of ligand L1

In a three-necked round-bottomed flask, 2-hydroxy-3, 5-dimethylbenzeneboronic acid (1.83g, 11mmol), 2-bromo-6-acetylpyridine (2.00g, 10mmol), tris (dibenzylideneacetone) dipalladium (1.83g,2mmol), triphenylphosphine (1.05g, 4mmol), cesium carbonate (8.15g, 25mmol), toluene (50mL), and ethanol (20mL) were added in this order. The mixture was refluxed for 18 hours. After cooling, 2mL of hydrogen peroxide (30%) and 30mL of water were added, the organic phase solvent was removed under reduced pressure, and the remaining brown viscous substance was washed with methanol to give intermediate 2- (2-hydroxy-3, 5-dimethylphenyl) -6-acetylpyridine (2.19g, 91%).

In a single neck round bottom flask, 2- (2-hydroxy-3, 5-dimethylphenyl) -6-acetylpyridine (1.21g, 5mmol), 2, 6-diisopropylaniline (1.77g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with microwave, filtered, and the filtrate was cooled to crystallize L1(1.26g, 63%).

¹H NMR(CDCl₃,400MHz):9.11(s,1H,OH),7.90(s,1H,Ar-H),7.62-7.01(m,7H,Ar-H),2.99(m,2H,J＝6.8Hz,CH(CH₃)₂),2.36(s,3H,ArCH₃),2.15(s,3H,ArCH₃),1.81(s,3H,NCCH₃),1.18(d,12H,J＝6.8Hz,CH(CH₃)₂).

Example 2:

synthesis of ligand L2

In a three-necked round-bottomed flask, 2-hydroxy-3, 5-dichlorophenylboronic acid (2.27g, 11mmol), 2-bromo-6-acetylpyridine (2.00g, 10mmol), tris (dibenzylideneacetone) dipalladium (1.83g,2mmol), triphenylphosphine (1.05g, 4mmol), cesium carbonate (8.15g, 25mmol), toluene (50mL) and ethanol (20mL) were added in this order. The mixture was refluxed for 18 hours. After cooling, 2mL of hydrogen peroxide (30%) and 30mL of water were added, the organic phase solvent was removed under reduced pressure, and the remaining brown viscous substance was washed with methanol to give intermediate 2- (2-hydroxy-3, 5-dichlorophenyl) -6-acetylpyridine (2.26g, 80%).

In a single neck round bottom flask, 2- (2-hydroxy-3, 5-dichlorophenyl) -6-acetylpyridine (1.41g, 5mmol), 2, 6-diisopropylaniline (1.77g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with a microwave, filtered, and the filtrate was cooled to crystallize L2(1.21g, 55%).

¹H NMR(CDCl₃,400MHz):9.58(s,1H,OH),8.25(s,1H,Ar-H),7.70-7.22(m,7H,Ar-H),2.88(m,2H,J＝6.8Hz,CH(CH₃)₂),1.87(s,3H,NCCH₃),1.16(d,12H,J＝6.8Hz,CH(CH₃)₂).

Example 3:

synthesis of ligand L3

In a three-necked round-bottomed flask, 2-hydroxy-3-phenylphenylboronic acid (2.35g, 11mmol), 2-bromo-6-acetylpyridine (2.00g, 10mmol), tris (dibenzylideneacetone) dipalladium (1.83g,2mmol), triphenylphosphine (1.05g, 4mmol), cesium carbonate (8.15g, 25mmol), toluene (50mL) and ethanol (20mL) were added in this order. The mixture was refluxed for 18 hours. After cooling, 2mL of hydrogen peroxide (30%) and 30mL of water were added, the organic phase solvent was removed under reduced pressure, and the remaining brown viscous substance was washed with methanol to give intermediate 2- [ (2-hydroxy-3-phenyl) phenyl ] -6-acetylpyridine (2.75g, 95%).

In a single neck round bottom flask, 2- [ (2-hydroxy-3-phenyl) phenyl ] -6-acetylpyridine (1.45g, 5mmol), 2, 6-dimethylaniline (1.21g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with a microwave, filtered, and the filtrate was cooled to crystallize L3(1.33g, 68%).

¹H NMR(CDCl₃,400MHz):10.95(s,1H,OH),8.75(d,1H,J＝7.2Hz,ArH),7.92(d,1H,J＝7.0Hz,Ar-H),7.59-7.14(m,12H,Ar-H),2.25(s,6H,ArCH₃),1.90(s,3H,NCCH₃).

Example 4:

synthesis of ligand L4

In a three-necked round-bottomed flask, 2-hydroxy-3, 5-dicumylphenylboronic acid (2.35g, 11mmol), 2-bromo-4-phenyl-6-acetylpyridine (2.00g, 10mmol), tris (dibenzylideneacetone) dipalladium (1.83g,2mmol), triphenylphosphine (1.05g, 4mmol), cesium carbonate (8.15g, 25mmol), toluene (50mL) and ethanol (20mL) were added in this order. The mixture was refluxed for 18 hours. After cooling, 2mL of hydrogen peroxide (30%) and 30mL of water were added, the organic phase solvent was removed under reduced pressure, and the remaining brown viscous substance was washed with methanol to give intermediate 2- [ (2-hydroxy-3, 5-dicumyl) phenyl ] -4-phenyl-6-acetylpyridine (2.75g, 95%).

In a single neck round bottom flask, 2- [ (2-hydroxy-3, 5-dicumyl) phenyl ] -4-phenyl-6-acetylpyridine (1.45g, 5mmol), aniline (0.93g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with microwave, filtered, and the filtrate was cooled to crystallize L4(0.82g, 45%).

¹H NMR(CDCl₃,400MHz):10.84(s,1H,OH),8.71(d,1H,J＝7.2Hz,ArH),7.91(d,1H,J＝7.0Hz,Ar-H),7.67-6.93(m,20H,Ar-H),2.53-1.92(m,15H,CH₃).

Example 5:

synthesis of ligand L5

In a single neck round bottom flask, 2- [ (2-hydroxy-3-phenyl) phenyl ] -6-acetylpyridine (1.45g, 5mmol), 2,4, 6-trimethylaniline (1.35g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with a microwave, filtered, and the filtrate was cooled to crystallize L5(1.24g, 61%).

¹H NMR(CDCl₃,400MHz):10.90(s,1H,OH),8.76(d,1H,J＝7.2Hz,ArH),7.88(d,1H,J＝7.0Hz,Ar-H),7.60-7.29(m,9H,Ar-H),6.96(s,2H,Ar-H),2.33(s,6H,ArCH₃),2.18(s,3H,ArCH₃),1.78(s,3H,NCCH₃).

Example 6:

synthesis of ligand L6

In a three-necked round-bottomed flask, 2-hydroxy-phenylboronic acid (1.52g, 11mmol), 2-bromo-4-methyl-6-propionylpyridine (2.28g, 10mmol), tris (dibenzylideneacetone) dipalladium (1.83g,2mmol), triphenylphosphine (1.05g, 4mmol), cesium carbonate (8.15g, 25mmol), toluene (50mL) and ethanol (20mL) were added in this order. The mixture was refluxed for 18 hours. After cooling, 2mL of hydrogen peroxide (30%) and 30mL of water were added, the organic phase solvent was removed under reduced pressure, and the remaining brown viscous substance was washed with methanol to give intermediate 2- (2-hydroxyphenyl) 4-methyl-6-propionylpyridine (1.86g, 77%).

In a single neck round bottom flask, 2- (2-hydroxyphenyl) 4-methyl-6-propionylpyridine (1.21g, 5mmol), 2, 6-diisopropylaniline (1.77g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10mL) were added. The mixture was reacted for 10 minutes with microwave, filtered, and the filtrate was cooled to crystallize L6(1.12g, 55%).

¹H NMR(CDCl₃,400MHz):8.92(s,1H,OH),8.65(d,1H,J＝7.2Hz,ArH),8.08(s,1H,Ar-H),7.52-6.96(m,7H,Ar-H),2.90(m,2H,J＝6.8Hz,CH(CH₃)₂),2.47(s,3H,ArCH₃),2.17(q,2H,J＝6.4Hz,CH₂CH₃),1.14(d,12H,J＝6.8Hz,CH(CH₃)₂),0.83(t,3H,J＝6.4Hz,CH₂CH₃).

Example 7:

synthesis of titanium Complex T1

Ligand L1(0.80g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL of dichloromethane were added to a 100mL Schlenk flask under the protection of argon, the mixture was stirred at room temperature for 10 hours, the solvent and volatile substances were removed under reduced pressure, and the mixture was dissolved in toluene, filtered and recrystallized to obtain yellow crystals (1.20g, yield: 92%).

¹H NMR(CDCl₃,400MHz):8.06(d,1H,J＝7.2Hz,Ar-H),7.71-7.48(m,4H,Ar-H),7.22(d,2H,J＝7.0Hz,Ar-H),7.00(s,1H,Ar-H),2.98(m,2H,J＝6.8Hz,CH(CH₃)₂),2.38(s,3H,ArCH₃),2.19(s,3H,ArCH₃),2.14(s,15H,Cp-CH₃),1.94(s,3H,NCCH₃),1.13(d,12H,J＝6.8Hz,CH(CH₃)₂).

Example 8:

synthesis of titanium Complex T2

Ligand L2(0.88g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL chloroform were added to a 100mL Schlenk flask under an argon atmosphere, and the reaction was stirred at 60 ℃ for 5 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.33g, yield: 96%).

¹H NMR(CDCl₃,400MHz):8.12(s,1H,Ar-H),8.06(d,1H,J＝7.2Hz,Ar-H),7.79-7.48(m,4H,Ar-H),7.22(d,2H,J＝7.0Hz,Ar-H),2.90(m,2H,J＝6.8Hz,CH(CH₃)₂),2.19(s,15H,Cp-CH₃),1.81(s,3H,NCCH₃),1.17(d,12H,J＝6.8Hz,CH(CH₃)₂).

Example 9:

synthesis of titanium Complex T3

Ligand L3(0.78g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL chloroform were added to a 100mL Schlenk flask under an argon atmosphere, and the reaction was stirred at 60 ℃ for 24 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.16g, yield: 90%).

¹H NMR(CDCl₃,400MHz):8.92(d,1H,J＝6.8Hz,ArH),8.10(d,1H,J＝7.2Hz,Ar-H),7.88(d,1H,J＝7.0Hz,Ar-H),7.56-7.10(m,11H,Ar-H),2.34(s,6H,ArCH₃),2.18(s,15H,Cp-CH₃),1.79(s,3H,NCCH₃).

Example 10:

synthesis of titanium Complex T4

Ligand L4(0.73g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL chloroform were added to a 100mL Schlenk flask under an argon atmosphere, and the reaction was stirred at 60 ℃ for 24 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.11g, yield: 90%).

¹H NMR(CDCl₃,400MHz):8.92(d,1H,J＝6.8Hz,ArH),8.10(d,1H,J＝7.2Hz,Ar-H),7.88(d,1H,J＝7.0Hz,Ar-H),7.56-7.10(m,20H,Ar-H),2.18(s,15H,Cp-CH₃),2.31-1.79(m,15H,CH₃).

Example 11:

synthesis of titanium Complex T5

Ligand L5(0.81g, 2mmol), indenyl titanium trichloride (0.54g, 2mmol) and 10mL chloroform were added to a 100mL Schlenk flask under argon protection, and the reaction was heated to 60 ℃ and stirred for 12 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.14g, yield: 89%).

¹H NMR(CDCl₃,400MHz):8.95(d,1H,J＝6.8Hz,ArH),8.02(d,1H,J＝7.2Hz,Ar-H),7.95(d,1H,J＝7.0Hz,Ar-H),7.71-7.18(m,12H,Ar-H),7.03(s,2H,Ar-H),6.46(m,3H,Ind-H),2.37(s,6H,ArCH₃),2.18(s,3H,ArCH₃),1.72(s,3H,NCCH₃).

Example 12:

synthesis of titanium Complex T6

Ligand L6(0.90g, 2mmol), fluorenyltitanium trichloride (0.64g, 2mmol) and 10mL chloroform were added to a 100mL Schlenk flask under an argon atmosphere, and the reaction was heated to 50 ℃ and stirred for 12 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in toluene, filtered and recrystallized to give yellow crystals (1.04g, yield: 82%).

¹H NMR(CDCl₃,400MHz):8.83(d,1H,J＝7.2Hz,ArH),8.14(s,1H,Ar-H),7.61-7.00(m,11H,Ar-H),6.42-6.20(m,7H),2.95(m,2H,J＝6.8Hz,CH(CH₃)₂),2.40(s,3H,ArCH₃),2.11(q,2H,J＝6.4Hz,CH₂CH₃),1.20(d,12H,J＝6.8Hz,CH(CH₃)₂),0.80(t,3H,J＝6.4Hz,CH₂CH₃).

Example 13:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 30 ℃, 0.1 mu mol of catalyst T1 is weighed and added into a reaction kettle, the ethylene pressure is adjusted to 0.5MPa and timing is started, the polymerization is stopped after 10 minutes of reaction, the white solid polyethylene is obtained after filtration, the white solid polyethylene is obtained, vacuum drying is carried out until the constant weight is achieved, the yield is 3.9g, and the catalytic activity is 2.3 × 10⁸g/mol·h，M_η＝1.5×10⁶g/mol, molecular weight distribution PDI 2.3.

Example 14:

under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5mol/L) were charged into a polymerization vessel, the temperature was adjusted to 50 ℃, and 0.1. mu. mol of catalyst T1 was weighed into the reaction vessel. Adjusting the ethylene pressure to 1.0MPa, starting timing, stopping polymerization after reacting for 10 minutes, and filtering to obtain white solid polyethylene.Vacuum drying until constant weight, yield 6.6g, catalytic activity 4.0 × 10⁸g/mol·h，M_η＝2.1×10⁶g/mol, molecular weight distribution PDI 2.1.

Example 15:

under the protection of nitrogen, 150mL of toluene and 5mmol of tris (pentafluorophenyl) borane are added into a polymerization kettle, the temperature is adjusted to 50 ℃, 0.1 mu mol of catalyst T2 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa and timing is started, the polymerization is stopped after 10 minutes of reaction, filtration is carried out, white solid polyethylene is obtained, vacuum drying is carried out until the constant weight is achieved, the yield is 2.9g, and the catalytic activity is 1.7 × 10⁸g/mol·h，M_η＝7.5×10⁵g/mol, molecular weight distribution PDI 1.5.

Example 16:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution (1.5mol/L) of ethyl aluminoxane are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T3 is weighed and added into a reaction kettle, the ethylene pressure is adjusted to 0.5MPa and timing is started, the polymerization is stopped after 10 minutes of reaction, white solid polyethylene is obtained after filtration, the white solid polyethylene is obtained, vacuum drying is carried out until the constant weight is achieved, the yield is 1.8g, and the catalytic activity is 1.1 × 10⁸g/mol·h，M_η＝1.0×10⁶g/mol, molecular weight distribution PDI 1.1.

Example 17:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 100 ℃, 0.1 mu mol of catalyst T4 is weighed and added into a reaction kettle, the ethylene pressure is adjusted to 0.5MPa and timing is started, the polymerization is stopped after 10 minutes of reaction, the white solid polyethylene is obtained after filtration, the white solid polyethylene is obtained, vacuum drying is carried out until the constant weight is achieved, the yield is 7.2g, and the catalytic activity is 4.3 × 10⁸g/mol·h，M_η＝2.5×10⁶g/mol, molecular weight distribution PDI 1.7.

Example 18:

under the protection of nitrogen, 150mL of toluene and 5. mu. mol of tetrakis (pentafluorophenyl) boron salt were charged into a polymerization vessel, the temperature was adjusted to 120 ℃, and 0.1. mu. mol of catalyst T5 was weighed into the reaction vessel. Adjusting ethylene pressure to 0.5MPa, starting timing, reacting for 10 min, terminating polymerization, and filteringObtaining white solid polyethylene, vacuum drying till constant weight, 6.3g of yield and 5.6 × 10 of catalytic activity⁸g/mol·h，M_η＝4.4×10⁶g/mol, molecular weight distribution PDI 2.1.

Example 19:

under the protection of nitrogen, 150mL of toluene, 0.2g of heat-activated silica gel and 5 mu mol of tris (pentafluorophenyl) borane are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T4 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 0.5MPa and timing is started, the polymerization is stopped after 30 minutes of reaction, and the white solid polyethylene is obtained after filtration, vacuum drying is carried out until the weight is constant, the yield is 0.8g, the catalytic activity is 8 × 10⁶g/mol·h，M_η＝2.0×10⁶g/mol, molecular weight distribution PDI 1.3.

Example 20:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 50 ℃, 0.1 mu mol of catalyst T1 is weighed and added into a reaction kettle, the propylene pressure is adjusted to 2.0MPa and timing is started, the polymerization is stopped after 10 minutes of reaction, filtration is carried out, white solid polypropylene is obtained, vacuum drying is carried out until the constant weight is achieved, the yield is 0.9g, and the catalytic activity is 5.4 × 10⁷g/mol·h，M_η＝5.4×10⁵g/mol, molecular weight distribution PDI 2.5.

Example 21:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution (1.5mol/L) of ethyl aluminoxane are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T4 is weighed and added into a reaction kettle, the propylene pressure is adjusted to 2.0MPa and timing is started, the polymerization is stopped after the reaction is carried out for 60 minutes, the white solid polypropylene is obtained after filtration, the white solid polypropylene is obtained, the vacuum drying is carried out until the constant weight is achieved, the yield is 8.0g, and the catalytic activity is 8 × 10⁷g/mol·h，M_η＝6.7×10⁵g/mol, molecular weight distribution PDI 2.3.

Example 22:

under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5mol/L) were charged into a polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. mu. mol of catalyst T5 was weighed into the reaction vessel. Regulating propyleneThe pressure is increased to 1.0MPa and the timing is started, the polymerization is stopped after the reaction is carried out for 60 minutes, the white solid polypropylene is obtained after filtration, the vacuum drying is carried out until the constant weight is achieved, the yield is 1.3g, and the catalytic activity is 1.3 × 10⁷g/mol·h，M_η＝7.1×10⁵g/mol, molecular weight distribution PDI 1.6.

Example 23:

under the protection of nitrogen, 150mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T5 is weighed and added into a reaction kettle, the propylene pressure is adjusted to 2.0MPa and timing is started, the polymerization is stopped after the reaction is carried out for 60 minutes, the white solid polypropylene is obtained after filtration, vacuum drying is carried out until the constant weight is achieved, the yield is 5.1g, and the catalytic activity is 5.1 × 10⁷g/mol·h，M_η＝9.3×10⁵g/mol, molecular weight distribution PDI 2.2.

Example 24:

under the protection of nitrogen, 150mL of toluene, 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) and 0.3g of magnesium chloride powder are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T4 is weighed and added into the reaction kettle, the propylene pressure is adjusted to 2.0MPa and the timing is started, the polymerization is stopped after the reaction is carried out for 60 minutes, the white solid polypropylene is obtained by filtration, the vacuum drying is carried out until the constant weight is achieved, the yield is 3.6g, and the catalytic activity is 3.6 × 10⁷g/mol·h，M_η＝6.7×10⁵g/mol, molecular weight distribution PDI 2.5.

Example 25:

under the protection of nitrogen, 200mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 70 ℃, 0.1 mu mol of catalyst T4 is weighed and added into a reaction kettle, the ethylene pressure is adjusted to 1.0MPa, propylene gas is charged again, the total pressure is 2.0MPa, the reaction is stopped for 1 hour, the white solid ethylene and propylene copolymer is obtained by filtration, and the vacuum drying is carried out until the constant weight yield is 8.4g, the catalytic activity is 8.4 × 10⁷g/mol·h，M_η＝1.1×10⁶g/mol, molecular weight distribution PDI 2.3.

Example 26:

under the protection of nitrogen, 200mL of toluene and3.33mL of a toluene solution of methylaluminoxane (1.5mol/L), adjusting the temperature to 100 ℃, weighing 0.1. mu. mol of a catalyst T4, adding the catalyst into a reaction kettle, adjusting the ethylene pressure to 1.0MPa, charging propylene gas, reacting for 1 hour under the total pressure of 3.0MPa, terminating the polymerization, filtering to obtain a white solid copolymer of ethylene and propylene, and drying in vacuum until the constant weight is obtained, wherein the yield is 10.0g, and the catalytic activity is 1 × 10⁸g/mol·h，M_η＝2.7×10⁶g/mol, molecular weight distribution PDI 2.4.

Example 27:

under the protection of nitrogen, 200mL of toluene and 3.33mL of toluene solution of methylaluminoxane (1.5mol/L) are added into a polymerization kettle, the temperature is adjusted to 120 ℃, 0.1 mu mol of catalyst T5 is weighed and added into a reaction kettle, the ethylene pressure is adjusted to 1.0MPa, propylene gas is charged again, the total pressure is 3.0MPa, the polymerization is stopped after 1 hour of reaction, white solid ethylene and propylene copolymer is obtained by filtration, and vacuum drying is carried out until the constant weight yield is 7.9g, the catalytic activity is 7.9 × 10⁷g/mol·h，M_η＝1.4×10⁶g/mol, molecular weight distribution PDI 1.7.

Example 28:

under the protection of nitrogen, 200mL of toluene, 3.33mL of toluene solution (1.5mol/L) of modified methylaluminoxane and 2.5mmol of 1-hexene are sequentially added into a polymerization kettle, the temperature is adjusted to 100 ℃, 0.1 mu mol of catalyst T1 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa, the polymerization is stopped after 1 hour of reaction, the white solid copolymer of ethylene and 1-hexene is obtained by filtration, and the vacuum drying is carried out until the constant weight yield is 4.1g, the catalytic activity is 4.1 × 10⁷g/mol·h，M_η＝1.7×10⁶g/mol, molecular weight distribution PDI 1.1.

Example 29:

under the protection of nitrogen, 200mL of toluene, 3.33mL of toluene solution (1.5mol/L) of modified methylaluminoxane and 5mmol of 1-octene are sequentially added into a polymerization kettle, the temperature is adjusted to 100 ℃, 0.1 mu mol of catalyst T4 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa, the polymerization is stopped after 1 hour of reaction, the white solid ethylene and 1-octene copolymer is obtained after filtration, the vacuum drying is carried out until the constant weight is obtained, the yield is 4.5g, and the catalytic activity is 4.5 × 10⁷g/mol·h，M_η＝1.6×10⁶g/mol, molecular weight distribution PDI 1.8.

Example 30:

under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set to be 30 ℃, 50mmol of methyl acrylate and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L) are added, 0.50 mu mol of catalyst T1 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa, the polymerization reaction is started, the polymerization is stopped after 1 hour of reaction, the copolymer of ethylene and methyl acrylate is obtained by filtering, the vacuum drying is carried out until the constant weight is achieved, the yield is 8.5g, the catalytic activity is 1.7 × 10⁷g/mol·h，M_η＝2.0×10⁵g/mol, comonomer insertion 25%, molecular weight distribution PDI 1.8.

Example 31:

under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set to be 30 ℃, 50mmol of ethyl acrylate and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L) are added, 0.50 mu mol of catalyst T2 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa, the polymerization reaction is started, the polymerization is stopped after 1 hour of reaction, the copolymer of ethylene and ethyl acrylate is obtained by filtration, the vacuum drying is carried out until the constant weight is achieved, the yield is 5.7g, the catalytic activity is 1.1 × 10⁷g/mol·h，M_η＝9.5×10⁵g/mol, comonomer insertion 23%, molecular weight distribution PDI 1.9.

Example 32:

under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set to be 40 ℃, 50mmol of butyl acrylate and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L) are added, 0.50 mu mol of catalyst T3 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to 1.0MPa, the polymerization reaction is started, the polymerization is stopped after 1 hour of reaction, the ethylene and butyl acrylate copolymer is obtained by filtering, the vacuum drying is carried out until the constant weight is achieved, the yield is 7.3g, the catalytic activity is 1.5 × 10⁷g/mol·h，M_η＝8.5×10⁵g/mol, comonomer insertion 15%, molecular weight distribution PDI 2.5.

Example 33:

adding into a polymerization kettle under the protection of nitrogen200mL of toluene, setting the polymerization reaction temperature to 40 ℃, adding 50mmol of methyl methacrylate and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L), weighing 0.50 mu mol of catalyst T4, adding the catalyst into a reaction kettle, adjusting the ethylene pressure to 1.0MPa, starting the polymerization reaction, stopping the polymerization after 1 hour of reaction, filtering to obtain the copolymer of ethylene and methyl methacrylate, drying in vacuum until the constant weight is obtained, the yield is 10.7g, and the catalytic activity is 2.1 × 10⁷g/mol·h，M_η＝8.1×10⁵g/mol, comonomer insertion 24%, molecular weight distribution PDI 2.3.

Example 34:

under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set to be 50 ℃, 50mmol of acrylonitrile and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L) are added, 0.50 mu mol of catalyst T5 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to be 1.0MPa, the polymerization reaction is started, the polymerization is stopped after 1 hour of reaction, the copolymer of ethylene and acrylonitrile is obtained by filtration, the yield is 6.6g, the catalytic activity is 1.3 × 10⁷g/mol·h，M_η＝1.5×10⁵g/mol, comonomer insertion 17%, molecular weight distribution PDI 2.1.

Example 35:

under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set to be 50 ℃, 50mmol of butenamide and 3.0mL of toluene solution of methylaluminoxane (1.5mol/L) are added, 0.50 mu mol of catalyst T6 is weighed and added into the reaction kettle, the ethylene pressure is adjusted to be 1.0MPa, the polymerization reaction is started, the polymerization is stopped after 1 hour of reaction, the ethylene and butenamide copolymer is obtained by filtering, the vacuum drying is carried out until the constant weight is achieved, the yield is 5.2g, and the catalytic activity is 1 × 10⁷g/mol·h，M_η＝3.5×10⁵g/mol, comonomer insertion 19%, molecular weight distribution PDI 1.6.

The substituent groups in the nitrogen-containing aryloxy titanocene compound, the component types and proportions in the compound preparation process, the process parameters and the like in the above embodiments can be selected according to actual conditions and actual requirements, for example:

in the formula (I), the compound is shown in the specification,

R¹～R⁴each independently selected from one of the following groups: hydrogen, C₁～C₁₀Alkyl of linear, branched or cyclic structure, C₇～C₂₀Mono-or poly-aryl substituted alkyl (e.g., cumyl), phenyl, halo;

R⁵～R¹³each independently selected from one of the following groups: hydrogen, C₁～C₁₀Alkyl of linear, branched or cyclic structure, phenyl;

The preparation method of the nitrogen-containing aryloxy titanocene compound comprises the following steps: reacting a nitrogen-containing phenol ligand compound with a titanocene trichloride compound in an organic solvent, and then filtering, concentrating and recrystallizing to obtain a nitrogen-containing aryloxy titanocene compound;

the cyclopentadienyl titanium trichloride compound is R¹⁴TiCl₃。

The organic solvent comprises one or two of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether or n-hexane. The molar ratio of the nitrogen-containing phenol ligand compound to the titanocene trichloride compound is 1 (1.0-2.0), such as 1:1.2, 1:1.5 and 1:1.7, the reaction temperature is-78-110 ℃ (such as-20 ℃, 0 ℃,20 ℃, 40 ℃, 60 ℃ and 80 ℃), and the reaction time is 1-96 h (such as 12h, 24h, 36h, 48h, 60h, 72h and 84 h).

The nitrogen-containing aryloxy titanocene compound is used as a catalyst for olefin polymerization reaction or copolymerization reaction of olefin and polar monomer. When the catalyst is used, the cocatalyst and/or the carrier (for example, the cocatalyst is added only or the cocatalyst and the carrier are added simultaneously) are added, and homopolymerization or copolymerization is carried out by adopting a solution polymerization mode, an emulsion polymerization mode, a gas phase polymerization mode or a slurry polymerization mode.

The cocatalyst is alkyl aluminoxane or boron fluorine compound, the alkyl aluminoxane is selected from methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane or isopropyl aluminoxane, and the boron fluorine compound is selected from bis (pentafluorophenyl) borane, tris (pentafluorophenyl) borane or tetrakis (pentafluorophenyl) boron salt;

the carrier is one or two selected from porous silica gel, magnesium chloride, alumina, molecular sieve or clay;

the olefin is selected from ethylene, propylene, 1-hexene or 1-octene;

the polar monomer is an olefin derivative containing a polar group, and the polar group is selected from carbonyl, hydroxyl, carboxyl, ester group, alkoxy, amine group, amide group or thioether group.

When olefin monomers are homopolymerized, the nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as a cocatalyst, the olefin monomers are homopolymerized at 0-150 ℃ (for example, 20 ℃, 50 ℃, 80 ℃ and 120 ℃), and the molar ratio of the main catalyst to the cocatalyst is 1 (1-100000), for example, 1:10, 1:100, 1:1000 and 1: 10000;

when olefin monomers are copolymerized, a nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as a cocatalyst, at least two olefin monomers are copolymerized under the condition of 0-150 ℃ (such as 20 ℃, 50 ℃, 80 ℃ and 120 ℃), the molar ratio of the main catalyst to the cocatalyst is 1 (1-100000), such as 1:10, 1:100, 1:1000 and 1:10000, the pressure of the olefin monomers is 0.1-10.0 MPa (such as 1MPa and 5MPa), and the molar ratio of the catalyst to the olefin monomers is 1 (1000-100000), such as 1:1000 and 1: 10000;

when olefin and polar monomer are copolymerized, the nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as an auxiliary catalyst, the olefin monomer and the polar monomer are copolymerized under 0-150 ℃ (for example, 20 ℃, 50 ℃, 80 ℃ and 120 ℃), the molar ratio of the main catalyst to the auxiliary catalyst is 1 (1-100000), for example, 1:10, 1:100, 1:1000 and 1:10000, the pressure of the olefin monomer is 0.1-10.0 MPa (for example, 1MPa and 5MPa), the molar ratio of the polar monomer to the olefin monomer is 1 (1-1000), for example, 1:10 and 1:100, and the molar ratio of the catalyst to the olefin monomer is 1 (1000-100000), for example, 1:1000 and 1: 10000.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The nitrogen-containing aryloxy titanocene compound is characterized by having the following chemical structural formula:

in the formula (I), the compound is shown in the specification,

R¹⁴one selected from the following groups: a cyclopentadienyl group, a cyclopentadienyl group and a cyclopentadienyl group,indenyl, fluorenyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted cyclopentadienyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted indenyl, C₁～C₁₅Monoalkyl-or polyalkyl-substituted fluorenyl.

2. The nitrogen-containing aryloxycarbonyl titanocene compound of claim 1, wherein in formula (I),

3. A method for producing the nitrogen-containing aryloxycarbonyl titanium compound as claimed in claim 1 or 2, wherein the method comprises: reacting a nitrogen-containing phenol ligand compound with a titanocene trichloride compound in an organic solvent, and then filtering, concentrating and recrystallizing to obtain the nitrogen-containing aryloxy titanocene compound;

the titanocene trichloride compound is R¹⁴TiCl₃。

4. The method of claim 3, wherein the organic solvent comprises one or two of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether, and n-hexane.

5. The method for preparing the nitrogen-containing aryloxy titanocene compound according to claim 3, wherein the molar ratio of the nitrogen-containing phenolic ligand compound to the titanocene trichloride compound is 1 (1.0-2.0), the reaction temperature is-78-110 ℃, and the reaction time is 1-96 hours.

6. The method for preparing a nitrogen-containing aryloxycarbonyl titanocene compound as claimed in claim 5, wherein the reaction temperature is 0-70 ℃ and the reaction time is 1-24 h.

7. The use of a nitrogen-containing aryloxycarbonyl titanium compound as claimed in claim 1 or 2, wherein the nitrogen-containing aryloxycarbonyl titanium compound is used as a catalyst in olefin polymerization or copolymerization of an olefin and a polar monomer.

8. The use of a nitrogen-containing aryloxycarbonyl titanocene compound as in claim 7, wherein a cocatalyst and/or a support is further added during the use, and the homopolymerization or copolymerization is carried out by solution polymerization, emulsion polymerization, gas phase polymerization or slurry polymerization.

9. The use of a nitrogen-containing aryloxycarbonyl titanocene compound as claimed in claim 8, wherein the cocatalyst is alkylaluminoxane or borofluoride compound, the alkylaluminoxane is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isopropylaluminoxane, and the borofluoride compound is selected from bis (pentafluorophenyl) borane, tris (pentafluorophenyl) borane or tetrakis (pentafluorophenyl) boron salt;

the olefin is selected from ethylene, propylene, 1-hexene or 1-octene;

10. The use of a nitrogen-containing aryloxycarbonyl titanocene compound as claimed in claim 9,

when olefin monomers are homopolymerized, a nitrogen-containing aryloxy cyclopentadienyl titanium compound is used as a main catalyst, alkyl aluminoxane or a boron fluorine compound is used as an auxiliary catalyst, the olefin monomers are homopolymerized at 0-150 ℃, and the molar ratio of the main catalyst to the auxiliary catalyst is 1 (1-100000);