CN113527351A - Pyridine amino hafnium compound and preparation method and application thereof - Google Patents

Pyridine amino hafnium compound and preparation method and application thereof Download PDF

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CN113527351A
CN113527351A CN202010300446.1A CN202010300446A CN113527351A CN 113527351 A CN113527351 A CN 113527351A CN 202010300446 A CN202010300446 A CN 202010300446A CN 113527351 A CN113527351 A CN 113527351A
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hafnium
pyridylamine
formula
catalyst
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王雄
高海洋
徐人威
龚光碧
王申鸣
马艳萍
杨世元
陈旭
李广全
王凌志
钟柳
刘芸
韩晓昱
郭义
樊洁
穆蕊娟
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Petrochina Co Ltd
Sun Yat Sen University
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Petrochina Co Ltd
Sun Yat Sen University
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    • 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
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    • 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
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    • 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

Abstract

The invention discloses a pyridine amido hafnium compound, a preparation method thereof and application thereof in olefin polymerization reaction. The structural formula of the pyridine amino hafnium compound is shown as a formula I:
Figure DDA0002453787170000011
wherein R represents hydrogen and methyl, and X represents methyl, methoxy, fluorine, chlorine and bromine. The pyridine amino hafnium compound can be used as a main catalyst to catalyze olefin polymerization, has high activity and strong orientation capability, shows very strong copolymerization capability and active polymerization performance, and can catalyze ethylene and alpha-olefin to obtain high-performance polyolefin materials.

Description

Pyridine amino hafnium compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a pyridine amino hafnium compound, and a preparation method and application thereof.
Background
Polyolefin is a widely used material. It has the advantages of easy processing and use, low price, etc. Olefin polymerization catalysts are key to the polyolefin industry because of their ability to regulate polyolefin structure and properties. Therefore, the design and development of new polyolefin catalysts are core technologies that have pushed the development of the polyolefin industry.
Hafnium pyridylamide catalysts were first developed by DOW chemical company and showed good catalytic olefin polymerization performance. The pyridine amido hafnium catalyst can catalyze ethylene polymerization with high activity to prepare linear polyethylene. It can also catalyze propylene and other alpha-olefin polymerization at high temperature to prepare isotactic polypropylene, and has the characteristics of high activity, high polymer molecular weight, stereoselectivity and the like. Meanwhile, the catalyst shows good copolymerization performance, and can catalyze the copolymerization of ethylene and alpha-olefin to prepare the polyolefin elastomer with high alpha-olefin insertion rate. In particular, it can also be used as one of the chain shuttling catalysts, together with a zirconium-based catalyst, to catalyze the copolymerization of ethylene and octene to produce a polyolefin block copolymer. DOW chemical company has successfully prepared commercial high performance polyolefin block copolymers (OBC) using hafnium pyridyl amide catalysts via chain shuttling polymerization techniques. Thus, hafnium pyridyl amide catalysts have attracted considerable attention in the polyolefin field.
The structure of the hafnium pyridylamide catalyst has an important influence on the catalytic performance of the catalyst. Besides the influence of the substituents on the skeleton on the activity, molecular weight and polymer regularity, the ortho-substituents of aromatic amines also have an important influence on the polymerization properties. Researches show that the introduction of substituent with large steric hindrance at the ortho position of arylamine can further improve the thermal stability of the catalyst and simultaneously enhance the catalytic activity and the stereoselectivity for alpha-olefin polymerization. Thus, the ortho position of the arylamine of the current pyridylamine hafnium catalyst is generally replaced by isopropyl. The subject group of the teaching of Coates reports that a tert-butyl substituted hafnium pyridylamide catalyst catalyzes propylene polymerization, shows better activity, obtains higher molecular weight polypropylene, and obviously improves the isotacticity of the polypropylene. The substituent at the ortho position of the prior arylamine is mainly aliphatic alkyl, and the catalyst for substituting aryl is not available.
Disclosure of Invention
The ortho-substituent of the existing pyridine amino hafnium compound is isopropyl, and the compound has no larger substituent. If rigid aromatic rings are substituted, on the one hand, the aromatic rings can significantly improve the thermal stability of the catalyst and also can improve the molecular weight of the catalyzed olefin polymerization product. Meanwhile, the occurrence of chain transfer can be inhibited due to large steric hindrance, and a narrowly distributed polymer is obtained. On the other hand, the larger steric hindrance substituent can generate steric repulsion action with the growing chain and the monomer, the stereoregularity of alpha-olefin polymerization is controlled, and the polymer with higher regularity is obtained. In addition, the para position of aniline does not currently have substituents with different electronic effects. And the olefin polymerization can be remarkably regulated and controlled through the electronic effect of the para position of the aniline.
Therefore, the invention provides a novel arylamine hafnium compound containing diphenylmethyl at ortho position and containing substituent groups with different electronic effects at para position, and a preparation method and application thereof.
The pyridine amino hafnium compound has the following structure:
Figure BDA0002453787150000021
in the formula I, R represents hydrogen and methyl, X represents methyl, methoxy, fluorine, chlorine and bromine, and the electronic effect can be regulated. The compound can perform homopolymerization and copolymerization of ethylene and alpha-olefin under the action of a cocatalyst. The cocatalyst is a boron-containing compound, or a mixture of an aluminum alkyl and a boron-containing compound.
The first purpose of the invention is to provide a hafnium pyridylamido compound.
The second purpose of the invention is to provide a preparation method of the hafnium pyridylamido compound.
The third purpose of the invention is to provide an application of the pyridylamine hafnium compound in catalyzing olefin polymerization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pyridylamine hafnium compound having the structural formula:
Figure BDA0002453787150000031
in the formula I, R represents hydrogen and methyl, and X represents methyl, methoxy, fluorine, chlorine and bromine.
The preparation method of the hafnium pyridylamidoaluminate compound comprises the following operation steps:
1) the pyridone compound and naphthalene boric acid are subjected to coupling reaction to obtain the aryl-substituted 2-naphthyl-pyridone compound.
Figure BDA0002453787150000032
2) Reacting 4-substituted aniline with benzhydrol to obtain substituted aniline compound.
Figure BDA0002453787150000033
3) The 2-aryl-pyridone compound and substituted aniline are subjected to condensation reaction to obtain a substituted pyridimine compound.
Figure BDA0002453787150000034
4) And carrying out reduction reaction on the substituted pyridimine compound and a strong reducing agent to prepare the substituted pyridylamine compound ligand.
Figure BDA0002453787150000041
5) The pyridylamine compound and strong base are subjected to deprotonation reaction, and then metal salt of hafnium tetrachloride is added to prepare the corresponding pyridylamine hafnium chloride compound. And continuously carrying out methylation reaction on the pyridylamine hafnium chloride compound and a methyl magnesium bromide Grignard reagent to prepare the corresponding pyridylamine hafnium methyl compound.
Figure BDA0002453787150000042
The invention also provides the use of the novel hafnium compound for the catalysis of olefin polymerization under the activation of a cocatalyst.
The cocatalyst is a boron-containing compound or a mixture of alkyl aluminum and the boron-containing compound. The boron-containing compound group catalyst may include triethylammoniumtetra (phenyl) boron, tributylammoniumtetra (phenyl) boron, trimethylammonium tetrakis (phenyl) boron, tripropylammoniumtetra (phenyl) boron, trimethylammonium tetrakis (p-butylphenyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, N-diethylaniliniumtetrakis (phenyl) boron, N-diethylaniliniumtetrakis (pentafluorophenyl) boron, trimethylphosphinetetraphenyl) boron, tripropylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (p-trifluoromethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tri (p-tolylboron, tri (p-tolylamino) boron, tri (p-t, Tributylammonium tetrakis (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphine tetrakis (phenyl) boron, tris (pentafluorophenyl) borane, triphenylcarbenium tetrakis (pentafluorophenyl) boron, triphenylcarbenium tetrakis (p-trifluoromethylphenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) boron, and triphenylcarbenium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, etc.
The alkyl aluminum may include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl aluminum chloride, triisopropyl aluminum, tri-sec-butyl aluminum, tripentylaluminum, triisopentyl aluminum, tricyclopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-methylphenyl aluminum, dimethyl methoxy aluminum, and the like. The cocatalyst is preferably tri (pentafluorobenzene) borane or triphenylcarbonium tetra (pentafluorobenzene) borate or N, N-dimethylanilinium tetra (pentafluorophenyl) borate or triisobutylaluminum and the composition of the boron-containing compounds, and can catalyze homopolymerization and copolymerization of ethylene and alpha-olefin with high activity under the action of the cocatalyst.
The main catalyst, the cocatalyst and Hf of the alkyl aluminum: b: the Al ratio is 1: 1.0-5.0: 100-500 (molar ratio).
The olefin monomer is ethylene, propylene, hexene, octene or the mixture of two or more monomers.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the benzhydryl with high steric hindrance rigidity is introduced at the ortho position of the pyridine amido hafnium compound arylamine, so that the thermal stability of the catalyst can be improved, and the activity of catalyzing olefin polymerization and the molecular weight of the polymer are improved.
(2) The benzhydryl with high steric hindrance rigidity can generate space repulsion with the chain-lengthening chain and the monomer in the polymerization process, and can control the stereoselectivity in the alpha-olefin polymerization process to obtain a polymerization product with high isotacticity.
(3) When the hafnium compound is used for catalyzing olefin polymerization, the occurrence of chain transfer chain can be inhibited by large steric hindrance, and the obtained polyolefin material has narrow molecular weight distribution.
(4) The para-position of the aniline of the hafnium compound can easily introduce substituent groups with different electronic effects to regulate and control the electronic effect of the catalyst, so that the performance of catalyzing olefin polymerization is easier to regulate and control.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a hafnium pyridylamine compound obtained in example 18.
FIG. 2 is a nuclear magnetic carbon spectrum of the hafnium pyridylamidoaluminate compound obtained in example 18.
FIG. 3 is a DSC of polyethylene obtained in example 24.
FIG. 4 is a DSC of an ethylene-octene copolymer obtained in example 44.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
For the sake of clarity of the ligands and complexes in the examples, the following are illustrated:
n1 is a substituted aniline represented by formula III wherein X is methyl;
n2 is a substituted aniline represented by formula III wherein X is methoxy;
n3 is a substituted aniline represented by formula III wherein X is fluorine;
n4 is a substituted aniline represented by formula III wherein X is chloro;
n5 is a substituted aniline represented by formula III wherein X is bromine;
b1 is a pyridimine compound represented by formula IV, wherein R is hydrogen and X is methyl;
b2 is a pyridimine compound represented by formula IV, wherein R is hydrogen and X is methoxy;
b3 is a pyridimine compound represented by formula IV, wherein R is hydrogen and X is fluorine;
b4 is a pyridimine compound represented by formula IV, wherein R is hydrogen and X is chlorine;
b5 is a pyridimine compound represented by formula IV, wherein R is hydrogen and X is bromine;
b6 is a pyridimine compound represented by formula IV, wherein R is methyl and X is methyl;
ligand L1 is a pyridylamine ligand shown in formula V, wherein R is hydrogen and X is methyl;
ligand L2 is a pyridylamine ligand shown in formula V, wherein R is hydrogen and X is methoxy;
ligand L3 is a pyridylamine ligand shown in formula V, wherein R is hydrogen and X is fluorine;
ligand L4 is a pyridylamine ligand shown in formula V, wherein R is hydrogen and X is chlorine;
ligand L5 is a pyridylamine ligand shown in formula V, wherein R is hydrogen and X is bromine;
ligand L6 is a pyridylamine ligand shown in formula V, wherein R is methyl and X is methyl;
the complex C1 is a pyridylamine hafnium complex shown in formula I, wherein R is hydrogen, and X is methyl;
the complex C2 is a pyridylamine hafnium complex shown in formula I, wherein R is hydrogen, and X is methoxy;
the complex C3 is a pyridylamine hafnium complex shown in formula I, wherein R is hydrogen and X is fluorine;
the complex C4 is a pyridylamine hafnium complex shown in formula I, wherein R is hydrogen and X is chlorine;
the complex C5 is a pyridylamine hafnium complex shown in formula I, wherein R is hydrogen, and X is bromine;
the complex C6 is a pyridylamine hafnium complex shown in formula I, wherein R is methyl and X is methyl;
preparation of ligands
Example 1
Synthesis of pyridone compounds
Under a nitrogen atmosphere, 1.86g (10mmol) of 2-acetyl-6-bromopyridine, 1.72g (10mmol) of naphthalene boronic acid, 15mg of tetrakis (triphenylphosphine) palladium and 6g of potassium carbonate were sequentially added to a vial, and 30mL of ethanol, 20mL of toluene and 10mL of water were added thereto, followed by reflux overnight. The resulting mixture was subjected to liquid separation extraction, washed with water and dried to obtain 2.17g of pyridine aldehyde compound A in a yield of 93%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(300MHz,C6D6):δ8.19-8.15(m,1H,ArH),8.01(dd,2.0Hz,1H,ArH),7.71-7.66(m,2H,ArH),7.45(dd,1H,ArH),7.33-7.28(m,3H,ArH),7.18-7.13(m,2H,ArH),2.59(s,3H,(CH3)CO).
example 2
Synthesis of substituted Aniline N1
Adding 13.3g (72.2mmol) of benzhydrol and 3.66 g (34mmol) of 4-methylaniline into a bottle, heating to 80 ℃ for melting, adding 2.4g (17.6mmol) of zinc chloride dissolved in hydrochloric acid, heating to 150 ℃, reacting for 2h, cooling, dissolving with dichloromethane, neutralizing redundant acid with sodium bicarbonate, performing liquid separation extraction, performing spin drying, and performing leaching with ethanol to obtain 13.3g of white powder with the yield of 89%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(400MHz,CDCl3):δ7.34-7.27(d,8H,Ph),7.24-7.18(d,4H,Ph),7.12-7.06(d,8H,Ph),6.38(s,2H,Ar-H),5.45(s,2H,CHPh2),3.27(s,2H,NH2),2.02(s,3H,Me).
example 3
Synthesis of substituted Aniline N2
According to the synthesis method in example 2, 4-methylaniline in example 2 was replaced with 4-methoxyaniline, and the yield was 67%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(400MHz,CDCl3):δ3.24(2H,bs,NH2),3.55(3H,s,OCH3),5.64(2H,s,CHPh2),6.40(2H,s,Ar-H),7.25-7.43(20H,m,Ar-H).
example 4
Synthesis of substituted Aniline N3
According to the synthesis method in example 2, 4-methylaniline in example 2 was replaced with 4-fluoroaniline, and the yield was 48%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(400MHz,CDCl3):δ7.44-7.37(d,8H,Ph),7.24-7.15(d,4H,Ph),7.12-7.06(d,8H,Ph),6.42(s,2H,Ar),5.44(s,2H,CHPh2),3.26(s,2H,NH2).
example 5
Synthesis of substituted Aniline N4
According to the synthesis method in example 2, 4-methylaniline in example 2 was replaced with 4-chloroaniline, and the yield was 71%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(400MHz,CDCl3):δ7.44-7.37(d,8H,Ph),7.24-7.15(d,4H,Ph),7.12-7.06(d,8H,Ph),6.42(s,2H,Ar),5.44(s,2H,CHPh2),3.26(s,2H,NH2).
example 6
Synthesis of substituted Aniline N5
The synthesis procedure of example 2 was followed to replace 4-methylaniline in example 2 with 4-bromoaniline in 32% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(400MHz,CDCl3):δ7.35-7.28(d,8H,Ph),7.24-7.17(d,4H,Ph),7.12-7.07(d,8H,Ph),6.37(s,2H,Ar),5.43(s,2H,CHPh2),3.25(s,2H,NH2).
example 7
Synthesis of pyridimine Compound B1
Under a nitrogen atmosphere, 2.33g (10mmol) of the pyridone compound, N14.62g (10.5mmol) of aniline, and 10mg of p-toluenesulfonic acid were dissolved in 50mL of toluene, and the mixture was refluxed for 48 hours with water. The solvent was dried by evaporation to give a pyridimine compound B1(6.53g) in 94% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(CDCl3,400MHz):δ8.51(s,1H,Nap-H),8.24-8.17(d,1H,Py-H),8.01-7.78(m,6H,Nap-H),7.57-7.47(m,2H,Py-H),7.25-7.01(m,20H,Ar-H),6.71(s,2H,Ar-H),5.33(s,2H,CH),2.19(s,3H,Ar-CH3),1.21(s,3H,C＝N-CH3).
example 8
Synthesis of pyridimine Compound B2
According to the synthesis procedure in example 7, N1 in example 7 was replaced with N2, yield 81%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(CDCl3,400MHz):δ8.52(s,1H,Nap-H),8.25-8.17(d,1H,Py-H),8.02-7.77(m,6H,Nap-H),7.57-7.47(m,2H,Py-H),7.25-7.01(m,20H,Ar-H),6.71(s,2H,Ar-H),5.33(s,2H,CH),2.23(s,3H,Ar-OCH3),1.23(s,3H,C＝N-CH3).
example 9
Synthesis of pyridimine Compound B3
Following the synthetic procedure in example 7, N1 in example 7 was replaced with N3 in 74% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(CDCl3,400MHz):δ8.51(s,1H,Nap-H),8.23-8.17(d,1H,Py-H),8.01-7.76(m,6H,Nap-H),7.57-7.47(m,2H,Py-H),7.25-7.01(m,20H,Ar-H),6.72(s,2H,Ar-H),5.31(s,2H,CH),1.23(s,3H,C＝N-CH3).
example 10
Synthesis of pyridimine Compound B4
Following the synthetic procedure in example 7, N1 in example 7 was replaced with N4 in 65% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(CDCl3,400MHz):δ8.52(s,1H,Nap-H),8.25-8.17(d,1H,Py-H),8.02-7.77(m,6H,Nap-H),7.57-7.47(m,2H,Py-H),7.25-7.01(m,20H,Ar-H),6.71(s,2H,Ar-H),5.33(s,2H,CH),1.22(s,3H,C＝N-CH3).
example 11
Synthesis of pyridimine Compound B5
Following the synthetic procedure in example 7, N1 in example 7 was replaced with N5 in 65% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(CDCl3,400MHz):δ8.53(s,1H,Nap-H),8.25-8.16(d,1H,Py-H),8.02-7.77(m,6H,Nap-H),7.57-7.47(m,2H,Py-H),7.25-7.01(m,20H,Ar-H),6.71(s,2H,Ar-H),5.33(s,2H,CH),1.23(s,3H,C＝N-CH3).
example 12
Synthesis of ligand pyridylamino compound L1
The pyridimine compound was dissolved in dry toluene under a nitrogen atmosphere, and a solution of lithium aluminum hydride (1.1eq) was added dropwise at 0 ℃ under reflux overnight, followed by liquid separation, drying, and recrystallization to give 5.65g of white crystals, 88% yield, as pyridylamine ligand L1. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.16(s,2H,CHPh2),4.59(d,1H,C-NH),4.38(m,1H,CH-N),1.85(s,3H,Ar-CH3),1.55(d,3H,NC-CH3).
example 13
Synthesis of ligand pyridylamino compound L2
The procedure was followed for the synthesis of example 12 substituting aniline N1 in example 12 with N2 in 64% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.16(s,2H,CHPh2),4.59(d,1H,C-NH),3.48(s,1H,Ar-OCH3),1.55(m,6H,NC(CH3)).
example 14
Synthesis of ligand pyridylamino compound L3
The procedure was followed for the synthesis of example 12 except that the aniline N1 in example 12 was replaced with N3, in 73% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.16(s,2H,CHPh2),4.59(d,1H,C-NH),3.48(s,1H,Ar-OCH3),1.55(m,6H,NC(CH3)2).
example 15
Synthesis of ligand pyridylamino compound L4
According to the synthesis procedure in example 12, aniline N1 in example 12 was replaced with N4, yield 77%. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.33(s,2H,CHPh2),4.62(d,1H,C-NH),1.61(m,3H,NC(CH3)).
example 16
Synthesis of ligand pyridylamino compound L5
The procedure was followed for the synthesis of example 12 substituting aniline N1 in example 12 with N2 in 62% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.46(s,2H,CHPh2),4.67(d,1H,C-NH),1.65(m,3H,NC(CH3)).
example 17
Synthesis of ligand pyridylamino compound L6
The procedure was followed for the synthesis of example 12 except that the aniline N1 in example 12 was replaced with N6, in 86% yield.1H NMR(C6D6,400MHz):δ8.24-8.17(d,1H,Ar-H),7.69-7.59(dd,2H,Ar-H),7.44-7.39(d,1H,Ar-H),7.27-7.18(m,7H,Ar-H),7.11-6.93(m,18H,Ar-H),6.87(s,2H,Ar-H),6.46(dd,1H,Ar-H),6.46(s,2H,CHPh2),4.67(d,1H,C-NH),1.49(m,6H,NC(CH3)2).
Preparation of bis-hafnium complexes
Example 18
Synthesis of Complex C1
L1(1.7mmol) was weighed out and dissolved in 10mL of toluene, and an n-butyllithium solution (1.14mL,1.6M) was added dropwise at 0 ℃ to react for 3 hours. The toluene was drained, washed with n-hexane and the supernatant decanted to give a yellow lithium salt. Redissolving the lithium salt with toluene and adding HfCl4(0.61g, 1.9mmol) was transferred to the reaction system and the temperature was raised to 90 ℃ and refluxed overnight. The temperature of the solution was then lowered to room temperature, and MeMgBr solution (2.13mL,3mol/L) was added dropwise and stirred at room temperature for 3h. The solvent was drained, the solid was washed 3 times with n-hexane, filtered and the n-hexane filtrate was collected. The solvent was concentrated to about 3mL and crystallized at-35 ℃ overnight. The crystals were filtered, washed with chilled n-hexane and dried. Orange yellow crystals were obtained with a yield of 46%.1H NMR(C6D6,400MHz):δ8.43(d,1H,Ar-H),8.39(d,1H,Ar-H),7.82(d,1H,Ar-H),7.78(d,1H,Ar-H),7.59(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.98(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,1H,NCH),1.97(s,3H,Ar-CH3),1.07(d,3H,CCH3),0.82(s,3H,Hf-CH3),0.37(s,3H,Hf-CH3).
Example 19
Synthesis of Complex C2
Following the synthetic procedure in example 18, ligand L1 in example 18 was replaced with L2 in 35% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.44(d,1H,Ar-H),8.39(d,1H,Ar-H),7.82(d,1H,Ar-H),7.78(d,1H,Ar-H),7.59(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.98(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,2H,NCH),1.11(d,3H,CCH3),1.07(d,3H,OCH3),0.82(s,3H,Hf-CH3),0.37(s,3H,Hf-CH3).
example 20
Synthesis of Complex C3
Following the synthetic procedure in example 18, ligand L1 in example 18 was replaced with L3 in 37% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.42(d,1H,Ar-H),8.39(d,1H,Ar-H)，7.82(d,1H,Ar-H),7.78(d,1H,Ar-H),7.56(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.98(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,2H,NCH),1.07(d,3H,CCH3),0.82(s,3H,Hf-CH3),0.38(s,3H,Hf-CH3).
example 21
Synthesis of Complex C4
Following the synthetic procedure in example 18, ligand L1 in example 18 was replaced with L4 in 27% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.42(d,1H,Ar-H),8.39(d,1H,Ar-H)，7.82(d,1H,Ar-H),7.78(d,1H,Ar-H),7.56(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.98(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,2H,NCH),1.07(d,3H,CCH3),0.82(s,3H,Hf-CH3),0.38(s,3H,Hf-CH3).
example 22
Synthesis of Complex C5
Following the synthetic procedure in example 18, ligand L1 in example 18 was replaced with L5 in 28% yield. The nuclear magnetic hydrogen spectrum is as follows:1H NMR(C6D6,400MHz):δ8.45(d,1H,Ar-H),8.39(d,1H,Ar-H)，7.84(d,1H,Ar-H),7.78(d,1H,Ar-H),7.56(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.96(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,2H,NCH),1.07(d,3H,CCH3),0.83(s,3H,Hf-CH3),0.38(s,3H,Hf-CH3).
example 23
Synthesis of Complex C6
L6(1.5mmol) was weighed out and dissolved in 10mL of toluene, an n-butyllithium solution (1.04mL,1.6M) was added dropwise at 0 ℃ and reacted for 3 hours, toluene was drained and washed with n-hexane, and the supernatant was poured out to obtain a yellow lithium salt. Redissolving the lithium salt with toluene and adding HfCl4(1.65mmol) was transferred to the system with toluene rinse and warmed to 90 ℃ under reflux overnight. Cooled to room temperature and MeMgBr solution (2mL,3[ M ]) is added dropwise]) Stirred at room temperature for 3h. The solvent was drained, the solid was washed 3 times with n-hexane, filtered and the n-hexane filtrate was collected, the solvent was concentrated to about 3mL and crystallized overnight at-35 ℃. The crystals were filtered, washed with chilled n-hexane and dried. Orange yellow crystals were obtained with a yield of 37%.1H NMR:(C6D6,400MHz):δ8.43(d,1H,Ar-H),8.39(d,1H,Ar-H)，7.82(d,1H,Ar-H),7.78(d,1H,Ar-H),7.59(d,2H,Ar-H),7.55(d,2H,Ar-H),7.51(d,2H,Ar-H),7.43-6.98(m,16H,Ar-H),6.90-6.78(m,5H,Ar-H),6.28(d,1H,Ar-H),5.80(s,1H,HCPh2),5.08(pseudo d,1H,NCH),1.97(s,3H,Ar-CH3),1.57(d,6H,C(CH3)2),0.82(s,3H,Hf-CH3),0.37(s,3H,Hf-CH3).
Three, catalyzing olefin polymerization
Example 24
This example provides a method for homopolymerization of ethylene catalyzed by pyridylamine hafnium compound C1, comprising the following steps:
100mL of dry toluene and 500. mu. mol of triisobutylaluminum (Hf: Al 1:100) were added to a reaction vessel under anhydrous and oxygen-free conditions, 5. mu. mol of pyridylamine hafnium compound C1 and 6. mu. mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Hf: B1: 1.2) were mixed and activated, and then added to the reaction vessel, 10atm of ethylene was introduced, an ethylene homopolymerization reaction was performed at 80 ℃ for 10min, polymerization was terminated with 5% by mass hydrochloric acid-acidified ethanol, stirring for 1h, filtration was performed, washing with ethanol was performed three times, and vacuum drying was performed at 70 ℃ for 12h, to obtain a linear polyethylene polymer.
The catalyst activity of the hafnium pyridylamidoamine compound C1 in this example was 1.21X 106g PE/(mol Hf h), the weight average molecular weight of the linear polyethylene obtained is 635kg/mol, the molecular weight distribution index is 2.3, and the melting temperature is 132.2 ℃.
Example 25
This example provides a process for the homopolymerization of ethylene catalyzed by a hafnium pyridylamido compound C2, which is the same as that described in example 24.
The catalyst activity of the hafnium pyridylamidoamine compound C2 in this example was 1.43X 106g PE/(mol Hf. h), the linear polyethylene obtained had a weight-average molecular weight of 448kg/mol, a molecular weight distribution index of 2.5 and a melting temperature of 131.6 ℃.
Example 26
This example provides a process for the homopolymerization of ethylene catalyzed by a hafnium pyridylamido compound C3, which is the same as that described in example 24.
The catalyst activity of the hafnium pyridylamidoamine compound C3 in this example was 0.89X 106g PE/(mol Hf h), the linear polyethylene obtained had a weight average molecular weight of 278kg/mol, a molecular weight distribution index of 2.6 and a melting temperature of 130.4 ℃.
Example 27
This example provides a process for the homopolymerization of ethylene catalyzed by a hafnium pyridylamido compound C4, which is the same as that described in example 24.
The catalyst activity of the hafnium pyridylamidoamine compound C4 in this example was 0.56X 106g PE/(mol Hf h), the linear polyethylene obtained has a weight-average molecular weight of 147kg/mol, a molecular weight distribution index of 2.6 and a melting temperature of 130.2 ℃.
Example 28
This example provides a process for the homopolymerization of ethylene catalyzed by a hafnium pyridylamido compound C5, which is the same as that described in example 24.
The catalyst activity of the hafnium pyridylamidoamine compound C5 in this example was 0.15X 106g PE/(mol Hf h), the linear polyethylene obtained had a weight average molecular weight of 89kg/mol, a molecular weight distribution index of 2.4 and a melting temperature of 128.1 ℃.
Example 29
This example provides a process for the homopolymerization of ethylene catalyzed by a hafnium pyridylamido compound C6, which is the same as that described in example 24.
Catalysis of the hafnium pyridylamido compound C6 in this exampleThe activation activity was 1.65X 106g PE/(mol Hf h), the weight average molecular weight of the linear polyethylene prepared is 752kg/mol, the molecular weight distribution index is 1.6, and the melting temperature is 133.1 ℃.
Example 30
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. The experimental procedure described in example 24 was followed, the polymerization temperature being 100 ℃.
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 2.13X 106g polymer/(mol Hf. h), the weight average molecular weight of the linear polyethylene prepared was 661kg/mol, the molecular weight distribution index was 1.7, and the melting temperature was 131.7 ℃.
Example 31
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. The polymerization temperature was 120 ℃ according to the experimental procedure in example 24.
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.03X 106g polymer/(mol Hf. h), the weight average molecular weight of the linear polyethylene prepared was 314kg/mol, the molecular weight distribution index was 1.7, and the melting temperature was 130.7 ℃.
Example 32
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental procedure of example 24, the amount of triphenylcarbenium tetrakis (pentafluorobenzene) borate as a co-catalyst was 5. mu. mol (Hf: B ═ 1: 1).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.33X 106g polymer/(mol Hf. h), the weight average molecular weight of the linear polyethylene prepared is 648kg/mol, the molecular weight distribution index is 1.7, and the melting temperature is 131.4 ℃.
Example 33
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental procedure of example 24, the amount of triphenylcarbenium tetrakis (pentafluorobenzene) borate as a co-catalyst was 7.5. mu. mol (Hf: B ═ 1: 1.5).
Catalysis of the hafnium pyridylamido compound C6 in this exampleThe activation activity was 1.61X 106g polymer/(mol Hf. h), the weight average molecular weight of the linear polyethylene prepared is 659kg/mol, the molecular weight distribution index is 1.6, and the melting temperature is 131.7 ℃.
Example 34
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental procedure of example 24, the amount of triphenylcarbenium tetrakis (pentafluorobenzene) borate as a co-catalyst was 25. mu. mol (Hf: B ═ 1: 5).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.63X 106g PE/(mol Hf h), the linear polyethylene obtained had a weight average molecular weight of 542kg/mol, a molecular weight distribution index of 1.7 and a melting temperature of 131.4 ℃.
Example 35
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental procedure in example 24, tris (pentafluorobenzene) borane was used in an amount of 7.5 μmol (Hf: B ═ 1: 1.5).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.32X 106g PE/(mol Hf h), the weight average molecular weight of the linear polyethylene prepared is 551kg/mol, the molecular weight distribution index is 1.5, and the melting temperature is 131.5 ℃.
Example 36
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental procedure in example 24, the cocatalyst N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used in an amount of 7.5 μmol (Hf: B ═ 1: 1.5).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.12X 106g PE/(mol Hf h), the linear polyethylene obtained has a weight-average molecular weight of 502kg/mol, a molecular weight distribution index of 1.7 and a melting temperature of 131.4 ℃.
Example 37
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental method in example 24, triisobutylaluminum was used in an amount of 1.25mmol (Hf: Al ═ 1: 250).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.24X 106g PE/(mol Hf. h), the linear polyethylene obtained had a weight average molecular weight of 473kg/mol, a molecular weight distribution index of 1.7 and a melting temperature of 131.3 ℃.
Example 38
This example provides a method for homopolymerization of ethylene catalyzed by a pyridylamine hafnium compound C6. According to the experimental method in example 24, triisobutylaluminum was used in an amount of 2.5mmol (Hf: Al ═ 1: 500).
The catalyst activity of the hafnium pyridylamidoamine compound C6 in this example was 1.36X 106g PE/(mol Hf. h), the weight average molecular weight of the linear polyethylene obtained by the preparation is 459kg/mol, the molecular weight distribution index is 1.8, and the melting temperature is 131.3 ℃.
Example 39
This example provides a process for the homopolymerization of propylene catalyzed by the pyridine amino hafnium catalyst C6.
Adding 100mL of dry toluene and 500 mu mol of triisobutylaluminum into a reaction kettle under the anhydrous and oxygen-free conditions, mixing and activating 5 mu mol of pyridylamine hafnium compound C6 and 6 mu mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate for 5min, adding into the reaction kettle, introducing 5atm of propylene, carrying out propylene homopolymerization reaction at 80 ℃ for 30min, terminating polymerization in 5% hydrochloric acid acidified ethanol, stirring for 10h, filtering, washing with ethanol for three times, and vacuum drying at 70 ℃ for 12h to obtain the polypropylene polymer.
The catalyst activity of the hafnium pyridylamido catalyst C6 in this example was 0.96X 106g PP/(mol Hf. h), the weight-average molecular weight of the polypropylene obtained by the preparation is 573kg/mol, the molecular weight distribution index is 3.3, the isotacticity is 95 percent, and the melting temperature is 148.1 ℃.
Example 40
This example provides a process for the homopolymerization of 1-hexene catalyzed by the pyridinium aminohafnium catalyst C6.
6mL of dry toluene, 4mL of 1-hexene and 1mmol of triisobutylaluminum were charged into a reaction flask filled with nitrogen under anhydrous and oxygen-free conditions, 10. mu. mol of the pyridylamine hafnium compound C6 and 12. mu. mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate were mixed and activated, and then the mixture was charged into the reaction flask and reacted at 30 ℃ for 2 hours. Terminating the polymerization in 5 percent hydrochloric acid acidified ethanol, stirring for 10 hours, filtering, washing with ethanol for three times, and vacuum drying at 70 ℃ for 12 hours to obtain the polymer.
The catalyst activity of the hafnium pyridylamido catalyst C6 in this example was 0.74X 106g polymer/(mol Hf. h), the weight average molecular weight of the obtained polymer was 18.4kg/mol, the molecular weight distribution index was 1.2, and the monomer conversion was 98%.
EXAMPLE 41
This example provides a process for the homopolymerization of 1-octene using hafnium pyridylamine catalyst C6.
6mL of dry toluene, 4mL of 1-octene and 1mmol of triisobutylaluminum were charged into a reaction flask filled with nitrogen under anhydrous and oxygen-free conditions, 10. mu. mol of the pyridylamine hafnium compound C6 and 12. mu. mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate were mixed and activated, and then the mixture was charged into the reaction flask and reacted at 30 ℃ for 2 hours. Terminating the polymerization in 5 percent hydrochloric acid acidified ethanol, stirring for 10 hours, filtering, washing with ethanol for three times, and vacuum drying at 70 ℃ for 12 hours to obtain the polymer.
The catalyst activity of the hafnium pyridylamido catalyst C6 in this example was 0.67X 106g polymer/(mol Hf. h), the weight average molecular weight of the obtained polymer was 15.2kg/mol, the molecular weight distribution index was 1.3, and the monomer conversion was 94%.
Example 42
This example provides a process for the copolymerization of ethylene and propylene catalyzed by hafnium pyridylamide catalyst C6.
Adding 100mL of dry toluene, 4g of propylene and 500 mu mol of triisobutylaluminum into a reaction kettle under the anhydrous and oxygen-free conditions, mixing and activating 5 mu mol of pyridylamine hafnium compound C6 and 6 mu mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate, adding into the reaction kettle, introducing 10atm of ethylene, carrying out copolymerization reaction at 80 ℃ for 10min, terminating polymerization in hydrochloric acid acidification ethanol with mass fraction of 5%, stirring for 10h, filtering, washing with ethanol for three times, and carrying out vacuum drying at 70 ℃ for 12h to obtain the polymer.
In this exampleThe catalyst activity of the pyridylamine hafnium catalyst C6 was 1.77X 106g polymer/(mol Hf · h), the copolymer obtained has a weight-average molecular weight of 970.9kg/mol and a molecular weight distribution index of 3.1.
Example 43
This example provides a process for the copolymerization of ethylene and 1-hexene catalyzed by the hafnium pyridylamide catalyst C6.
Adding 100mL of dry toluene, 3.37g of 1-hexene and 500 mu mol of triisobutylaluminum into a reaction kettle under the anhydrous and oxygen-free conditions, mixing and activating 5 mu mol of pyridylamine hafnium compound C6 and 6 mu mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate, adding into the reaction kettle, introducing 10atm of ethylene, carrying out copolymerization reaction for 10min at 80 ℃, terminating polymerization in 5 mass percent hydrochloric acid acidified ethanol, stirring for 10h, filtering, washing with ethanol for three times, and vacuum drying for 12h at 70 ℃ to obtain the polymer.
The catalyst activity of the hafnium pyridylamido catalyst C6 in this example was 2.03X 106g polymer/(mol Hf. h), the copolymer obtained had a weight-average molecular weight of 847.6kg/mol, a molecular weight distribution index of 3.7, an insertion rate of 1-hexene of 18%, and melting temperatures of 73.9 ℃ and 113.2 ℃.
Example 44
This example provides a process for the copolymerization of ethylene and 1-octene catalyzed by hafnium pyridylamine catalyst C6.
Adding 100mL of dry toluene, 5.76g of 1-octene and 500 mu mol of triisobutylaluminum into a reaction kettle under anhydrous and oxygen-free conditions, mixing and activating 5 mu mol of pyridylamine hafnium compound C6 and 6 mu mol of triphenylcarbenium tetrakis (pentafluorobenzene) borate, adding the mixture into the reaction kettle, introducing 10atm of ethylene, carrying out copolymerization reaction for 10min at 80 ℃, terminating polymerization in 5 mass percent hydrochloric acid acidified ethanol, stirring for 10h, filtering, washing with ethanol for three times, and drying in vacuum for 12h at 70 ℃ to obtain the polymer.
The catalyst activity of the hafnium pyridylamido catalyst C6 in this example was 1.89X 106g polymer/(mol Hf. h), the copolymer obtained had a weight-average molecular weight of 970.9kg/mol, a molecular weight distribution index of 3.4, an insertion rate of 1-octene of 15%, and a melting temperature of 77.9 DEG CAnd 115.2 ℃.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (13)

1. A pyridine amino hafnium compound is characterized in that the structural formula of the pyridine amino hafnium compound is shown as a formula I,
Figure FDA0002453787140000011
wherein R represents hydrogen or methyl, and X represents methyl, methoxy, fluorine, chlorine or bromine.
2. A method for preparing the hafnium pyridylamine compound of claim 1, comprising the steps of:
1) the pyridone compound and naphthalene boric acid are subjected to coupling reaction to obtain an aryl-substituted 2-naphthyl-pyridone compound;
2) reacting 4-substituted aniline with benzhydryl alcohol to obtain a substituted aniline compound;
3) carrying out condensation reaction on the 2-aryl-pyridone compound and substituted aniline to obtain a substituted pyridimine compound;
4) carrying out reduction reaction on the substituted pyridylimine compound and a strong reducing agent to prepare a substituted pyridylamine compound ligand;
5) the pyridylamine compound and strong base are subjected to deprotonation reaction, then metal salt of hafnium tetrachloride is added for reaction, and further methylation reaction is continuously performed on the pyridylamine compound and methyl magnesium bromide, so that the corresponding pyridylamine hafnium methyl compound is prepared.
3. The method for preparing hafnium pyridylamidoacetate compound according to claim 2, wherein the structural formula of the 2-aryl-pyridinone compound in step 1) is shown in formula II,
Figure FDA0002453787140000012
4. the method for preparing a hafnium pyridylamine compound according to claim 2, wherein the substituted aniline compound obtained in step 2) has a structural formula represented by formula III,
Figure FDA0002453787140000021
in formula III, X represents methyl, methoxy, fluorine, chlorine or bromine.
5. The method of claim 2, wherein the substituted pyridylamine compound of step 3) has a structure represented by formula IV,
Figure FDA0002453787140000022
in formula IV, X represents methyl, methoxy, fluorine, chlorine or bromine.
6. The method for preparing the pyridylamine-hafnium compound of claim 2, wherein the substituted pyridylamine compound of step 4) has a formula as shown in formula V,
Figure FDA0002453787140000023
in formula V, R represents hydrogen or methyl, and X represents methyl, methoxy, fluorine, chlorine or bromine.
7. The method for preparing the hafnium pyridylamine compound of claim 2, wherein in step 5), the structural formula of the hafnium pyridylamine compound is represented by formula I,
Figure FDA0002453787140000024
in the formula I, R represents hydrogen or methyl, and X represents methyl, methoxy, fluorine, chlorine or bromine.
8. Use of the hafnium pyridylamidoamine compound of claim 1 as a catalyst in the polymerization of olefins.
9. The use of the hafnium pyridylamine compound as claimed in claim 8 as a catalyst in olefin polymerization, wherein the hafnium pyridylamine compound as a main catalyst needs to be activated by a cocatalyst for catalytic polymerization.
10. The use of a hafnium pyridylamine compound as in claim 9 as a catalyst in the polymerization of olefins, wherein the co-catalyst is a combination of an aluminum alkyl and a boron compound, or a boron containing compound.
11. The use of a hafnium pyridylamine compound as a catalyst in olefin polymerization according to claim 10, wherein the cocatalyst is at least one of tris (pentafluorobenzene) borane, triphenylcarbenium tetrakis (pentafluorobenzene) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and a combination of an aluminum alkyl and the boron salts described above.
12. The use of the hafnium pyridylamine compound of claim 10 as a catalyst in the polymerization of olefins, wherein when the cocatalyst contains an aluminum alkyl, the molar ratio of the procatalyst to cocatalyst and aluminum alkyl is Hf: b: al is 1: 1.0-5.0: 100-500.
13. The use of the hafnium pyridylamine compound of claim 8 as a catalyst in the polymerization of olefins, wherein the olefin comprises at least one of ethylene, propylene, hexene, and octene.
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CN115947882A (en) * 2023-03-14 2023-04-11 江苏欣诺科催化剂股份有限公司 Preparation method of pyridine amido hafnium catalyst

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Application publication date: 20211022