CN111747995B - Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof - Google Patents

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

Info

Publication number
CN111747995B
CN111747995B CN202010749068.5A CN202010749068A CN111747995B CN 111747995 B CN111747995 B CN 111747995B CN 202010749068 A CN202010749068 A CN 202010749068A CN 111747995 B CN111747995 B CN 111747995B
Authority
CN
China
Prior art keywords
nitrogen
compound
olefin
catalyst
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010749068.5A
Other languages
Chinese (zh)
Other versions
CN111747995A (en
Inventor
王原
郭建双
郑浩
王新威
李济祥
徐绍魁
赵志成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Research Institute of Chemical Industry SRICI
Original Assignee
Shanghai Research Institute of Chemical Industry SRICI
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Research Institute of Chemical Industry SRICI filed Critical Shanghai Research Institute of Chemical Industry SRICI
Priority to CN202010749068.5A priority Critical patent/CN111747995B/en
Publication of CN111747995A publication Critical patent/CN111747995A/en
Application granted granted Critical
Publication of CN111747995B publication Critical patent/CN111747995B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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 available raw materials, simple synthesis route, high product yield, relatively stable property and relatively high catalytic activity, can obtain polyethylene and polypropylene with ultrahigh molecular weight, 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 method, the molecular weight and the polymer chain, there are 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, degree of branching and short-chain branch distribution, crystallization and entanglement behavior of molecular chains, and the like, and the fundamental factor controlling the molecular chain structure lies in 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 catalyst framework structure is designed to regulate and control the performance 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 moderate polymerization activity of catalyzing ethylene, the obtained polymer has narrow molecular weight distribution and active polymerization characteristics, 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, 6685-6689). 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 produce copolymers of ethylene and 1-hexene and ethylene and 1-octene with a certain short chain branching 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 copolymerize with propylene, 1-hexene or 1-octene to obtain 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:
Figure BDA0002609412220000031
in the formula (I), the compound is shown in the specification,
R 1 ～R 4 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, phenyl, halogen;
R 5 ～R 13 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, phenyl;
R 14 one selected from the following groups: cyclopentadienyl, indenyl, fluorenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted cyclopentadienyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted indenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted fluorenyl.
Preferably, in the formula (I),
R 1 ～R 4 each independently selected from one of the following groups: hydrogen, C 1 ～C 6 Alkyl of straight, branched or cyclic structure, cumyl, phenyl, halogen;
R 5 ～R 13 each independently selected from one of the following groups: hydrogen, C 1 ～C 6 Alkyl of linear, branched or cyclic structure, phenyl;
R 14 one selected from the following groups: a cyclopentadienyl group, a cyclopentadienyl group and a cyclopentadienyl group,indenyl, fluorenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted cyclopentadienyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted indenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted fluorenyl.
A typical nitrogen-containing aryloxycarbonyl titanium compound has the following structural formula:
Figure BDA0002609412220000041
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 nitrogenous phenolic ligand compound is as follows:
Figure BDA0002609412220000051
the titanocene trichloride compound is R 14 TiCl 3 Preferably pentamethylcyclopentadienyltitanium trichloride or indenyl titanium trichloride.
The reaction formula is shown as follows:
Figure BDA0002609412220000052
in the nitrogen-containing phenol ligand compound and titanocene trichloride compound represented by the above reaction formula (II), the substituent R 1 ～R 14 Is consistent with the requirement of meeting each corresponding group 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 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 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 the 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 titanocene compound is used as a main catalyst, alkyl aluminoxane or 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, 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 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:
researches show that the complex with large steric hindrance substituent on the ligand not only shows high catalytic activity, but also can obtain a polymer with higher regularity. Therefore, increasing the steric hindrance of the metal center is beneficial to protecting the active center and can improve the stereoselectivity and regioselectivity of the polymerization process. In addition, the ligand is provided with a cyclopentadienyl electron-donating substituent which can form eta with the metal center 6 The stability of the complex is greatly improved by the coordination mode. The quinoline imine ligand titanocene compound catalyzes ethylene polymerization to show moderate activity, and the analysis is probably due to the following reasons: 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 coordination atoms are closer to each other in space, so that the space around the active center of the catalyst is crowded, and the two factors are not favorable for coordination insertion of monomers. Therefore, the invention considers adjusting 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 more 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 available 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, 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 (50 mL) and ethanol (20 mL) were sequentially added. 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 mass 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, 5 mmol), 2, 6-diisopropylaniline (1.77g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol), and methanol (10 mL) were charged. The mixture was reacted for 10 minutes by microwave, filtered, and the filtrate was cooled to crystallize to obtain ligand L1 (1.26g, 63%).
Figure BDA0002609412220000071
1 H NMR(CDCl 3 ,400MHz):δ9.11(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(CH 3 ) 2 ),2.36(s,3H,ArCH 3 ),2.15(s,3H,ArCH 3 ),1.81(s,3H,NCCH 3 ),1.18(d,12H,J＝6.8Hz,CH(CH 3 ) 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 (50 mL) and ethanol (20 mL) 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 material 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, 5 mmol), 2, 6-diisopropylaniline (1.77g, 10 mmol), anhydrous magnesium sulfate (3.02g, 25mmol), and methanol (10 mL) were added. The mixture was reacted for 10 minutes by microwave, filtered, and the filtrate was cooled and crystallized to obtain ligand L2 (1.21g, 55%).
Figure BDA0002609412220000081
1 H NMR(CDCl 3 ,400MHz):δ9.58(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(CH 3 ) 2 ),1.87(s,3H,NCCH 3 ),1.16(d,12H,J＝6.8Hz,CH(CH 3 ) 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 (50 mL) and ethanol (20 mL) 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 material 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, 5 mmol), 2, 6-dimethylaniline (1.21g, 10mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10 mL) were charged. The mixture was reacted for 10 minutes by microwave, filtered, and the filtrate was cooled to crystallize, to obtain ligand L3 (1.33g, 68%).
Figure BDA0002609412220000091
1 H NMR(CDCl 3 ,400MHz):δ10.95(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,ArCH 3 ),1.90(s,3H,NCCH 3 ).
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 (50 mL) and ethanol (20 mL) were sequentially added. 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 material was washed with methanol to give intermediate 2- [ (2-hydroxy-3, 5-dicumyl) phenyl ] -4-phenyl-6-acetylpyridine (2.75g, 95%).
In a single-necked round-bottomed flask, 2- [ (2-hydroxy-3, 5-dicumyl) phenyl ] -4-phenyl-6-acetylpyridine (1.45g, 5 mmol), aniline (0.93g, 10 mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10 mL) were charged. The mixture was reacted for 10 minutes by microwave, filtered, and the filtrate was cooled to crystallize, to obtain ligand L4 (0.82g, 45%).
Figure BDA0002609412220000092
1 H NMR(CDCl 3 ,400MHz):δ10.84(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,CH 3 ).
Example 5:
synthesis of ligand L5
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 (50 mL) and ethanol (20 mL) 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 material was washed with methanol to give intermediate 2- [ (2-hydroxy-3-phenyl) phenyl ] -6-acetylpyridine (2.75g, 95%).
In a single-necked round-bottomed flask, 2- [ (2-hydroxy-3-phenyl) phenyl ] -6-acetylpyridine (1.45g, 5 mmol), 2,4, 6-trimethylaniline (1.35g, 10 mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10 mL) were charged. The mixture was reacted for 10 minutes by microwave, filtered, and the filtrate was cooled to crystallize to obtain ligand L5 (1.24g, 61%).
Figure BDA0002609412220000101
1 H NMR(CDCl 3 ,400MHz):δ10.90(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,ArCH 3 ),2.18(s,3H,ArCH 3 ),1.78(s,3H,NCCH 3 ).
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 (50 mL) and ethanol (20 mL) were sequentially added. 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, 5 mmol), 2, 6-diisopropylaniline (1.77g, 10 mmol), anhydrous magnesium sulfate (3.02g, 25mmol) and methanol (10 mL) were charged. The mixture was reacted for 10 minutes with microwave, filtered, and the filtrate was cooled and crystallized to obtain ligand L6 (1.12g, 55%).
Figure BDA0002609412220000111
1 H NMR(CDCl 3 ,400MHz):δ8.92(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(CH 3 ) 2 ),2.47(s,3H,ArCH 3 ),2.17(q,2H,J＝6.4Hz,CH 2 CH 3 ),1.14(d,12H,J＝6.8Hz,CH(CH 3 ) 2 ),0.83(t,3H,J＝6.4Hz,CH 2 CH 3 ).
Example 7:
synthesis of titanium Complex T1
Under the protection of argon, ligand L1 (0.80g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL of dichloromethane are added into a 100mL Schlenk bottle, the mixture is stirred at room temperature for reaction for 10 hours, the solvent and volatile substances are removed under reduced pressure, and the mixture is dissolved in toluene, filtered and recrystallized to obtain yellow crystals (1.20 g, yield: 92%).
Figure BDA0002609412220000112
1 H NMR(CDCl 3 ,400MHz):δ8.06(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(CH 3 ) 2 ),2.38(s,3H,ArCH 3 ),2.19(s,3H,ArCH 3 ),2.14(s,15H,Cp-CH 3 ),1.94(s,3H,NCCH 3 ),1.13(d,12H,J＝6.8Hz,CH(CH 3 ) 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 argon protection, heated to 60 ℃ and stirred for reaction for 5 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.33 g, yield: 96%).
Figure BDA0002609412220000121
1 H NMR(CDCl 3 ,400MHz):δ8.12(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(CH 3 ) 2 ),2.19(s,15H,Cp-CH 3 ),1.81(s,3H,NCCH 3 ),1.17(d,12H,J＝6.8Hz,CH(CH 3 ) 2 ).
Example 9:
synthesis of titanium Complex T3
Ligand L3 (0.78g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL chloroform were charged in a 100mL Schlenk flask under an argon shield, and the reaction mixture was heated to 60 ℃ and stirred for 24 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.16 g, yield: 90%).
Figure BDA0002609412220000122
1 H NMR(CDCl 3 ,400MHz):δ8.92(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,ArCH 3 ),2.18(s,15H,Cp-CH 3 ),1.79(s,3H,NCCH 3 ).
Example 10:
synthesis of titanium Complex T4
Ligand L4 (0.73g, 2mmol), pentamethylcyclopentadienyltitanium trichloride (0.57g, 2mmol) and 10mL chloroform were charged in a 100mL Schlenk flask under argon protection, and the reaction mixture was heated to 60 ℃ and stirred for 24 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.11 g, yield: 90%).
Figure BDA0002609412220000131
1 H NMR(CDCl 3 ,400MHz):δ8.92(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-CH 3 ),2.31-1.79(m,15H,CH 3 ).
Example 11:
synthesis of titanium Complex T5
Ligand L5 (0.81g, 2mmol), indenyl titanium trichloride (0.54g, 2mmol) and 10mL of chloroform were charged in a 100mL Schlenk flask under an argon atmosphere, and the reaction was stirred at 60 ℃ for 12 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in dichloromethane, filtered and recrystallized to give yellow crystals (1.14 g, yield: 89%).
Figure BDA0002609412220000132
1 H NMR(CDCl 3 ,400MHz):δ8.95(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,ArCH 3 ),2.18(s,3H,ArCH 3 ),1.72(s,3H,NCCH 3 ).
Example 12:
synthesis of titanium Complex T6
Ligand L6 (0.90g, 2mmol), fluorenyl titanium trichloride (0.64g, 2mmol) and 10mL of chloroform were added to a 100mL Schlenk flask under argon protection, heated to 50 ℃ and stirred for reaction for 12 hours. The solvent and volatile substances were removed under reduced pressure, dissolved in toluene, filtered and recrystallized to give yellow crystals (1.04 g, yield: 82%).
Figure BDA0002609412220000141
1 H NMR(CDCl 3 ,400MHz):δ8.83(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(CH 3 ) 2 ),2.40(s,3H,ArCH 3 ),2.11(q,2H,J＝6.4Hz,CH 2 CH 3 ),1.20(d,12H,J＝6.8Hz,CH(CH 3 ) 2 ),0.80(t,3H,J＝6.4Hz,CH 2 CH 3 ).
Example 13:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were added to a polymerization vessel, the temperature was adjusted to 30 ℃, and 0.1. Mu. Mol of catalyst T1 was weighed and added to the reaction vessel. Adjusting the ethylene pressure to 0.5MPa, starting timing, reacting for 10 minutes, terminating the polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 3.9g, catalytic activity 2.3X 10 8 g/mol·h，M η ＝1.5×10 6 g/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 (1.5 mol/L) were charged into a polymerization vessel, the temperature was adjusted to 50 ℃, and 0.1. Mu. Mol of catalyst T1 was weighed and charged into the reaction vessel. Adjusting the ethylene pressure to 1.0MPa, starting timing, reacting for 10 minutes, stopping polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 6.6g, catalytic activity 4.0X 10 8 g/mol·h，M η ＝2.1×10 6 g/mol, molecular weight distribution PDI =2.1.
Example 15:
under the protection of nitrogen, 150mL of toluene and 5mmol of tris (pentafluorophenyl) borane were added to the polymerization kettle, the temperature was adjusted to 50 ℃, and 0.1. Mu. Mol of catalyst T2 was weighed into the reaction kettle. Adjusting the ethylene pressure to 1.0MPa, starting timing, stopping polymerization after reacting for 10 minutes, and filtering to obtain white solid polyethylene. Drying in vacuum until constant weight. Yield: 2.9g, catalytic activity 1.7X 10 8 g/mol·h，M η ＝7.5×10 5 g/mol, molecular weight distribution PDI =1.5.
Example 16:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of ethyl aluminoxane (1.5 mol/L) were added to the polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T3 was weighed and added to the reaction vessel. Adjusting the ethylene pressure to 0.5MPa, starting timing, reacting for 10 minutes to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying until constant weight. Yield: 1.8g, catalytic activity 1.1X 10 8 g/mol·h，M η ＝1.0×10 6 g/mol, molecular weight distribution PDI =1.1.
Example 17:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were charged into a polymerization vessel, the temperature was adjusted to 100 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and charged into the reaction vessel. Adjusting the ethylene pressure to 0.5MPa, starting timing, reacting for 10 minutes, terminating the polymerization, and filtering to obtain white solid polyethylene. Drying in vacuum until constant weight. Yield: 7.2g, catalytic activity 4.3X 10 8 g/mol·h，M η ＝2.5×10 6 g/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 added to the polymerization vessel, the temperature was adjusted to 120 ℃, and 0.1. Mu. Mol of catalyst T5 was weighed and added to the reaction vessel. Adjusting the ethylene pressure to 0.5MPa, starting timing, reacting for 10 minutes, terminating the polymerization, and filtering to obtain white solid polyethylene. Drying in vacuum until constant weight. Yield: 6.3g, catalytic activity 5.6X 10 8 g/mol·h，M η ＝4.4×10 6 g/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 were added to a polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and added to the reaction vessel. Adjusting the ethylene pressure to 0.5MPa, starting timing, reacting for 30 minutes to terminate polymerization, and filtering to obtain white solid polyethylene. Vacuum drying apparatusTo constant weight. Yield: 0.8g, catalytic activity 8X 10 6 g/mol·h，M η ＝2.0×10 6 g/mol, molecular weight distribution PDI =1.3.
Example 20:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were charged into a polymerization vessel, the temperature was adjusted to 50 ℃, and 0.1. Mu. Mol of catalyst T1 was weighed and charged into the reaction vessel. Adjusting the pressure of the propylene to 2.0MPa, starting timing, reacting for 10 minutes, terminating the polymerization, and filtering to obtain white solid polypropylene. Vacuum drying until constant weight. Yield: 0.9g, catalytic activity 5.4X 10 7 g/mol·h，M η ＝5.4×10 5 g/mol, molecular weight distribution PDI =2.5.
Example 21:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of ethyl aluminoxane (1.5 mol/L) were added to the polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and added to the reaction vessel. Adjusting the propylene pressure to 2.0MPa, starting timing, reacting for 60 minutes, terminating the polymerization, and filtering to obtain white solid polypropylene. Vacuum drying until constant weight. Yield: 8.0g, catalytic activity 8X 10 7 g/mol·h，M η ＝6.7×10 5 g/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 (1.5 mol/L) were added to a polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T5 was weighed and added to the reaction vessel. Adjusting the propylene pressure to 1.0MPa, starting timing, reacting for 60 minutes, terminating the polymerization, and filtering to obtain white solid polypropylene. Vacuum drying until constant weight. Yield: 1.3g, catalytic activity 1.3X 10 7 g/mol·h，M η ＝7.1×10 5 g/mol, molecular weight distribution PDI =1.6.
Example 23:
under the protection of nitrogen, 150mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were charged into a polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T5 was weighed and charged into the reaction vessel. Adjusting the propylene pressure to 2.0MPa, starting timing, and reacting for 60 minutes to endStopping polymerization, and filtering to obtain white solid polypropylene. Vacuum drying until constant weight. Yield: 5.1g, catalytic activity 5.1X 10 7 g/mol·h，M η ＝9.3×10 5 g/mol, molecular weight distribution PDI =2.2.
Example 24:
under the protection of nitrogen, 150mL of toluene, 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) and 0.3g of magnesium chloride powder were added to a polymerization vessel, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and added to the reaction vessel. Adjusting the propylene pressure to 2.0MPa, starting timing, reacting for 60 minutes, terminating the polymerization, and filtering to obtain white solid polypropylene. Vacuum drying until constant weight. Yield: 3.6g, catalytic activity 3.6X 10 7 g/mol·h，M η ＝6.7×10 5 g/mol, molecular weight distribution PDI =2.5.
Example 25:
under the protection of nitrogen, 200mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were added to a polymerization kettle, the temperature was adjusted to 70 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and added to the reaction kettle. The ethylene pressure was adjusted to 1.0MPa, and propylene gas was introduced thereinto to make the total pressure 2.0MPa. After 1 hour of reaction, the polymerization was terminated and filtered to obtain a white solid copolymer of ethylene and propylene. Vacuum drying until constant weight. Yield: 8.4g, catalytic activity 8.4X 10 7 g/mol·h，M η ＝1.1×10 6 g/mol, molecular weight distribution PDI =2.3.
Example 26:
200mL of toluene and 3.33mL of a toluene solution of methylaluminoxane (1.5 mol/L) were charged into a polymerization vessel under nitrogen protection, the temperature was adjusted to 100 ℃, and 0.1. Mu. Mol of catalyst T4 was weighed and charged into the reaction vessel. The ethylene pressure was adjusted to 1.0MPa, and propylene gas was introduced thereinto to make the total pressure to be 3.0MPa. After 1 hour of reaction, the polymerization was terminated and filtered to obtain a white solid copolymer of ethylene and propylene. Vacuum drying until constant weight. Yield: 10.0g, catalytic activity 1X 10 8 g/mol·h，M η ＝2.7×10 6 g/mol, molecular weight distribution PDI =2.4.
Example 27:
under the protection of nitrogen, 200mL of toluene and 3.33mL of methyl were added to the polymerization kettleToluene solution of aluminoxane (1.5 mol/L), adjusting the temperature to 120 ℃, and adding 0.1. Mu. Mol of catalyst T5 into the reaction kettle. The ethylene pressure was adjusted to 1.0MPa, and propylene gas was introduced thereinto to make the total pressure to be 3.0MPa. After 1 hour of reaction, the polymerization was terminated and filtered to obtain a white solid copolymer of ethylene and propylene. Drying in vacuum until constant weight. Yield: 7.9g, catalytic activity 7.9X 10 7 g/mol·h，M η ＝1.4×10 6 g/mol, molecular weight distribution PDI =1.7.
Example 28:
under the protection of nitrogen, 200mL of toluene, 3.33mL of a toluene solution of modified methylaluminoxane (1.5 mol/L) and 2.5mmol of 1-hexene were sequentially added to a polymerization kettle, and the temperature was adjusted to 100 ℃. 0.1. Mu. Mol of catalyst T1 was weighed out and introduced into the reaction vessel. Adjusting the ethylene pressure to 1.0MPa, terminating the polymerization after reacting for 1 hour, and filtering to obtain a white solid ethylene and 1-hexene copolymer. Vacuum drying until constant weight. Yield: 4.1g, catalytic activity 4.1X 10 7 g/mol·h，M η ＝1.7×10 6 g/mol, molecular weight distribution PDI =1.1.
Example 29:
200mL of toluene, 3.33mL of a toluene solution of modified methylaluminoxane (1.5 mol/L) and 5mmol of 1-octene were sequentially added to the polymerization vessel under nitrogen protection, and the temperature was adjusted to 100 ℃. 0.1. Mu. Mol of catalyst T4 was weighed into the reaction vessel. Adjusting the ethylene pressure to 1.0MPa, terminating the polymerization after reacting for 1 hour, and filtering to obtain white solid ethylene and 1-octene copolymer. Vacuum drying until constant weight. Yield: 4.5g, catalytic activity 4.5X 10 7 g/mol·h，M η ＝1.6×10 6 g/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 at 30 ℃, 50mmol of methyl acrylate and 3.0mL of methyl aluminoxane solution in toluene (1.5 mol/L) are added, 0.50 mu mol of catalyst T1 is weighed and added into the reaction kettle, and 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 filtration, and the copolymer is dried in vacuum until the constant weight is reached. Yield: 8.5g, catalytic activity 1.7X 10 7 g/mol·h，M η ＝2.0×10 5 g/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 methyl aluminoxane toluene solution (1.5 mol/L) are added, 0.50 mu mol of catalyst T2 is weighed and added into the reaction kettle, and the ethylene pressure is adjusted to be 1.0MPa. Starting polymerization reaction, terminating polymerization after 1 hour of reaction, filtering to obtain ethylene and ethyl acrylate copolymer, and vacuum drying until constant weight. Yield: 5.7g, catalytic activity 1.1X 10 7 g/mol·h，M η ＝9.5×10 5 g/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 at 40 ℃, 50mmol of butyl acrylate and 3.0mL of toluene solution of methylaluminoxane (1.5 mol/L) are added, 0.50 mu mol of catalyst T3 is weighed and added into the reaction kettle, and the ethylene pressure is adjusted to 1.0MPa. Starting the polymerization reaction, stopping the polymerization after 1 hour of reaction, filtering to obtain the copolymer of ethylene and butyl acrylate, and drying in vacuum until the weight is constant. Yield: 7.3g, catalytic activity 1.5X 10 7 g/mol·h，M η ＝8.5×10 5 g/mol, comonomer insertion 15%, molecular weight distribution PDI =2.5.
Example 33:
under the protection of nitrogen, 200mL of toluene is added into a polymerization kettle, the polymerization temperature is set at 40 ℃, 50mmol of methyl methacrylate and 3.0mL of toluene solution of methylaluminoxane (1.5 mol/L) are added, 0.50 mu mol of catalyst T4 is weighed and added into the reaction kettle, and the ethylene pressure is adjusted to 1.0MPa. Starting polymerization reaction, terminating polymerization after 1 hour of reaction, filtering to obtain the copolymer of ethylene and methyl methacrylate, and drying in vacuum until constant weight is obtained. Yield: 10.7g, catalytic activity 2.1X 10 7 g/mol·h，M η ＝8.1×10 5 g/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 at 50 ℃, 50mmol of acrylonitrile and 3.0mL of methyl aluminoxane solution in toluene (1.5 mol/L) are added, 0.50 mu mol of catalyst T5 is weighed and added into the reaction kettle, and the ethylene pressure is adjusted to 1.0MPa. Starting polymerization reaction, terminating polymerization after 1 hour of reaction, filtering to obtain ethylene and acrylonitrile copolymer, and vacuum drying until constant weight. Yield: 6.6g, catalytic activity 1.3X 10 7 g/mol·h，M η ＝1.5×10 5 g/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 at 50 ℃, 50mmol of butenamide and 3.0mL of methyl aluminoxane solution in toluene (1.5 mol/L) are added, 0.50 mu mol of catalyst T6 is weighed and added into the reaction kettle, and the ethylene pressure is adjusted to 1.0MPa. Starting the polymerization reaction, stopping the polymerization after 1 hour of reaction, filtering to obtain the copolymer of ethylene and butenamide, and drying in vacuum until the weight is constant. Yield: 5.2g, catalytic activity 1X 10 7 g/mol·h，M η ＝3.5×10 5 g/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:
a nitrogen-containing aryloxy titanocene compound, which has the following chemical structural formula:
Figure BDA0002609412220000191
in the formula (I), the compound is shown in the specification,
R 1 ～R 4 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl (e.g., cumyl), phenyl, halo;
R 5 ～R 13 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, phenyl;
R 14 one selected from the following groups: cyclopentadienyl, indenyl, fluorenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted cyclopentadienyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted indenyl, C 1 ～C 15 Monoalkyl-or polyalkyl-substituted fluorenyl.
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 chemical structural formula of the nitrogen-containing phenolic ligand compound is as follows:
Figure BDA0002609412220000201
the cyclopentadienyl titanium trichloride compound is R 14 TiCl 3 。
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 phenolic ligand compound to the titanocene trichloride compound is 1 (1.0-2.0), such as 1.2, 1.5 and 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 tetra (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, amino, amido or thioether group.
When an olefin monomer is homopolymerized, a nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or a boron fluoride compound is used as a cocatalyst, the olefin monomer is 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;
when olefin monomers are copolymerized, a nitrogen-containing aryloxy titanocene compound is used as a main catalyst, an alkyl aluminoxane or a boron fluoride compound is used as a cocatalyst, at least two olefin monomers are copolymerized under the conditions 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;
when olefin and polar monomer are copolymerized, a nitrogen-containing aryloxy titanocene compound is used as a main catalyst, an alkyl aluminoxane or a boron fluoride compound is used as a cocatalyst, the olefin monomer and the polar monomer are copolymerized under 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.
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 (10)

1. The nitrogen-containing aryloxy titanocene compound is characterized by having the following chemical structural formula:
Figure FDA0003914925700000011
in the formula (I), the compound is shown in the specification,
R 1 ～R 4 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, phenyl, halogen;
R 5 ～R 13 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, phenyl;
R 14 one selected from the following groups: pentamethylcyclopentadienyl, indenyl or fluorenyl.
2. The nitrogen-containing aryloxycarbonyl titanocene compound of claim 1, wherein in formula (I),
R 1 ～R 4 each independently selected from one of the following groups: hydrogen, C 1 ～C 6 Alkyl of linear, branched or cyclic structure, cumyl, phenyl, halogen;
R 5 ～R 13 are respectively independentIs selected from one of the following groups: hydrogen, C 1 ～C 6 Alkyl with linear, branched or cyclic structure, phenyl.
3. A method for producing a 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 chemical structural formula of the nitrogenous phenolic ligand compound is as follows:
Figure FDA0003914925700000021
the titanocene trichloride compound is R 14 TiCl 3 ，
R 1 ～R 4 Each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, C 7 ～C 20 Mono-or poly-aryl substituted alkyl, phenyl, halogen;
R 5 ～R 13 each independently selected from one of the following groups: hydrogen, C 1 ～C 10 Alkyl of linear, branched or cyclic structure, phenyl;
R 14 one selected from the following groups: pentamethylcyclopentadienyl, indenyl or fluorenyl.
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 nitrogen-containing aryloxy titanocene compound according to claim 3, wherein 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.
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 titanium compound as claimed in claim 7, wherein the co-catalyst and/or the carrier are further added to the solution polymerization, the emulsion polymerization, the gas phase polymerization or the slurry polymerization for homopolymerization or copolymerization.
9. The use of a nitrogen-containing aryloxycarbonyl titanium 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 carrier is selected from one or two of 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, amino, amido or thioether group.
10. The use of a nitrogen-containing aryloxycarbonyl titanocene compound as claimed in claim 9,
when olefin monomers are homopolymerized, the nitrogen-containing aryloxy cyclopentadienyl titanium compound is used as a main catalyst, alkyl aluminoxane or boron fluorine compound is used as an auxiliary catalyst, so that the olefin monomers are homopolymerized at 0-150 ℃, and the molar ratio of the main catalyst to the auxiliary catalyst is 1 (1-100000);
when olefin monomers are copolymerized, a nitrogen-containing aryloxy titanocene compound is used as a main catalyst, alkyl aluminoxane or a boron fluoride compound is used as an auxiliary catalyst, at least two olefin monomers are copolymerized at the temperature of 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, 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 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).
CN202010749068.5A 2020-07-30 2020-07-30 Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof Active CN111747995B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010749068.5A CN111747995B (en) 2020-07-30 2020-07-30 Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010749068.5A CN111747995B (en) 2020-07-30 2020-07-30 Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111747995A CN111747995A (en) 2020-10-09
CN111747995B true CN111747995B (en) 2023-02-21

Family

ID=72712359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010749068.5A Active CN111747995B (en) 2020-07-30 2020-07-30 Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111747995B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798313B1 (en) * 1994-12-13 2001-03-21 Asahi Kasei Kogyo Kabushiki Kaisha Olefin polymerization catalyst
US5637660A (en) * 1995-04-17 1997-06-10 Lyondell Petrochemical Company Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety
CN1132856C (en) * 2000-11-02 2003-12-31 中国石油化工股份有限公司 Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application
EP1373332B1 (en) * 2001-03-05 2004-09-22 Stichting Dutch Polymer Institute Olefin polymerization catalyst component and catalyst system and polymerization process using such a catalyst system
CN101812094B (en) * 2010-04-01 2012-04-18 中国科学院化学研究所 cyclopentadiene-N- (2-methylquinoline) titanium benzoate complex and preparation method and application thereof
CN102850391B (en) * 2011-07-01 2015-12-09 中国石油化工股份有限公司 The method of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and ethylene polymerization
CN103772439B (en) * 2012-10-26 2016-07-13 中国石油化工股份有限公司 A kind of quinoline benzimidazole Group IVB list half metallocene and its preparation method and application and the method for olefinic polyreaction
CN112778378B (en) * 2021-01-29 2024-07-02 安徽师范大学 Coordination compound with half-sandwich iridium structure and solid-phase synthesis method

Also Published As

Publication number Publication date
CN111747995A (en) 2020-10-09

Similar Documents

Publication Publication Date Title
US7273940B2 (en) Catalysts for the polymerization of unsaturated compounds
JP2017533174A (en) Metallocene compound, catalyst composition containing the same, and method for producing olefin polymer using the same
CN110092744B (en) High-thermal-stability tertiary-butyl-containing asymmetric diimine pyridine complex, and preparation method and application thereof
KR101600583B1 (en) Dinuclear metallocene compound, and method for preparing the same
CN109956980B (en) Ethylidene acenaphthene asymmetric alpha-diimine nickel catalyst and preparation method and application thereof
CN110655538A (en) Mono-metallocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof
CN111747995B (en) Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof
JP5759074B2 (en) Transition metal catalyst composition containing transition metal compound and method for producing polyolefin using the catalyst composition
Alonso-Moreno et al. Niobium, titanium, zirconium and hafnium complexes incorporating germanium bridged ansa ligands. X-Ray crystal structures of [Zr {Me2Ge (η5-C5Me4) 2} Cl2] and [M {Me2Ge (η5-C5Me4)(η5-C5H4)} Cl2](M= Zr, Hf)
CN111747977A (en) Arylamine ether metal complexes, and preparation method and application thereof
KR20210107735A (en) Heterocyclic-Heterocyclic Group IV Transition Metal Catalyst for Olefin Polymerization
KR20120092977A (en) New transition metal compound, new organic ligand compound, catalysts composition comprising the transition metal compound and preparation method of poly-olefin using the catalysts composition
KR102189654B1 (en) Method for preparation of novel ligand compound and transition metal compound
CN109320559B (en) Nickel-palladium metal complex, preparation method and application thereof, product and application thereof
KR101601935B1 (en) Dinuclear metallocene compound, catalyst composition and method for preparing polyolefin using the same
KR102024327B1 (en) Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same
KR101705850B1 (en) Novel ligand compound and transition metal compound comprising the same
KR101648137B1 (en) Method of preparing ligand compound and transition metal compound
KR20220094138A (en) Metal-ligand complex, catalyst composition for preparing ethylene-based polymer containing the same, and preparation method of ethylene-based polymer using the same
Ivancheva et al. Ethylene polymerization on titanium phenoxyimine complexes with different structures
KR102191461B1 (en) Novel ligand compound and transition metal compound comprising the same
KR20200060279A (en) Transition metal compound, and catalystic composition comprising the same
KR101238785B1 (en) Multinuclear nonmetallocene compounds and process for preparation of olefin polymers using the same
CN111592561B (en) Asymmetric diimine titanium metal complex and preparation method and application thereof
KR102694342B1 (en) Pyridine-based transition metal compounds and catalytic compositions comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant