Group IVB metal compound based on polyamine ligand, and preparation method therefor and use thereof

Abstract

Disclosed in the present application are a Group IVB metal compound based on a polyamine ligand, and a preparation method therefor and the use thereof. The Group IVB metal compound based on a polyamine ligand has general formula 1, wherein M is Ti, Zr or Hf; R1 to R3 are each independently selected from H and a C1-C6 group; R4 to R8 are each independently selected from H and a C1-C6 group, and at least one of R4 to R8 is selected from a C1-C6 group; R9 and R10 are each independently selected from a C1-C6 group; and m and n are each independently selected from 1, 2 and 3. The metal compound of the present application has high thermal stability and a high vapor pressure, and can be used as an organic catalyst for olefin polymerization, such that the catalyst still maintains catalytic activity at high temperatures; and the metal compound can be used as a precursor for the preparation of a functional material, especially a thin film, such that the thickness of the thin film can be ensured to be uniform, defects can be reduced, and by-products that cause adverse effects are not generated during the deposition process.

Description

Polyamine ligand-based group IVB metal compound, its preparation method and application TECHNICAL FIELD

[0001] The present application relates to group IVB metal organic compounds, in particular to a polyamine ligand-based group IVB metal compound, its preparation method and application. BACKGROUND

[0002] Group IVB metal (Ti, Zr, Hf) organic compounds have been widely studied and applied in the field of organic catalysis and functional material preparation. In the field of organic catalysis, from Ziegler-Natta catalyst system to single catalytically active center group IVB metallocene, in recent years, various types of non-metallocene metal catalysts have been studied, which is one of the cores to promote the development of polyolefin materials. Non-metallocene metal catalysts have attracted the attention of academia and industry due to their easy modification, simple synthesis and low price, but a common problem of this type of catalyst is that the catalytic activity is high at room temperature, but the catalytic activity will decrease significantly at high temperature, which limits its application under current industrial conditions. Moreover, the reaction speed and selectivity of the current non-metallocene metal catalysts are generally not as good as that of metallocene catalysts.

[0003] In the field of functional material preparation, thin films are prepared by using group IVB metal precursor compounds through gas deposition and other processes to improve the performance of substrates or provide specific functions, which is widely used in the fields of photovoltaics, displays, sensors and chip manufacturing. In the aspect of chip manufacturing, group IVB metal oxides are widely used as iteration materials of SiO2 in the manufacturing of semiconductor materials with large-scale integration or high-capacity storage due to their high dielectric constant (high-K) properties.

[0004] The IVB group metal precursors commonly used in the metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) processes have one or more problems of low vapor pressure, poor thermal stability or generation of by-products having adverse effects on the deposition process, thereby resulting in defects in the thickness or uniformity of the deposited metal oxide or nitride film. Specifically, chlorides have excellent economy when used as precursors for preparing corresponding oxide or nitride thin films, but their corrosion problems caused by the introduction of chlorine atoms restrict their application in many scenarios. Tetra(methyl ethyl amino) zirconium (TEMAZ) or tetra(methyl ethyl amino) hafnium (TEMAH) are liquid precursors with high saturated vapor pressure and are widely used in MOCVD and ALD processes (D. Hausmann, Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors, Chemistry of Materials 2002, 14(10), 4350-4358), but their low thermal stability causes capacitance leakage and poor step coverage, which limits their application. Tetra(dimethyl amino) zirconium (CpTDMAZ) and other metal precursors synthesized by introducing a cyclopentadiene structure have significantly improved thermal stability while retaining high vapor pressure (Jaakko et al, Novel mixed alkylamido-cyclopentadienyl precursors for ALD of ZrO2 thin films, Journal of Materials Chemistry 2008, 18(43), 5243-5247.), but they also have the problem of by-product generation. SUMMARY

[0005] One of the objects of the present application is to provide a polyamine ligand-based IVB group metal compound that can be used as an organic catalyst for olefin polymerization and as an IVB group metal precursor for processes such as MOCVD and ALD, to solve the problems of low vapor pressure, poor thermal stability or generation of by-products having adverse effects on the deposition process, etc. of the commonly used IVB group metal precursors.

[0006] To this end, the present application provides a polyamine ligand-based IVB group metal compound having the following general formula 1:

[0007]

General Formula 1

[0008] wherein M is Ti, Zr or Hf;

[0009] R1to R3are each independently selected from H, a C1to C6group;

[0010] R4to R8are each independently selected from H, a C1to C6group, and at least one of R4to R8is selected from a C1to C6group;

[0011] R9to R 10 are each independently selected from a C1to C6group;

[0012] m, n are each independently selected from: 1, 2, 3;

[0013] C1to C6groups are saturated or unsaturated straight, branched, or cyclic groups, optionally substituted with a fluorine atom.

[0014] In one embodiment, m and n are both 2 in general formula 1, and the polyamine ligand based Group IVB metal compound has the following general formula 2:

[0015] [General Formula 2]

[0016] In one embodiment, m and n are both 2 in general formula 1, and R1and R3are methyl, R2is H, and the polyamine ligand based Group IVB metal compound has the following general formula 3:

[0017] [General Formula 3]

[0018] In one embodiment, m and n are both 2 in general formula 1, and R1to R3are each methyl, and the polyamine ligand based Group IVB metal compound has the following general formula 4:

[0019] [General Formula 4]

[0020] In yet another embodiment, the Group IVB metal compound is selected from the following:

[0021] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0022] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0023] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0024] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0025] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0026] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0027] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0028] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0029] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0030] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0031] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0032] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0033] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0034] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0035] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0036] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr),

[0037] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr),

[0038] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2),

[0039] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr),

[0040] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2),

[0041] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0042] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0043] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0044] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0045] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0046] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0047] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0048] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0049] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0050] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0051] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0052] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0053] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0054] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0055] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0056] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr),

[0057] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr),

[0058] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2),

[0059] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr),

[0060] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2),

[0061] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i PrCp),

[0062] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt), i PrCp),

[0063] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), n PrCp),

[0064] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), i PrCp),

[0065] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0066] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0067] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0068] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0069] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0070] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0071] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0072] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0073] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0074] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0075] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0076] i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt​​​​​​​​​​​​n Pr)2,

[0077] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr)2,

[0078] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr2,

[0079] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr i Pr)2,

[0080] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr2,

[0081] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0082] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0083] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr)2,

[0084] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr)2,

[0085] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0086] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr)2,

[0087] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr)2,

[0088] (n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0089] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0090] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0091] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0092] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0093] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0094] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0095] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0096] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr),

[0097] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr),

[0098] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2),

[0099] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(Nn Pr i Pr),

[0100] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2),

[0101] ( n PrCp)M(CF3NCH2CH2NCF3CH2CH2NCF3)(N(CF3)2),

[0102] (CF3Cp)M(CycloAmNCH2CH2NMeCH2CH2NH)(NMe2),

[0103] (MeCp)M(MeNCH2CH2N(Allyl)CH2CH2NMe)(NMeCycloAm),

[0104] (Allyl-Cp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeAllyl),

[0105] (MeCp)M(MeNCH2CH2CH2NHCH2NH)(NMe2),

[0106] (MeCp)M(MeNCH2NMeCH2CH2NMe)(NMe2),

[0107] (1,2,3-3 i Pr-Cp)M(HNCH2CH2NHCH2CH2NH)(NMeEt),

[0108] (1,2,3,4-4Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0109] (1,2,3,4,5-5Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0110] or (1-Me-3-Et-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2);

[0111] wherein M is Ti, Zr or Hf, i Pr represents isopropyl, n Pr represents n-propyl, Cp represents cyclopentadienyl, Allyl represents allyl, CycloAm represents cyclopentyl.

[0112] The application also provides a preparation method of the polyamine ligand-based IVB group metal compound, comprising the following steps: S100 cyclopentadienization: reacting the compound of general formula 5 and the compound of general formula 6 to obtain an intermediate product; S200 polydentate amine introduction: reacting the intermediate product and the compound of general formula 7 to obtain the IVB group metal compound of general formula 1.

[0113] [General formula 5]

[0114] [General formula 6]

[0115] [General formula 7]

[0116] [General formula 1]

[0117] Wherein, M is Ti, Zr or Hf;

[0118] R1 to R3 are each independently selected from H, a C1 to C6 group;

[0119] R4 to R8 are each independently selected from H, a C1 to C6 group, and at least one of R4 to R8 is selected from a C1 to C6 group;

[0120] R9 to R 10 are each independently selected from a C1 to C6 group;

[0121] m, n are each independently selected from 1, 2, 3;

[0122] The C1 to C6 group is a saturated or unsaturated straight chain, branched chain or cyclic group, which is optionally substituted by a fluorine atom.

[0123] In an embodiment, the S100 cyclopentadienization step can be: dispersing the compound of general formula 5 in an organic solvent, dropwise adding the compound of general formula 6 to the organic solvent under cooling stirring, then heating to a reaction temperature for reaction, and obtaining the intermediate product by rectification after the reaction is completed.

[0124] In an embodiment, the S200 polydentate amine introduction step can be: dispersing the intermediate product in an organic solvent, dropwise adding the compound of general formula 7 to the organic solvent under cooling stirring, then heating to a reaction temperature for reaction, and obtaining the polyamine ligand-based IVB group metal compound by rectification after the reaction is completed.

[0125] In an embodiment, the organic solvent can be selected from a hydrocarbon or an ether solvent.

[0126] In an embodiment, the compound of general formula 5 and the compound of general formula 6, or the intermediate product and the compound of general formula 7 can be reacted under an inert atmosphere.

[0127] In one embodiment, the molar ratio of the compound of general formula 5, the compound of general formula 6 and the compound of general formula 7 can be 1 : (1-1.05) : (1-1.3).

[0128] The present application also provides a composition comprising 0.1 wt% to 99.9 wt% of the compound of general formula 1 and the balance of one or more organic compounds selected from hydrocarbons, ethers, esters, alcohols, amines, sulfides, phosphines;

[0129]

General Formula 1

[0130] In general formula 1, M is Ti, Zr or Hf;

[0131] R1to R3are each independently selected from H, C1to C6groups;

[0132] R4to R8are each independently selected from H, C1to C6groups, and at least one of R4to R8is selected from C1to C6groups;

[0133] R9to R 10 are each independently selected from C1to C6groups;

[0134] m, n are each independently selected from 1, 2, 3;

[0135] C1to C6groups are saturated or unsaturated linear, branched or cyclic groups, which are optionally substituted with fluorine atoms.

[0136] The present application also provides an olefin polymerization method, comprising using the polyamine ligand-based IVB group metal compound or the polyamine ligand-based IVB group metal compound prepared by the above method as an organic catalyst.

[0137] The present application also provides a method for preparing a functional material containing a IVB group metal element, comprising using the polyamine ligand-based IVB group metal compound or the polyamine ligand-based IVB group metal compound prepared by the above method as a precursor.

[0138] In one embodiment, the functional material is preferably in the form of a film. In another embodiment, the film containing the IVB group metal element can be prepared by a chemical vapor deposition process or an atomic layer deposition process. The film containing the IVB group metal element can comprise a compound of the following formula: (M 1-a O b M’ a )N c C dwherein: 0≤a<1, 0≤b<3, 0≤c<1, 0≤d<1, and b+c≠0; M represents Ti, Zr or Hf; M' represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La or Ce; and M is different from M'.

[0139] Compared with the prior art, the polyamine ligand-based IVB group metal compound of the present application has high thermal stability and vapor pressure. When used as an organic catalyst for olefin polymerization, the catalyst has significantly improved catalytic activity at high temperature. When used as a precursor for the preparation of functional materials, especially for the preparation of thin films, the thickness of the thin film is uniform, defects are reduced, and no harmful by-products are produced during the deposition process. BRIEF DESCRIPTION OF DRAWINGS

[0140] Fig. 1 is an NMR spectrum of the polyamine ligand-based IVB group metal compound prepared in Example 1;

[0141] Fig. 2 is an NMR spectrum of the polyamine ligand-based IVB group metal compound prepared in Example 2;

[0142] Fig. 3 is an NMR spectrum of the polyamine ligand-based IVB group metal compound prepared in Example 3;

[0143] Fig. 4 is a thermogravimetric curve of the polyamine ligand-based IVB group metal compound prepared in Example 1 and a commonly used IVB group metal precursor.

[0144] Fig. 5 is an atomic force microscope characterization of the hafnium oxide thin film formed by the polyamine ligand-based IVB group metal compound prepared in Example 1 for thin film deposition. DETAILED DESCRIPTION

[0145] The present application will be described in detail below with reference to the accompanying drawings.

[0146] The IVB group metal includes titanium (Ti), zirconium (Zr) and hafnium (Hf), which are chemically active and can form compounds with a variety of non-metallic elements. IVB group metal organic compounds have been widely used in the field of organic catalysis and the field of functional material preparation.

[0147] In the field of organic catalysis, such as catalytic olefin polymerization and synthesis of stereoselective compounds, since the Ziegler-Natta catalyst system with multiple active centers was introduced in the 1950s, it has gradually developed to single active center IVB group metallocene, and in recent years various non-metallocene catalysts have been developed, which are one of the cores to promote the development of polyolefin materials. Non-metallocene catalysts have attracted the attention of academia and industry due to their easy modification, simple synthesis and low price, but a common problem with this type of catalyst is that the catalytic activity is high at room temperature, but the catalytic activity decreases significantly at high temperature, which limits its application under current industrial conditions.

[0148] In the field of functional material preparation, especially in chip manufacturing, IVB group metal oxides such as titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2) and rare earth oxides, due to their high dielectric constant (high-K) properties, are widely used as iteration materials of SiO2 in the manufacture of semiconductor materials with large-scale integration or high-capacity storage. Therefore, it is crucial to select a suitable precursor material for forming thin films of this type of metal oxide or nitride. In the thin film preparation process, such as chemical vapor deposition (CVD) or atomic layer deposition (ALD), metal compound precursors need to have high vapor pressure, thermal stability and chemical stability, low toxicity and other properties.

[0149] Adjusting the type of organic ligand is the key to optimizing the properties of IVB group metal organic compounds. The application of high-K materials in microelectronic ALD has been studied for more than 30 years, and the overall process can be divided into the following stages: 1) Initially, metal chlorides were used as metal sources, and water was used as an oxygen source to prepare HfO2 gate oxides, but the presence of chlorides and other by-products makes this type of precursor unsuitable for uniform deposition on high aspect ratio structures; Moreover, the film growth rate of this type of precursor is also limited; 2) The demand of the DRAM industry gave birth to the iteration product, and the introduction of the homoleptic precursor tetra(ethylmethylamino)zirconium Zr(NEtMe)4(TEMAZ) solved the problems of chloride contamination and growth rate, but the poor thermal stability problem followed; 3) On this basis, further proposed the precursor with cyclopentadiene as ligand, which made the thermal stability of the precursor reach 350℃, and at the same time, the film uniformity of high aspect ratio structure was also guaranteed, but compared with alkylamine precursors, the growth rate of the film was limited.

[0150] Currently, the IVB group metal precursors commonly used as MOCVD and ALD processes still have problems such as low vapor pressure, poor thermal stability, or the production of by-products that have adverse effects on the deposition process, which in turn leads to defects in the thickness and uniformity of the deposited metal oxide or nitride film.

[0151] To solve the above problems, the inventors have developed a new type of Group IVB metal compound, which introduces a cyclopentadiene structure and a polyamine ligand, has high thermal stability and high vapor pressure, and can be used as an organic catalyst for olefin polymerization to effectively improve the catalytic efficiency of the catalyst at high temperatures, or can be used for the preparation of functional materials, especially thin films in chip manufacturing, so that no by-products that have adverse effects on the deposition process are produced, ensuring the uniformity of the film thickness and avoiding defects.

[0152] Specifically, the polyamine ligand-based Group IVB metal compound of the present application has the general formula 1:

[0153]

General Formula 1

[0154] In general formula 1, M can be Ti, Zr or Hf;

[0155] R1 to R3 can each independently be selected from H, a C1 to C6 group;

[0156] R4 to R8 can each independently be selected from H, a C1 to C6 group, and at least one of R4 to R8 can be selected from a C1 to C6 group;

[0157] R9 to R 10 may each independently be selected from a C1 to C6 group.

[0158] The C1 to C6 group can be a saturated or unsaturated linear, branched or cyclic group, which is optionally substituted with a fluorine atom; in particular, the C1 to C6 group can be an alkyl group.

[0159] As can be seen from the structure of general formula 1, the polyamine ligand forms a hydrogenated cyclic structure with the Group IVB metal ion, which has a relative molecular mass similar to that of the currently commonly used Group IVB metal precursor compounds, but improves the thermal stability of the compound, and in combination with the cyclopentadiene ligand group, especially the stability of the cyclopentadiene ligand itself with substituents, the compound as a whole has high thermal stability and good vapor pressure, and can be used as an organic catalyst for olefin polymerization and a metal precursor for the preparation of chip thin films, thereby solving the problems of poor thermal stability and low vapor pressure of conventional Group IVB metal precursors.

[0160] In particular, the molecular structure of the compound of general formula 1 determines that the carbon impurity pollution and particle pollution produced during the pyrolysis process are less, thereby avoiding the production of by-products that have adverse effects on the deposition process when used as a precursor.

[0161] In one embodiment, m and n in general formula 1 can each be 2, and the polyamine ligand-based Group IVB metal compound of the present application can have the following general formula 2:

[0162] [Formula 2]

[0163] In one embodiment, R1, R3of Formula 2 can be methyl, R2can be H, and the polyamine ligand based Group IVB metal compound of the present application can have the following Formula 3:

[0164] [Formula 3]

[0165] In another embodiment, R1, R2, R3of Formula 2 can each be methyl, and the polyamine ligand based Group IVB metal compound of the present application can have the following Formula 4:

[0166] [Formula 4]

[0167] In other embodiments, m of Formula 1 can be 1, n can be 3, for example; or R1, R2, and R3may each be independently ethyl, isopropyl, hydrogen, cyclopentyl, and the like, for example.

[0168] Some specific structural formulas of the Group IVB metal compounds of the present application are listed below:

[0169] Specifically, representative compounds of Formula 1 above are listed as follows:

[0170] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0171] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0172] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0173] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0174] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0175] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0176] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0177] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), n Pr,

[0178] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), n Pr i Pr,

[0179] (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), i Pr2,

[0180] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0181] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0182] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), n Pr,

[0183] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), i Pr,

[0184] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0185] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), n Pr,

[0186] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), i Pr,

[0187] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), n Pr2,

[0188] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), n Pr i Pr,

[0189] (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), i Pr2,

[0190] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0191] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0192] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0193] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0194] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0195] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0196] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0197] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0198] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0199] (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0200] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0201] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0202] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0203] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0204] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0205] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr),

[0206] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr),

[0207] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr2),

[0208] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr i Pr),

[0209] (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr2),

[0210] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0211] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0212] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0213] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0214] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0215] i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0216] i ​​​​​​​PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr)2,

[0217] ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr2)2,

[0218] ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr2, i Pr)2,

[0219] ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr2)2,

[0220] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2)2,

[0221] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt)2,

[0222] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr2,

[0223] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr2,

[0224] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2)2,

[0225] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr2,

[0226] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr2,

[0227] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N nPr2),

[0228] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr),

[0229] ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2),

[0230] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0231] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt),

[0232] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr),

[0233] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr),

[0234] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2),

[0235] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr),

[0236] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr),

[0237] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2),

[0238] ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr),

[0239] (n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2),

[0240] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2),

[0241] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt),

[0242] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr),

[0243] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr),

[0244] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2),

[0245] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr),

[0246] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr),

[0247] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2),

[0248] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr),

[0249] ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2),

[0250] ( nPrCp)M(CF3NCH2CH2NCF3CH2CH2NCF3)(N(CF3)2),

[0251] (CF3Cp)M(CycloAmNCH2CH2NMeCH2CH2NH)(NMe2),

[0252] (MeCp)M(MeNCH2CH2N(Allyl)CH2CH2NMe)(NMeCycloAm),

[0253] (Allyl-Cp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeAllyl),

[0254] (MeCp)M(MeNCH2CH2CH2NHCH2NH)(NMe2),

[0255] (MeCp)M(MeNCH2NMeCH2CH2NMe)(NMe2),

[0256] (1,2,3-3 i Pr-Cp)M(HNCH2CH2NHCH2CH2NH)(NMeEt),

[0257] (1,2,3,4-4Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0258] (1,2,3,4,5-5Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2),

[0259] or (1-Me-3-Et-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2);

[0260] wherein M is Ti, Zr or Hf, i Pr represents n-propyl, Cp represents cyclopentadienyl, Allyl represents allyl, CycloAm represents cyclopentyl. n Pr represents n-propyl, Cp represents cyclopentadienyl, Allyl represents allyl, CycloAm represents cyclopentyl.

[0261] The present application also provides a method for preparing the polyamine ligand-based group IVB metal compound as described above, comprising:

[0262] S100 cyclopentadienization: reacting the compound of general formula 5 and the compound of general formula 6 to obtain an intermediate product,

[0263]

General Formula 5

[0264]

General Formula 6

[0265] The specific reaction formula can be as follows:

[0266] That is, a cyclopentadiene substituent is introduced into the compound system of general formula 5 to obtain an intermediate product, wherein R1 to R 10 each of the groups is defined as in general formula 1.

[0267] In one embodiment, the above reaction can be carried out in an organic solvent, which can be a conventional solvent for such a reaction, preferably a hydrocarbon or an ether. The hydrocarbon solvent can be hexane, heptane, decane, benzene, toluene, etc., and the ether solvent can be tetrahydrofuran, ethylene glycol dimethyl ether, diethyl ether, etc. Preferably, a hydrocarbon solvent is used, which can reduce the cost and toxicity of the synthesis reaction and has better operability.

[0268] In one embodiment, the cyclopentadienization reaction can be carried out at room temperature, and the reaction time can be 3 to 6 hours.

[0269] In one embodiment, in order to improve the yield of the reaction, the molar ratio of the compound of general formula 5 to the compound of general formula 6 can be 1: (1-1.05).

[0270] In one embodiment, the above reaction can be carried out under an inert atmosphere such as nitrogen, argon, or helium.

[0271] Specifically, the cyclopentadienization reaction process can be as follows: the compound of general formula 5 is dispersed in an organic solvent, cooled to -15 to -10°C, and the compound of general formula 6 is added dropwise to the organic solvent under stirring, and then warmed to the reaction temperature for reaction. After the reaction is completed, the intermediate product is obtained by rectification.

[0272] S200 Multi-dentate amine introduction: the intermediate product and the compound of general formula 7 are reacted to obtain the multi-amine ligand-based IVB group metal compound of general formula 1.

[0273]

General formula 7

[0274] The specific reaction formula can be as follows:

[0275] That is, the multi-dentate amine ligand compound of general formula 7 is introduced into the intermediate product system to obtain a multi-amine ligand-based IVB group metal compound containing a multi-dentate amine ligand and a cyclopentadiene ligand, wherein R1 to R 10 each of the groups is defined as in general formula 1.

[0276] In one embodiment, the above reaction can be carried out in an organic solvent, which can be selected from hydrocarbons, ethers. The hydrocarbon solvent can be hexane, heptane, decane, benzene, toluene, etc.; the ether solvent can be tetrahydrofuran, glycol dimethyl ether, diethyl ether, etc. Preferably, a hydrocarbon solvent is used, which can reduce the cost and toxicity of the synthesis reaction and has better operability.

[0277] In one embodiment, the polydentate amine introduction reaction can be carried out at room temperature, and the reaction time can be 12 to 24 hours.

[0278] In one embodiment, in order to improve the yield of the reaction, the molar ratio of the compound of general formula 5 in S100 and the compound of general formula 7 in S200 can be 1: (1-1.3).

[0279] In one embodiment, the above reaction can be carried out under an inert atmosphere such as nitrogen, argon, helium.

[0280] Specifically, the polydentate amine introduction reaction process can be: dispersing the intermediate product in an organic solvent, cooling to -15 to -10℃, adding the compound of general formula 7 dropwise to the organic solvent under stirring, then warming to the reaction temperature for reaction, and obtaining the polyamine ligand-based group IVB metal compound of general formula 1 by rectification after the reaction is completed.

[0281] The present application also provides a composition comprising 0.1 wt% to 99.9 wt% of the polyamine ligand-based group IVB metal compound of the present application and the balance of one or more organic compounds selected from hydrocarbons, ethers, esters, alcohols, amines, sulfides, phosphines.

[0282] The organic compound in the composition is not limited as long as it can stabilize the polyamine ligand group IVB metal compound of general formula 1. As an example, the hydrocarbon can be an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, etc.; a cyclic hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, hexahydroindene, cyclooctane, etc.; an aromatic hydrocarbon such as benzene, toluene, xylene, mesitylene, etc.; or a mixture thereof. The ether can be tetrahydrofuran, diethyl ether, methyl tert-butyl ether, etc. or a mixture thereof. The ester can be methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, etc. or a mixture thereof. The alcohol can be methanol, ethanol, propanol, butanol, etc. or a mixture thereof. The amine can be N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. or a mixture thereof. The phosphine can be triphenylphosphine, tricyclohexylphosphine, etc. or a mixture thereof.

[0283] When the polyamine ligand group IVB metal compound of the present application is to be used in combination, it can be achieved by mixing the composition.

[0284] The present application also provides an olefin polymerization method including using the polyamine ligand group IVB metal compound of the present application as an organic catalyst. Since the polyamine ligand group IVB metal compound has high thermal stability, it can maintain catalytic activity at high temperature, thereby improving the polymerization reaction efficiency.

[0285] The present application also provides a method for preparing a functional material containing a Group IVB metal element including using the polyamine ligand group IVB metal compound of the present application as a precursor. In particular, the functional material can be in the form of a film. Accordingly, the present application also provides a film containing a Group IVB metal element, which comprises a compound (M 1-a O b M’ a )N c C dwherein 0 < a < 1, 0 < b < 3, 0 < c < 1, 0 < d < 1, and b + c ≠ 0; M represents Ti, Zr, or Hf; M' represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La, or Ce; and M is different from M'. Specifically, the polyamine ligand-based Group IVB metal compound of the present application can be vaporized to form a first vapor phase metal source; at least one M'-containing precursor can be vaporized to form an optional second vapor phase metal source; and the first vapor phase metal source and the optional second vapor phase metal source can be introduced into a reaction chamber to contact them with a substrate, thereby depositing a Group IVB metal element-containing film on the substrate.

[0286] Examples

[0287] The present application will be further described in detail below with reference to specific examples.

[0288] Example 1: Preparation of (MeCp)Hf(MeNCH2CH2NHCH2CH2NMe)(NMe2)

[0289] Under a nitrogen atmosphere, 73 mg (0.20 mmol) of tetrakis(dimethylamino)hafnium was dispersed in 150 mL of n-hexane and cooled to -15°C. While stirring, 16 mg (0.21 mmol) of methylcyclopentadiene was added dropwise thereto. After being raised to room temperature, the reaction was allowed to proceed for 5 hours, and desolventization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0290] Under a nitrogen atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane and cooled to -15°C. While stirring, 27 mg (0.20 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise thereto. After being raised to room temperature, the reaction was allowed to proceed for 12 hours, and desolventization was performed, and the target product was obtained by distillation under reduced pressure.

[0291] The polyamine ligand-based Group IVB metal compound thus obtained was subjected to nuclear magnetic resonance spectroscopy analysis. As shown in FIG. 1, the spectral data thereof was 1 H NMR (C6D6, ppm) was: δ 5.91-5.65 (4H, CpH), δ 3.32 (6H, s, HfN(CH3)2), δ 3.15 (2H, m, -CH2-), δ 2.98 (6H, s, Hf(NCH3)2), δ 2.69 (2H, m, -CH2-), δ 2.50 (2H, m, -CH2-), δ 2.34 (2H, m, -CH2-), δ 2.01 (3H, s, -CH3).

[0292] The polyamine ligand-based Group IVB metal compound thus obtained was subjected to thermal decomposition test, and a commonly used Group IVB metal precursor As a reference, the thermogravimetric curve shown in Figure 4 was obtained. As shown in Figure 4, the starting decomposition temperature of the Group IVB metal compound of Example 1 was 230.11°C, and the temperature T 1 / 2 at which 50% of mass was lost was 249.16°C. The starting decomposition temperature of the Group IVB metal precursor as a control was 151.69°C, and the temperature T 1 / 2 at which 50% of mass was lost was 169.00°C. Thus, it can be seen that the Group IVB metal compound of Example 1 has better thermal stability than the conventional Group IVB metal precursor.

[0293] Example 2: n Preparation of (MeNCH2CH2NHCH2CH2NMe)2Hf(NMe2)2

[0294] Under an argon atmosphere, 73 mg (0.20 mmol) of tetrakis(dimethylamino)hafnium was dispersed in 150 mL of n-hexane and cooled to -15°C. While stirring, 22 mg (0.21 mmol) of n-propylcyclopentadiene was added dropwise thereto. After being raised to room temperature, the reaction was allowed to proceed for 5 hours, and desolventization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0295] Under an argon atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane and cooled to -15°C. While stirring, 27 mg (0.20 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise thereto. After being raised to room temperature, the reaction was allowed to proceed for 24 hours, and desolventization was performed, and the target product was obtained by distillation under reduced pressure.

[0296] The Group IVB metal compound having a polyamine ligand prepared was subjected to nuclear magnetic resonance spectroscopy analysis. As shown in Figure 2, the spectral data 1 H NMR (C6D6, ppm) was: δ 5.88-5.62 (4H, CpH), δ 3.38-3.35 (6H, HfN(CH3)2), δ 3.24 (2H, m, -CH2-), δ 3.04-3.01 (6H, s, Hf(NCH3)2), δ 2.79 (2H, m, -CH2-), δ 2.47 (2H, t, -CH2CH2CH3), δ 2.36 (4H, m, -CH2-), δ 1.53 (2H, m, -CH2CH2CH3), δ 0.91 (3H, m, -CH2CH2CH3).

[0297] Example 3: n Preparation of (MeNCH2CH2NHCH2CH2NMe)2Zr(NMe2)2

[0298] Under argon atmosphere, 53 mg (0.20 mmol) of tetrakis(dimethylamino)zirconium was dispersed in 150 mL of n-hexane and cooled to -15 °C. 22 mg (0.21 mmol) of n-propylcyclopentadiene was added dropwise to it under stirring. After being raised to room temperature, the reaction was carried out for 5 hours and desolventized. The intermediate compound was obtained by distillation under reduced pressure.

[0299] Under argon atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane and cooled to -15 °C. 27 mg (0.20 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise to it under stirring. After being raised to room temperature, the reaction was carried out for 16 hours, desolventized and the target product was obtained by distillation under reduced pressure.

[0300] The prepared polyamine ligand-based IVB group metal compound was subjected to nuclear magnetic resonance spectrum analysis. As shown in FIG. 3, the spectrum data thereof was 1 H NMR (C6D6, ppm) was: δ 5.92-5.70 (4H, CpH), δ 3.32 (6H, HfN(CH3)2), δ 3.16 (2H, m, -CH2-), δ 2.98 (6H, s, Hf(NCH3)2), δ 2.71 (2H, m, -CH2-), δ 2.57 (2H, m, -CH2-), δ 2.52 (2H, m, -CH2-), δ 2.37 (2H, t, -CH2CH2CH3), δ 1.57 (2H, m, -CH2CH2CH3), δ 0.96 (3H, m, -CH2CH2CH3).

[0301] Example 4: Preparation of (1-Me-3-Et-Cp)Hf(MeNCH2CH2NHCH2CH2NMe)(NMe2)

[0302] Under nitrogen atmosphere, 73 mg (0.20 mmol) of tetrakis(dimethylamino)hafnium was dispersed in 150 mL of n-hexane and cooled to -15 °C. 22 mg (0.20 mmol) of 1-methyl-3-ethylcyclopentadiene was added dropwise to it under stirring. After being raised to room temperature, the reaction was carried out for 5 hours and desolventized. The intermediate compound was obtained by distillation under reduced pressure.

[0303] Under nitrogen atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane and cooled to -15 °C. 27 mg (0.20 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise to it under stirring. After being raised to room temperature, the reaction was carried out for 12 hours, desolventized and the final product was obtained by distillation under reduced pressure.

[0304] Example 5: Preparation of (1,2,3,4,5-5Me-Cp)Ti(MeNCH2CH2NHCH2CH2NMe)(NMe2)

[0305] Under helium atmosphere, 45 mg (0.20 mmol) of tetra(dimethylamino)titanium was dispersed in 150 mL of tetrahydrofuran, cooled to -10°C. To this, 27 mg (0.20 mmol) of (1,2,3,4,5-pentamethyl)cyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was allowed to proceed for 6 hours, and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0306] Under helium atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of tetrahydrofuran, cooled to -10°C. To this, 34 mg (0.26 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise under stirring. After being brought to room temperature, the reaction was allowed to proceed for 16 hours, and desolubilization was performed, and the final product was obtained by distillation under reduced pressure.

[0307] Example 6: Preparation of (1,2,3,4,5-5Me-Cp)Zr(MeNCH2CH2NHCH2CH2NMe)(NMe2) n PrCp)Zr(MeNCH2CH2NMeCH2CH2NMe)(NMe2) of Preparation

[0308] Under helium atmosphere, 45 mg (0.20 mmol) of tetra(dimethylamino)titanium was dispersed in 150 mL of tetrahydrofuran, cooled to -10°C. To this, 27 mg (0.20 mmol) of (1,2,3,4,5-pentamethyl)cyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was allowed to proceed for 6 hours, and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0309] Under helium atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of tetrahydrofuran, cooled to -10°C. To this, 34 mg (0.26 mmol) of N,N"-dimethyldiethylenetriamine was added dropwise under stirring. After being brought to room temperature, the reaction was allowed to proceed for 16 hours, and desolubilization was performed, and the final product was obtained by distillation under reduced pressure.

[0310] Example 7: Preparation of (1,2,3,4-4Me-Cp)Ti(MeNCH2CH2NHCH2CH2NMe)(NMe2)

[0311] Under helium atmosphere, 45 mg (0.20 mmol) of tetra(dimethylamino)titanium was dispersed in 150 mL of tetrahydrofuran, cooled to -10°C. To this, 27 mg (0.20 mmol) of (1,2,3,4,5-pentamethyl)cyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was allowed to proceed for 6 hours, and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0312] The intermediate compound purified in the previous step was dissolved in 100 mL of tetrahydrofuran under helium atmosphere and cooled to -10°C. To this was added dropwise 31 mg (0.26 mmol) of N,N"-dimethyldiethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 16 hours, desolved and distilled under reduced pressure to obtain the final product.

[0313] Example 8: Preparation of (1,2,3-3 i Preparation of (MeCp)Hf(HNCH2CH2NHCH2CH2NH)(NMe2)

[0314] Under nitrogen atmosphere, 82 mg (0.20 mmol) of tetrakis(methylethylamino)hafnium was dispersed in 150 mL of n-hexane and cooled to -12°C. To this was added dropwise 40 mg (0.21 mmol) of 1,2,3-triisopropylcyclopentadiene under stirring. After being allowed to warm to room temperature, the reaction was carried out for 3 hours, desolved. The intermediate compound was obtained by distillation under reduced pressure.

[0315] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under nitrogen atmosphere and cooled to -12°C. To this was added dropwise 27 mg (0.26 mmol) of diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 16 hours, desolved and distilled under reduced pressure to obtain the final product.

[0316] Example 9: Preparation of (MeCp)Zr(MeNCH2NMeCH2CH2NMe)(NMe2)

[0317] Under argon atmosphere, 53 mg (0.20 mmol) of tetrakis(dimethylamino)zirconium was dispersed in 150 mL of n-hexane and cooled to -15°C. To this was added dropwise 17 mg (0.21 mmol) of methylcyclopentadiene under stirring. After being allowed to warm to room temperature, the reaction was carried out for 5 hours, desolved. The intermediate compound was obtained by distillation under reduced pressure.

[0318] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 29 mg (0.20 mmol) of N,N',N"-trimethyl-methyleneethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 16 hours, desolved and distilled under reduced pressure to obtain the target product.

[0319] Example 10: Preparation of (MeCp)Ti(MeNCH2CH2CH2NHCH2NH)(NMe2)

[0320] Under helium atmosphere, 45 mg (0.20 mmol) of tetra(dimethylamino)titanium was dispersed in 150 mL of tetrahydrofuran and cooled to -15°C. To this, 16 mg (0.20 mmol) of methylcyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 4 hours and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0321] Under helium atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of tetrahydrofuran and cooled to -15°C. To this, 35 mg (0.24 mmol) of N-methyl-propylidene methylene triamine was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 14 hours and desolubilization was performed, and the final product was obtained by distillation under reduced pressure.

[0322] Example 11: Preparation of (Allyl-Cp)Zr(MeNCH2CH2NMeCH2CH2NMe)(NMeAllyl) (Allyl represents allyl group)

[0323] Under argon atmosphere, 74 mg (0.20 mmol) of tetra(methylallylamino)zirconium was dispersed in 150 mL of n-hexane and cooled to -15°C. To this, 22 mg (0.21 mmol) of allylcyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 5 hours and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0324] Under argon atmosphere, the intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane and cooled to -15°C. To this, 29 mg (0.20 mmol) of N,N',N"-trimethyl diethylenetriamine was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 20 hours and desolubilization was performed, and the target product was obtained by distillation under reduced pressure.

[0325] Example 12: Preparation of (MeCp)Ti(MeNCH2CH2N(Allyl)CH2CH2NMe)(NMeCycloAm)

[0326] Under argon atmosphere, 56 mg (0.20 mmol) of tetra(methylcyclopentylamino)titanium was dispersed in 150 mL of n-hexane and cooled to -15°C. To this, 16 mg (0.21 mmol) of methylcyclopentadiene was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 5 hours and desolubilization was performed. The intermediate compound was obtained by distillation under reduced pressure.

[0327] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 34 mg (0.20 mmol) of N,N"-dimethyl-N'-allyl diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 20 hours, desolved and distilled under reduced pressure to obtain the final product.

[0328] Example 13: Preparation of (CF3Cp)Hf(CycloAmNCH2CH2NMeCH2CH2NH)(NMe2)

[0329] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 34 mg (0.20 mmol) of N,N"-dimethyl-N'-allyl diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 20 hours, desolved and distilled under reduced pressure to obtain the final product.

[0330] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 34 mg (0.20 mmol) of N,N"-dimethyl-N'-allyl diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 20 hours, desolved and distilled under reduced pressure to obtain the final product.

[0331] Example 14: Preparation of (CF3Cp)Hf(CycloAmNCH2CH2NMeCH2CH2NMe)(NMe2) n Example 14: Preparation of (CF3Cp)Hf(CycloAmNCH2CH2NMeCH2CH2NMe)(NMe2)

[0332] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 34 mg (0.20 mmol) of N,N"-dimethyl-N'-allyl diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 20 hours, desolved and distilled under reduced pressure to obtain the final product.

[0333] The intermediate compound purified in the previous step was dissolved in 100 mL of n-hexane under argon atmosphere and cooled to -15°C. To this was added dropwise 34 mg (0.20 mmol) of N,N"-dimethyl-N'-allyl diethylenetriamine under stirring. After being allowed to warm to room temperature, the reaction was carried out for 20 hours, desolved and distilled under reduced pressure to obtain the final product.

[0334] Example 1: Ethylene catalytic polymerization experiment

[0335] Ethylene polymerization Example 1: 1 μmol of the polyamine ligand-based Group IVB metal compound prepared in Example 1 was used as the main catalyst, 0.05 mmol of methylaluminoxane was used as the cocatalyst, and 250 ml of cyclohexane was used as the reaction solvent. The reaction vessel was charged with ethylene gas to a pressure of 1 MPa, and the temperature was raised to 150°C. After 1 hour of reaction, the polymerization product was separated by filtration and dried to obtain 7.5 g of polymer. The weight average molecular weight (Mw) of the obtained polymer was 120,000 g / mol, and the molecular weight distribution (PDI) was 2.7, as determined by gel permeation chromatography.

[0336] To evaluate the catalytic performance of the polyamine ligand-based Group IVB metal compound of the present application, the following comparative experiments were performed using conventional olefin polymerization catalysts.

[0337] Ethylene polymerization Comparative Example 1: 1 μmol of methylcyclopentadienyl hafnium tris(dimethylamino) was used as the main catalyst, and the ethylene polymerization reaction was performed in the same manner as described above. After drying, 4.2 g of polymer was obtained. The weight average molecular weight (Mw) of the obtained polymer was 95,000 g / mol, and the molecular weight distribution (PDI) was 2.9, as determined by gel permeation chromatography.

[0338] Ethylene polymerization Comparative Example 2: 1 μmol of a commercial dichlorobis- cyclopentadienyl zirconium compound was used as the main catalyst, and the ethylene polymerization reaction was performed in the same manner as described above. After drying, 10.2 g of polymer was obtained. The weight average molecular weight (Mw) of the obtained polymer was 160,000 g / mol, and the molecular weight distribution (PDI) was 2.4, as determined by gel permeation chromatography.

[0339] As can be seen from the above, the polyamine ligand-based Group IVB metal compound prepared in Example 1 has good catalytic performance for olefin polymerization, and the synthesized polymer has a high molecular weight and a uniform molecular weight distribution, and the effect is comparable to that of a commercial cyclopentadienyl zirconium catalyst. This is related to the high thermal stability of the polyamine ligand-based Group IVB metal compound of the present application, which can maintain catalytic activity at high temperatures when used as an organic catalyst for olefin polymerization, thereby improving the polymerization efficiency at high temperatures.

[0340] Application Example 2: Film preparation experiment

[0341] A clean silicon substrate is selected and transferred to the reaction chamber of a thin film deposition device. The substrate is heated to 300°C. The Group IVB metal compound prepared in Example 1 is introduced into the reaction chamber under 50 seem argon as a carrier gas, and pulsed for 5 seconds. Then, 500 seem argon is introduced to purge the reaction chamber for 10 seconds. Next, 100 seem ozone is introduced as a reaction gas, and pulsed for 3 seconds. The pulsing is stopped, and 500 seem argon is introduced to purge the reaction chamber for 10 seconds to ensure that the ozone and byproducts not involved in the reaction are removed. This completes one cycle of thin film deposition. The above process is repeated 200 times to obtain a hafnium oxide thin film.

[0342] The hafnium oxide thin film prepared above is characterized and analyzed, and the atomic force microscope characterization image is shown in Figure 5. As shown in Figure 5, the thin film exhibits good roughness and uniformity in a 1 micron x 1 micron characterization area. Thus, the polyamine ligand-based Group IVB metal compound of the present application can effectively ensure the film quality when used as a precursor for preparing a film containing a Group IVB metal element.

[0343] Furthermore, the Group IVB metal compound prepared in the above example has less carbon impurities and particles generated during pyrolysis, and thus can avoid the generation of byproducts that have adverse effects on the deposition process when used as a precursor for a film containing a Group IVB metal element.

[0344] The foregoing description of specific exemplary embodiments of the application is intended to be illustrative only and is not intended to limit the application to the precise forms described. Many modifications and variations are possible in light of the above teachings without departing from the spirit or essential characteristics of the application. The exemplary embodiments were chosen and described in order to explain the principles of the application and its practical application and to allow others skilled in the art to understand the application for various exemplary embodiments with various modifications being suitable for specific applications and conditions.

Claims

1. A polyamine ligand-based group IVB metal compound, characterized in that, It has the following general formula 1: 【General Formula 1】 Wherein, metal M is Ti, Zr or Hf; R1 to R3 are each independently selected from H, C1 to C6 groups; R4 to R8 are each independently selected from H, C1 to C6 groups, and at least one of R4 to R8 is selected from C1 to C6 groups; R9 to R 10 Each group is independently selected from C1 to C6 groups; m and n are each independently 1, 2, and 3; The C1 to C6 groups are saturated or unsaturated straight-chain, branched, or cyclic groups, which may optionally be substituted with fluorine atoms.

2. The group IVB metal compound according to claim 1, characterized in that... In general formula 1, both m and n are 2, and it has general formula 2: 【General Formula 2】 3. The group IVB metal compound according to claim 2, characterized in that... In general formula 2, R1 and R3 are both methyl groups, and R2 is H, thus having general formula 3: 【Formula 3】 4. The group IVB metal compound according to claim 2, characterized in that... In general formula 2, R1, R2, and R3 are all methyl groups, which have general formula 4: 【General Formula 4】 5. The group IVB metal compound according to claim 1, characterized in that, The compound is selected from the following: (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr), (MeCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr), (MeCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr), (EtCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr), (EtCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr), ( i PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr), ( i PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMeEt), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe n Pr), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NMe i Pr), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt2), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt n Pr), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(NEt i Pr), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr2), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N n Pr i Pr), ( n PrCp)M(MeNCH2CH2NHCH2CH2NMe)(N i Pr2), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe2), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeEt), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe n Pr), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NMe i Pr), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt2), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt n Pr), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(NEt i Pr), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr2), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N n Pr i Pr), ( n PrCp)M(MeNCH2CH2NMeCH2CH2NMe)(N i Pr2), ( n PrCp)M(CF3NCH2CH2NCF3CH2CH2NCF3)(N(CF3)2), (CF3Cp)M(CycloAmNCH2CH2NMeCH2CH2NH)(NMe2), (MeCp)M(MeNCH2CH2N(Allyl)CH2CH2NMe)(NMeCycloAm), (Allyl-Cp)M(MeNCH2CH2NMeCH2CH2NMe)(NMeAllyl), (MeCp)M(MeNCH2CH2CH2NHCH2NH)(NMe2), (MeCp)M(MeNCH2NMeCH2CH2NMe)(NMe2), (1,2,3-3 i Pr-Cp)M(HNCH2CH2NHCH2CH2NH)(NMeEt), (1,2,3,4-4Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), (1,2,3,4,5-5Me-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2), Or (1-Me-3-Et-Cp)M(MeNCH2CH2NHCH2CH2NMe)(NMe2); Where M is Ti, Zr, or Hf, i Pr stands for isopropyl. n Pr represents n-propyl, Cp represents cyclopentadienyl, Allyl represents allyl, and CycloAm represents cyclopentyl.

6. A method for preparing a polyamine ligand-based group IVB metal compound, characterized in that, Includes the following steps: S100 cyclopentadienylation: Reacting compounds of general formula 5 and general formula 6 to obtain intermediate products; S200 polydentate amine introduction: The intermediate product is reacted with a compound of general formula 7 to obtain a group IVB metal compound of general formula 1; 【Formula 5】 【Formula 6】 【General Formula 7】 【General Formula 1】 In the above general formula, M is Ti, Zr, or Hf; R1 to R3 are each independently selected from H, C1 to C6 groups; R4 to R8 are each independently selected from H, C1 to C6 groups, and at least one of R4 to R8 is selected from C1 to C6 groups; R9 to R 10 Each group is independently selected from C1 to C6 groups; m and n are each independently selected from: 1, 2, 3; The C1 to C6 groups are saturated or unsaturated straight-chain, branched, or cyclic groups, which may optionally be substituted with fluorine atoms.

7. The preparation method according to claim 6, characterized in that... The S100 cyclopentadienylation step includes: The compound of general formula 5 was dispersed in an organic solvent, and the compound of general formula 6 was added dropwise to the organic solvent under cooling and stirring. The temperature was then raised to the reaction temperature to carry out the reaction. After the reaction was completed, the intermediate product was obtained by distillation.

8. The preparation method according to claim 6, characterized in that... The steps for introducing S200 polydentate amine include: The intermediate product was dispersed in an organic solvent. Under cooling and stirring, the compound of general formula 7 was added dropwise to the organic solvent. The temperature was then raised to the reaction temperature to carry out the reaction. After the reaction was completed, the compound of general formula 1 was obtained by distillation.

9. The preparation method according to claim 7 or 8, characterized in that... The organic solvent is selected from hydrocarbon or ether solvents.

10. The preparation method according to any one of claims 6 to 9, characterized in that, The molar ratio between compounds of general formula 5, general formula 6 and general formula 7 is 1:(1 to 1.05):(1 to 1.3).

11. A composition comprising 0.1% to 99.9% by weight of a compound of general formula 1 and the balance being one or more organic compounds selected from hydrocarbons, ethers, esters, alcohols, amines, sulfides, and phosphines; 【General Formula 1】 In general formula 1, the metal M is Ti, Zr, or Hf; R1 to R3 are each independently selected from H, C1 to C6 groups; R4 to R8 are each independently selected from H, C1 to C6 groups, and at least one of R4 to R8 is selected from C1 to C6 groups; R9 to R 10 Each group is independently selected from C1 to C6 groups; m and n are each independently 1, 2, and 3; The C1 to C6 groups are saturated or unsaturated straight-chain, branched, or cyclic groups, which may optionally be substituted with fluorine atoms.

12. An olefin polymerization method comprising using an IVB group metal compound as described in any one of claims 1 to 5 or an IVB group metal compound prepared by any one of claims 6 to 10 as an organic catalyst.

13. A method for preparing a functional material containing a Group IVB metal element, comprising using a Group IVB metal compound as described in any one of claims 1 to 5 or a Group IVB metal compound prepared by any one of claims 6 to 10 as a precursor, wherein the functional material is preferably in the form of a film.

14. The method according to claim 13, characterized in that, Films containing Group IVB metals are prepared by chemical vapor deposition or atomic layer deposition.

15. The method according to claim 14, characterized in that, Membranes containing Group IVB metals include compounds of the following formula: (M 1-a O b M' a )N c C d , Where: 0≤a<1, 0≤b<3, 0≤c<1, 0≤d<1, and b+c≠0; M represents Ti, Zr, or Hf; M' represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La, or Ce; and M is different from M'.

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