Group IVB metal compound, and preparation method therefor and use thereof

Abstract

The present application discloses a Group IVB metal compound, and a preparation method therefor and a use thereof. The Group IVB metal compound has general formula I, wherein M is Ti, Zr, or Hf; R1 to R10 are each independently selected from H and C1 to C6 groups, and R8 is not H; and m, n, and k are each independently selected from 1, 2, and 3. The Group IVB metal compound of the present application has high thermal stability and high vapor pressure and can be used as a precursor in the preparation of a functional material, especially in the preparation of a thin film, can ensure the uniformity of the thickness of the thin film, and reduce defects, without producing adverse by-products; in addition, the compound can also serve as an organic catalyst for olefin polymerization and exhibit significantly improved catalytic activity at high temperatures.

Description

Group IVB metal compound, its preparation method and application TECHNICAL FIELD

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

[0002] Group IVB metal (Ti, Zr and Hf) compounds have excellent performance in chemistry, optics and electricity, such as high temperature resistance, corrosion resistance, high dielectric constant, low leakage current, etc. These characteristics make them play an important role in the fields of ceramic material preparation, thin film and coating, nanomaterial synthesis, catalysis and optoelectronic materials, etc., and provide strong support for the development and technological progress of related industries.

[0003] In the thin film preparation process, metal organic compounds as precursors need to have the advantages of high volatility, high stability, high temperature difference between evaporation and cracking, low toxicity, and easy synthesis and purification. The structure and properties of the ligand in the metal organic compound have important influence on the performance of the final product. Therefore, how to design and synthesize metal organic compounds containing ligands with specific structure and function is a challenge.

[0004] At present, as the common group IVB metal precursor for metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) processes, there are problems of low vapor pressure, poor thermal stability or generation of by-products that have adverse effects on the deposition process, which further leads to defects in the thickness and uniformity of the deposited metal oxide or nitride film. For example, the cyclopentadienyl tris(dimethylamino) zirconium in the related art is a zirconium amide compound with very high reactivity, which is not easy to store for a long time, especially with low thermal stability, and is easy to decompose in the gasification process, which greatly affects the quality of the thin film. In order to improve the reactivity and thermal stability of such compounds, metal triamine compounds have appeared in the related art, but the nitrogen atoms at both ends of the dialkylene triamine of the metal triamine compound are bonded to the group IVB metal through two covalent bonds, and the remaining two are independent groups (amino, cyclopentadienyl, alkoxy) coordinated to the metal center. When the above two cyclopentadiene ligand compounds are used in the ALD method, unwanted by-products cyclopentadiene will be produced, because cyclopentadiene is not stable at high temperature and is easy to polymerize to form difficult-to-vaporize dicyclopentadiene, resulting in increased carbon deposition residue during film formation.

[0005] In addition, in the field of olefin catalysis, single catalytically active center IVB group metallocene, and various non-metallocene catalysts in recent years are important research directions for the development of polyolefin materials. Non-metallocene catalysts have attracted keen attention from academia and industry due to their easy modification, simple synthesis, and low price. However, a common problem with such catalysts is that they have high catalytic activity at room temperature, but the catalytic activity decreases significantly at high temperatures, thereby limiting their application under current industrial conditions. Moreover, the reaction speed and selectivity of current non-metallocene catalysts are not as good as those of metallocene catalysts. SUMMARY

[0006] One of the purposes of the present application is to provide an IVB group metal compound, a preparation method and application thereof, to solve the problems of IVB group metal compounds in the related art, such as low vapor pressure, poor thermal stability, or generation of by-products that have adverse effects on thin film deposition and olefin polymerization, thereby causing defects in the thickness and uniformity of the deposited metal oxide or nitride film, reducing the efficiency of catalytic reactions, and the like.

[0007] The present application provides an IVB group metal compound, having the following general formula 1:

[0008]

General Formula 1

[0009] wherein M is Ti, Zr or Hf;

[0010] R1 to R 10 are each independently selected from H, C1 to C6 groups, and R8 is not H;

[0011] m, n, k are each independently selected from 1, 2, 3;

[0012] The C1 to C6 groups are saturated or unsaturated linear, branched or cyclic groups, which are optionally substituted with fluorine atoms.

[0013] In an embodiment, R9, R 10 are H, the IVB group metal compound of the present application has general formula 2:

[0014]

General Formula 2

[0015] In an embodiment, when k is 1, and m, n are both 2 in general formula 2, the IVB group metal compound of the present application has general formula 3:

[0016]

General Formula 3

[0017] When k is 1, and m, n are both 3 in general formula 2, the IVB group metal compound of the present application has general formula 4:

[0018] [Formula 4]

[0019] In one embodiment, R9, R 10 each is CH3, k is 1, and when m, n are both 2, the Group IVB metal compound of the present application has the formula 5:

[0020] [Formula 5]

[0021] when m, n are both 3, the Group IVB metal compound of the present application has the formula 6:

[0022] [Formula 6]

[0023] In one embodiment, the compound can be selected from:

[0024] (CpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0025] (CpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0026] (CpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0027] (CpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0028] (MeCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0029] (MeCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0030] (MeCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0031] (MeCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0032] (EtCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0033] (EtCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0034] (EtCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0035] (EtCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0036] ( n PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0037] ( n PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0038] ( n PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0039] ( n PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0040] ( i PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0041] ( i PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0042] ( i PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0043] ( i PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0044] (CpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0045] (CpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0046] (CpCH2CH2Nn Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0047] (CpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0048] (MeCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0049] (MeCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0050] (MeCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0051] (MeCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0052] (EtCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0053] (EtCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0054] (EtCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0055] (EtCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0056] ( n PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0057] ( n PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0058] ( n PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0059] ( n PrCpCH2CH2Ni Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0060] ( i PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0061] ( i PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0062] ( i PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0063] ( i PrCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0064] (CpCH2CH2NMe)M(EtNCH2CH2NHCH2CH2NEt),

[0065] (CpCH2CH2NEt)M(EtNCH2CH2NHCH2CH2NEt),

[0066] (CpCH2CH2N n Pr)M(EtNCH2CH2NHCH2CH2NEt),

[0067] (CpCH2CH2N i Pr)M(EtNCH2CH2NHCH2CH2NEt),

[0068] (CpCH2CH2NMe)M(EtNCH2CH2NMeCH2CH2NEt),

[0069] (CpCH2CH2NEt)M(EtNCH2CH2NMeCH2CH2NEt),

[0070] (CpCH2CH2N n Pr)M(EtNCH2CH2NMeCH2CH2NEt),

[0071] (CpCH2CH2N i Pr)M(EtNCH2CH2NMeCH2CH2NEt),

[0072] (CpCH2CH2NMe)M( iPrNCH2CH2NHCH2CH2N i Pr),

[0073] (CpCH2CH2NEt)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0074] (CpCH2CH2N n Pr)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0075] (CpCH2CH2N i Pr)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0076] (CpCH2CH2NMe)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0077] (CpCH2CH2NEt)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0078] (CpCH2CH2N n Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0079] (CpCH2CH2N i Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr) ;

[0080] (CpCH2CH2CH2CH2NMe)M(HNCHAllylNHCHMeNCycloAm) ;

[0081] (2-AllylCpCH2CH2CH2CH2NMe)M(HNCH2CH2CH2NHCH2CH2CH2N i Bu) ;

[0082] (CpCH2CH2NMe)M(AllylNCH2CH2NHCH2CH2CH2NCF3) ;

[0083] (CpCH2CH2CH2NMe)M(MeNCH2NCF3CH2NMe);

[0084] (2,3,4,5-4MeCpCH2CH2CH2CH2NCF3)M(CycloAmNCH2CH2CHMeNMeCHMeCH2CH2NMe);

[0085] (2,4-2MeCpCH2CH2CH2NAllyl)M(MeNCHMeCH2NHCH2CHMeNMe);

[0086] (MeCpCH2CH2NMe)M(MeNCH2CHMeCH2NMeCH2CHMeCH2NMe);

[0087] (CpCH2CH2NMe)M(MeNCH2CH2CH2NHCH2CH2CH2NMe); or

[0088] (CpCH2CH2NMe)M(MeNCH2CHMeNHCHMeCH2NMe);

[0089] 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, i Bu represents isobutyl.

[0090] The application also provides a preparation method of the group IVB metal compound, comprising:

[0091] reacting the compound of general formula 7 and the compound of general formula 8 to obtain an intermediate product;

[0092] reacting the intermediate product and the compound of general formula 9 to obtain the group IVB metal compound of general formula 1;

[0093]

General formula 7

[0094]

General formula 8

[0095]

General formula 9

[0096]

General formula 1

[0097] wherein M is Ti, Zr or Hf;

[0098] R1 to R 10each independently selected from H, a C1 to C6 group, and R8 is not H;

[0099] R 11 to R 12 each independently selected from a C1 to C6 group;

[0100] m, n, k are each independently selected from: 1, 2, 3;

[0101] The C1 to C6 group is a saturated or unsaturated straight chain, branched chain or cyclic group, which is optionally substituted with a fluorine atom.

[0102] In an embodiment, the step of reacting the compound of general formula 7 and the compound of general formula 8 to obtain the intermediate product can be: dispersing the compound of general formula 7 in an organic solvent, dropwise adding the compound of general formula 8 to the organic solvent under cooling stirring, then warming to a reaction temperature to carry out the reaction, and obtaining the intermediate product by rectification after the reaction is completed.

[0103] In an embodiment, the step of reacting the intermediate product and the compound of general formula 9 to obtain the group IVB metal compound can be: dispersing the intermediate product in an organic solvent, dropwise adding the compound of general formula 9 to the organic solvent under cooling stirring, then warming to a reaction temperature to carry out the reaction, and obtaining the group IVB metal compound by rectification after the reaction is completed.

[0104] In an embodiment, the organic solvent can be selected from a hydrocarbon or an ether.

[0105] In an embodiment, the molar ratio of the compound of general formula 7, the compound of general formula 8 and the compound of general formula 9 can be 1: (1-1.2): (1-1.1).

[0106] The present application also provides a composition comprising 0.1 wt% to 99.9 wt% of the compound of general formula 1 and a balance of one or more organic compounds selected from a hydrocarbon, an ether, an ester, an alcohol, an amine, a sulfide, a phosphine;

[0107]

General Formula 1

[0108] wherein M is Ti, Zr or Hf;

[0109] R1 to R 10 each independently selected from H, a C1 to C6 group, and R8 is not H;

[0110] m, n, k are each independently selected from: 1, 2, 3;

[0111] The C1 to C6 group is a saturated or unsaturated straight chain, branched chain or cyclic group, which is optionally substituted with a fluorine atom.

[0112] The application also provides an olefin polymerization method, which comprises using the above-mentioned Group IVB metal compound or the Group IVB metal compound prepared by the above-mentioned method as an organic catalyst.

[0113] The application also provides a preparation method of a functional material containing a Group IVB metal element, which comprises using the above-mentioned Group IVB metal compound or the Group IVB metal compound prepared by the above-mentioned method as a precursor.

[0114] In one embodiment, the functional material is preferably in a film-form. In another embodiment, the film containing the Group IVB metal element can be prepared by a chemical vapor deposition process or an atomic layer deposition process. The film containing the Group IVB metal element can comprise a compound of the following formula: 1 a O b M 2 1-a )N c C d ; wherein 0 1 represents Ti, Zr or Hf; M 2 represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La or Ce; and M 1 is different from M 2 .

[0115] Compared with the prior art, the application has the following advantages: the thermal stability and vapor pressure of the Group IVB metal compound of the application are high. When used as an organic catalyst for olefin polymerization, the catalytic activity of the catalyst at high temperature is significantly improved. When used as a precursor for the preparation of functional materials, especially thin films, the thickness of the thin film is uniform, defects are reduced, and no harmful by-products are produced during the deposition process.

[0116] On the other hand, the preparation method of the application can obtain a high-purity semiconductor-grade Group IV metal compound, and only a single solvent such as a hydrocarbon is required. The method reduces the preparation cost and the toxicity of the reaction process, has better operability, higher yield, and is easy to scale up. After the reaction is completed, the product is subjected to steps such as rectification, purification, adsorption and filtration, and the purity and particle size of the final product can well meet the product requirements of the semiconductor industry. BRIEF DESCRIPTION OF DRAWINGS

[0117] Figure 1 is an NMR spectrum of the Group IVB metal compound prepared in Example 1;

[0118] Figure 2 is an NMR spectrum of the Group IVB metal compound prepared in Example 2;

[0119] Figure 3 is a NMR spectrum of the Group IVB metal compound prepared in Example 3;

[0120] Figure 4 is a thermogravimetric curve of the Group IVB metal compound prepared in Example 2 and a commonly used Group IVB metal precursor;

[0121] Figure 5 is an X-ray photoelectron spectrum of the zirconium dioxide film obtained using the Group IVB metal compound prepared in Example 2 for thin film preparation. DETAILED DESCRIPTION

[0122] The present application will be described in detail below with reference to the accompanying drawings.

[0123] Group IVB metals include titanium (Ti), zirconium (Zr) and hafnium (Hf), which have active chemical properties and can form compounds with a variety of non-metallic elements. Currently, as commonly used precursors for MOCVD and ALD processes, Group IVB metal compounds have low vapor pressure, poor thermal stability or produce by-products that have adverse effects on the deposition process, thereby resulting in defects in the thickness and uniformity of the deposited metal oxide or nitride film.

[0124] To solve the above problems, the present inventors have developed a Group IVB metal organic compound with high decomposition temperature and high volatility. When used as a precursor for MOCVD and ALD processes, the compound can prepare high-performance functional thin films or coatings due to its high thermal stability and high vapor pressure, and is expected to become an ideal material for preparing high-performance electronic devices such as capacitors and memories.

[0125] Specifically, the Group IVB metal compound of the present application has the general formula 1:

[0126]

General Formula 1

[0127] wherein M is Ti, Zr or Hf;

[0128] R1to R 10 each independently selected from H, C1to C6groups, and R8is not H;

[0129] m, n, k are each independently selected from 1, 2, 3;

[0130] The C1to C6groups can be saturated or unsaturated linear, branched or cyclic groups, which are optionally substituted with fluorine atoms. Preferably, the C1to C6groups are alkyl groups, which are optionally substituted with fluorine atoms.

[0131] In the Group IVB metal compound of the present application, the cyclopentadienyl group is chelated with the central Group IVB metal through an amino bridge, and then chelated with the metal through the nitrogen atoms at both ends of the triamine to form two covalent bonds. This chelation mode can increase the intramolecular cohesive force, and is conducive to improving the stability of the metal compound, so that the compound as a whole has high thermal stability and high vapor pressure. Therefore, when it is used as a precursor, the problems of poor thermal stability and low vapor pressure of the commonly used Group IVB metal precursors are solved; and when it is used as an organic catalyst for olefin polymerization, the catalytic activity at high temperature is significantly improved.

[0132] In addition, the cyclopentadiene and triamine ligand structure of the Group IVB metal compound of the present application is simple, and the substances released after the Group IVB metal compound participates in the film forming reaction are all low molecular weight and volatile, so that no by-products are introduced during the film forming process, and the increase of carbon deposition residues is avoided.

[0133] In one embodiment, R9 and R 10 The Group IVB metal compound of the present application can have the general formula 2:

[0134]

General formula 2

[0135] In one embodiment, m and n in the general formula 2 can both be 2 and k can be 1, and the Group IVB metal compound of the present application can have the general formula 3:

[0136]

General formula 3

[0137] In another embodiment, k in the general formula 2 can be 1 and m and n can both be 3, and the Group IVB metal compound of the present application can have the general formula 4:

[0138]

General formula 4

[0139] In still another embodiment, R9 and R 10 may both be methyl, m and n can both be 2 and k can be 1, and the Group IVB metal compound of the present application can have the general formula 5:

[0140]

General formula 5

[0141] In still another embodiment, R9 and R 10 may both be methyl, k can be 1 and m and n can both be 3, and the Group IVB metal compound of the present application can have the general formula 6:

[0142]

General formula 6

[0143] Some specific structural formulas of the Group IVB metal compounds of the present application are listed below:

[0144] wherein M can be Ti, Zr or Hf.

[0145] In summary, representative examples of compounds of Formula 1 can be listed as follows:

[0146] (CpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0147] (CpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0148] (CpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0149] (CpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0150] (MeCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0151] (MeCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0152] (MeCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0153] (MeCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0154] (EtCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe),

[0155] (EtCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe),

[0156] (EtCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0157] (EtCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe),

[0158] n PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe)2,

[0159] n PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe)2,

[0160] n PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe)2,

[0161] n PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe)2,

[0162] i PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe)2,

[0163] i PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe)2,

[0164] i PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe)2,

[0165] i PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe)2,

[0166] (CpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe)2,

[0167] (CpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe)2,

[0168] (CpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe)2,

[0169] (CpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe)2,

[0170] ​​​​​​​​(MeCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0171] (MeCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0172] (MeCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0173] (MeCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0174] (EtCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0175] (EtCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0176] (EtCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0177] (EtCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0178] ( n PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0179] ( n PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0180] ( n PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0181] ( n PrCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0182] ( i PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),

[0183] i PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),

[0184] i PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0185] i PrCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),

[0186] (CpCH2CH2NMe)M(EtNCH2CH2NHCH2CH2NEt),

[0187] (CpCH2CH2NEt)M(EtNCH2CH2NHCH2CH2NEt),

[0188] (CpCH2CH2N n Pr)M(EtNCH2CH2NHCH2CH2NEt),

[0189] (CpCH2CH2N i Pr)M(EtNCH2CH2NHCH2CH2NEt),

[0190] (CpCH2CH2NMe)M(EtNCH2CH2NMeCH2CH2NEt),

[0191] (CpCH2CH2NEt)M(EtNCH2CH2NMeCH2CH2NEt),

[0192] (CpCH2CH2N n Pr)M(EtNCH2CH2NMeCH2CH2NEt),

[0193] (CpCH2CH2N i Pr)M(EtNCH2CH2NMeCH2CH2NEt),

[0194] (CpCH2CH2NMe)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0195] (CpCH2CH2NEt)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0196] ​​​(CpCH2CH2N n Pr)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0197] (CpCH2CH2N i Pr)M( i PrNCH2CH2NHCH2CH2N i Pr),

[0198] (CpCH2CH2NMe)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0199] (CpCH2CH2NEt)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0200] (CpCH2CH2N n Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr),

[0201] (CpCH2CH2N i Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr);

[0202] (CpCH2CH2CH2CH2NMe)M(HNCHAllylNHCHMeNCycloAm);

[0203] (2-AllylCpCH2CH2CH2CH2NMe)M(HNCH2CH2CH2NHCH2CH2CH2N i Bu);

[0204] (CpCH2CH2NMe)M(AllylNCH2CH2NHCH2CH2CH2NCF3);

[0205] (CpCH2CH2CH2NMe)M(MeNCH2NCF3CH2NMe);

[0206] (2,3,4,5-4MeCpCH2CH2CH2CH2NCF3)M(CycloAmNCH2CH2CHMeNMeCHMeCH2CH2NMe);

[0207] (2,4-2MeCpCH2CH2CH2NAIlyl)M(MeNCHMeCH2NHCH2CHMeNMe);

[0208] (MeCpCH2CH2NMe)M(MeNCH2CHMeCH2NMeCH2CHMeCH2NMe);

[0209] (CpCH2CH2NMe)M(MeNCH2CH2CH2NHCH2CH2CH2NMe); or

[0210] (CpCH2CH2NMe)M(MeNCH2CHMeNHCHMeCH2NMe);

[0211] 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, i Bu represents isobutyl.

[0212] The application also provides a preparation method of the Group IVB metal compound of any one of the above embodiments, comprising:

[0213] S100, reacting the compound of general formula 7 and the compound of general formula 8 according to the following reaction formula to obtain an intermediate product,

[0214]

General formula 7

[0215]

General formula 8

[0216] Reaction formula:

[0217] wherein M is Ti, Zr or Hf, R 11 and R 12 are each independently selected from C1 to C6 groups; R4 to R7 are each independently selected from H, C1 to C6 groups; R8 is selected from C1 to C6 groups; k is selected from 1, 2, 3.

[0218] In one embodiment, the above reaction can be carried out in an organic solvent. The organic solvent can be a conventional solvent for such a reaction, and is preferably selected from hydrocarbons or ethers. The hydrocarbon solvent can be hexane, heptane, decane, benzene, toluene, etc.; 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.

[0219] In an embodiment, the above reaction can be carried out at 25 to 75°C, and the reaction time can be 4 to 8 hours.

[0220] In an embodiment, to improve the yield of the reaction, the molar ratio of the compound of Formula 7 to the compound of Formula 8 can be 1: (1-1.2).

[0221] In an embodiment, the above reaction can be carried out under an inert atmosphere such as nitrogen, argon, helium.

[0222] Specifically, the reaction process can be as follows: the compound of Formula 7 is dispersed in an organic solvent, cooled to -15 to -10°C, the compound of Formula 8 is added dropwise to the organic solvent under stirring, then warmed to the reaction temperature for reaction, and after the reaction is completed, the intermediate product is obtained by distillation.

[0223] S200, reacting the intermediate product and the compound of Formula 9 according to the following reaction formula to obtain the Group IVB metal compound of Formula 1.

[0224]

Formula 9

[0225] That is, the multi-dentate amine ligand compound of Formula 9 is introduced into the intermediate product system to obtain the Group IVB metal compound, wherein R1 to R 10 The definitions of the groups are the same as those of Formula 1.

[0226] In an 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, 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.

[0227] In an embodiment, the above reaction can be carried out at 25 to 75°C, and the reaction time can be 4 to 8 hours.

[0228] In an embodiment, to improve the yield of the reaction, the molar ratio of the compound of Formula 7 in S100 to the compound of Formula 9 in S200 can be 1: (1-1.1).

[0229] In an embodiment, the above reaction can be carried out under an inert atmosphere such as nitrogen, argon, helium.

[0230] Specifically, the reaction process can be as follows: the intermediate product is dispersed in an organic solvent, cooled to -15 to -10°C, the compound of Formula 9 is added dropwise to the organic solvent under stirring, then warmed to the reaction temperature for reaction, and after the reaction is completed, the Group IVB metal compound of Formula 1 is obtained by distillation.

[0231] By the preparation method of the present application, high purity semiconductor grade Group IV metal compounds can be obtained. Only a single solvent such as hydrocarbon can be used in the whole synthesis process, which reduces the cost of preparation and the toxicity of the reaction process, has better operability, higher yield, and is easy to scale up. After the reaction is completed, the product is subjected to rectification, purification, adsorption, filtration and other steps, and the purity and particle size of the final product can better meet the product requirements of the semiconductor industry.

[0232] The present application also provides a composition comprising 0.1 wt% to 99.9 wt% of the Group IVB metal compound of any of the above embodiments and the balance of one or more organic compounds selected from hydrocarbons, ethers, esters, alcohols, amines, sulfides, phosphines. Among them, the organic compound has no limitation as long as it can stabilize the Group IVB metal compound of general formula 1. The hydrocarbon can be selected from aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, ethylene, propylene, butene, pentene, hexene, heptene, octene, acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne; cyclic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, hexahydroindene, cyclooctane and the like; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like; or mixtures thereof. The ether can be selected from tetrahydrofuran, diethyl ether, methyl tert-butyl ether or mixtures thereof. The ester can be selected from methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate or mixtures thereof. The alcohol can be selected from methanol, ethanol, propanol, butanol or mixtures thereof. The amine can be selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or mixtures thereof. The phosphine can be selected from triphenylphosphine, tricyclohexylphosphine or mixtures thereof.

[0233] This composition can stabilize the Group IVB metal compound, thus facilitating the use of one or more Group IVB metal compounds of the present application in combination.

[0234] The present application also provides an olefin polymerization method, which comprises using the Group IVB metal compound of the present application as an organic catalyst. Since the Group IVB metal compound has high thermal stability, it can still maintain catalytic activity at high temperature, thereby improving the efficiency of the polymerization reaction. In an embodiment, the olefin can be selected from α-olefins.

[0235] The present application also provides a method for preparing a functional material containing Group IVB metal elements, which comprises using the Group IVB metal compound of the present application as a precursor. In particular, the functional material can be in the form of a film. Therefore, the present application also provides a film containing Group IVB metal elements, which comprises the compound (M1 a O b M 2 1-a )N c C d wherein 0 < a < 1, 0 < b < 3, 0 < c < 2, 0 < d < 1, and b + c ≠ 0; M 1 represents Ti, Zr or Hf; M 2 represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La or Ce; and M 1 and M 2 are different. Specifically, the Group IVB metal compound of the present application can be vaporized to form a first vapor phase metal source; at least one M 2 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 film containing a Group IVB metal element on the substrate.

[0236] The present application is further illustrated in detail below with reference to examples.

[0237] Example 1: Preparation of (CpCH2CH2NMe)Zr(MeNCH2CH2NHCH2CH2NMe)

[0238] Under a helium atmosphere, 26.60 mg (0.10 mmol) of tetra(dimethylamino)zirconium was dispersed in 100 ml of n-hexane and cooled to -15°C. To this was added dropwise 13.54 mg (0.11 mmol) of N-methyl-2-cyclopentadienyl ethylamine with stirring. After being allowed to warm to room temperature, the reaction was allowed to proceed for 5 hours, desolved, and subjected to reduced pressure distillation to obtain the intermediate compound.

[0239] Under a helium atmosphere, the intermediate compound purified in the previous step was dissolved in 100 ml of n-hexane and cooled to -15°C. To this was added dropwise 13.11 mg (0.10 mmol) of N,N"-dimethyl diethylenetriamine with stirring. After being allowed to warm to room temperature, the reaction was allowed to proceed for 5 hours, desolved, and subjected to reduced pressure distillation to obtain the target product.

[0240] The zirconium compound thus obtained was subjected to nuclear magnetic resonance spectroscopy. As shown in Fig. 1, the spectral data thereof were as follows: 1H NMR (C6D6, ppm) is: δ 6.11 (2H, CpH), δ 5.40 (2H, CpH), δ 3.69 (2H, t, NCH2CH2Cp), δ 3.25 (3H, s, NCH3), δ 3.17 (2H, m, -CH2-), δ 3.06 (6H, s, NCH3), δ 2.98 (2H, t, NCH2CH2Cp), δ 2.65 (2H, m, -CH2-), δ 2.46 (2H, m, -CH2-), δ 2.43 (2H, m, -CH2-), δ 1.39 (1H, s, -NH).

[0241] Example 2: Preparation of (CpCH2CH2NMe)Zr(MeNCH2CH2NMeCH2CH2NMe)

[0242] Under argon atmosphere, 39.3 mg (0.15 mmol) of tetra(dimethylamino)zirconium was dispersed in 150 ml of n-hexane and cooled to -15°C. To this, 20.93 mg (0.17 mmol) of N-methyl-2-cyclopentadienyl ethylamine was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 8 hours, desolved and the intermediate compound was obtained by distillation under reduced pressure.

[0243] Under argon atmosphere, the intermediate compound purified in the previous step was dissolved in 150 ml of n-hexane and cooled to -15°C. To this, 21.75 mg (0.15 mmol) of N,N',N"-trimethyl diethylenetriamine was added dropwise under stirring. After being brought to room temperature, the reaction was carried out for 8 hours, desolved and the target product was obtained by distillation under reduced pressure.

[0244] The zirconium compound obtained was subjected to nuclear magnetic resonance spectroscopy analysis. As shown in Figure 2, the spectral data thereof is 1 H NMR (C6D6, ppm) is: δ 6.12 (2H, CpH), δ 5.54 (2H, CpH), δ 3.95 (2H, t, NCH2CH2Cp), δ 3.23 (3H, s, NCH3), δ 3.16 (2H, m, -CH2-), δ 3.03 (6H, s, NCH3), δ 2.97 (2H, t, NCH2CH2Cp), δ 2.85 (2H, m, -CH2-), δ 2.69 (2H, m, -CH2-), δ 2.36 (2H, m, -CH2-), δ 1.85 (3H, s, -CH3).

[0245] The zirconium compound obtained was subjected to thermal decomposition test, while the commonly used Group IVB metal precursors As a reference, the thermogravimetric curve shown in Figure 4 was obtained. As shown in Figure 4, the Group IVB metal compound of Example 2 has an initial decomposition temperature of 223.96°C, and a temperature T50% of 245.23°C. 1 / 2 As a reference, the thermogravimetric curve shown in Figure 4 was obtained. As shown in Figure 4, the Group IVB metal compound of Example 2 has an initial decomposition temperature of 223.96°C, and a temperature T50% of 245.23°C. 1 / 2 As a reference, the thermogravimetric curve shown in Figure 4 was obtained. As shown in Figure 4, the Group IVB metal compound of Example 2 has an initial decomposition temperature of 223.96°C, and a temperature T50% of 245.23°C.

[0246] Example 3: Preparation of (CpCH2CH2NMe)Hf(MeNCH2CH2NHCH2CH2NMe)

[0247] Under a nitrogen atmosphere, 28.49 mg (0.08 mmol) of hafnium tetra(dimethylamide) was dispersed in 80 ml of n-hexane and cooled to -15°C. 12.31 mg (0.10 mmol) of N-methyl-2-cyclopentadienyl ethylamine was added dropwise thereto under stirring. After being raised to room temperature, the reaction was carried out for 4 hours, desolved, and the intermediate compound was obtained by reduced pressure distillation.

[0248] Under a nitrogen atmosphere, 28.49 mg (0.08 mmol) of hafnium tetra(dimethylamide) was dispersed in 80 ml of n-hexane and cooled to -15°C. 12.31 mg (0.10 mmol) of N-methyl-2-cyclopentadienyl ethylamine was added dropwise thereto under stirring. After being raised to room temperature, the reaction was carried out for 4 hours, desolved, and the intermediate compound was obtained by reduced pressure distillation.

[0249] The prepared hafnium compound was subjected to nuclear magnetic resonance spectroscopy analysis. As shown in Figure 3, the spectral data thereof 1 H NMR (C6D6, ppm) is: δ 6.11 (2H, CpH), δ 5.34 (2H, CpH), δ 4.01 (2H, t, NCH2CH2Cp), δ 3.26 (6H, s, NCH3), δ 3.10 (3H, s, NCH3), δ 2.73 (4H, m, -CH2-), δ 2.67 (2H, t, NCH2CH2Cp), δ 2.40 (4H, m, -CH2-).

[0250] Example 4: Preparation of (CpCH2CH2NMe)Ti(MeNCH2CHMeNHCHMeCH2NMe)

[0251] Under argon atmosphere, 22.42 mg (0.1 mmol) of tetra(dimethylamino)titanium was dispersed in 100 ml of tetrahydrofuran, and cooled to -15°C. To this, 13.54 mg (0.11 mmol) of N-methyl-2-cyclopentadienyl-ethylamine was added dropwise under stirring. After raising the temperature to 50°C, the reaction was carried out for 6 hours, desolventized, and the intermediate compound was obtained by distillation under reduced pressure.

[0252] Under argon atmosphere, the intermediate compound purified in the previous step was dissolved in 100 ml of tetrahydrofuran, and cooled to -15°C. To this, 17.51 mg (0.11 mmol) of N,N"-dimethyl-di(1-methyl-ethylene)-triamine was added dropwise under stirring. After raising the temperature to 50°C, the reaction was carried out for 6 hours, desolventized, and the target product was obtained by distillation under reduced pressure.

[0253] Example 5: Preparation of (CpCH2CH2NMe)Hf(MeNCH2CH2CH2NHCH2CH2CH2NMe)

[0254] Under argon atmosphere, 35.62 mg (0.10 mmol) of tetra(dimethylamino)hafnium was dispersed in 100 ml of n-hexane, and cooled to -15°C. To this, 14.77 mg (0.12 mmol) of N-methyl-2-cyclopentadienyl-ethylamine was added dropwise under stirring. After raising the temperature to 75°C, the reaction was carried out for 4 hours, desolventized, and the intermediate compound was obtained by distillation under reduced pressure.

[0255] 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, 15.92 mg (0.10 mmol) of N,N"-dimethyl-di(propylene)-triamine was added dropwise under stirring. After raising the temperature to 75°C, the reaction was carried out for 4 hours, desolventized, and the target product was obtained by distillation under reduced pressure.

[0256] Example 6: Preparation of (MeCpCH2CH2NMe)Zr(MeNCH2CHMeCH2NMeCH2CHMeCH2NMe)

[0257] Under argon atmosphere, 26.60 mg (0.1 mmol) of tetra(dimethylamino)zirconium was dispersed in 100 ml of n-hexane, and cooled to -15°C. To this, 15.08 mg (0.11 mmol) of N-methyl-2-(2-methyl-cyclopentadienyl)-ethylamine was added dropwise under stirring. After raising the temperature to room temperature, the reaction was carried out for 8 hours, desolventized, and the intermediate compound was obtained by distillation under reduced pressure.

[0258] ​​The intermediate compound purified in the previous step was dissolved in 100 ml of ethylene glycol dimethyl ether under argon atmosphere and cooled to -15°C. To this was added dropwise 15.92 mg (0.10 mmol) of N,N',N"-trimethyldi(2-methyl-ethylidene)triamine under stirring. N,N',N"-trimethyldi(2-methyl-ethylidene)triamine. After warming to room temperature, the reaction was allowed to proceed for 8 hours, desolubilized and distilled under reduced pressure to obtain the target product.

[0259] Example 7: Preparation of (2,4-2MeCpCH2CH2CH2NAIlyl)Ti(MeNCHMeCH2NHCH2CHMeNMe)

[0260] The intermediate compound purified in the previous step was dissolved in 100 ml of ethylene glycol dimethyl ether under argon atmosphere and cooled to -15°C. To this was added dropwise 15.92 mg (0.10 mmol) of N,N',N"-trimethyldi(2-methyl-ethylidene)triamine under stirring. N-allyl-3-(2,4-dimethyl-cyclopentadienyl)propylamine. After warming to room temperature, the reaction was allowed to proceed for 8 hours, desolubilized and distilled under reduced pressure to obtain the intermediate compound.

[0261] The intermediate compound purified in the previous step was dissolved in 100 ml of ethylene glycol dimethyl ether under argon atmosphere and cooled to -15°C. To this was added dropwise 15.92 mg (0.10 mmol) of N,N',N"-trimethyldi(2-methyl-ethylidene)triamine under stirring. N,N"-dimethyldi(2-methyl-ethylidene)triamine. After warming to room temperature, the reaction was allowed to proceed for 8 hours, desolubilized and distilled under reduced pressure to obtain the target product.

[0262] Example 8: Preparation of (2,3,4,5-4MeCpCH2CH2CH2CH2NCF3)Zr(CycloAmNCH2CH2CHMeNMeCHMeCH2CH2NMe)

[0263] The intermediate compound purified in the previous step was dissolved in 100 ml of ethylene glycol dimethyl ether under argon atmosphere and cooled to -15°C. To this was added dropwise 15.92 mg (0.10 mmol) of N,N',N"-trimethyldi(2-methyl-ethylidene)triamine under stirring. N-trifluoromethyl-4-(2,3,4,5-tetramethyl-cyclopentadienyl)butylamine. After warming to room temperature, the reaction was allowed to proceed for 8 hours, desolubilized and distilled under reduced pressure to obtain the intermediate compound.

[0264] The intermediate compound purified in the previous step was dissolved in 100 ml of ethylene glycol dimethyl ether under argon atmosphere and cooled to -15°C. To this was added dropwise 15.92 mg (0.10 mmol) of N,N',N"-trimethyldi(2-methyl-ethylidene)triamine under stirring. N-cyclopentyl-N',N"-dimethylbis(1-methyl-propylidene)amine. After 8 hours at room temperature, the reaction was worked up and the target product was obtained by distillation under reduced pressure.

[0265] Example 9: Preparation of (CpCH2CH2CH2NMe)Zr(MeNCH2NCF3CH2NMe)

[0266] Under an argon atmosphere, 26.60 mg (0.1 mmol) of tetra(dimethylamino)zirconium was dispersed in 100 ml of n-hexane and cooled to -15°C. To this, 16.45 mg (0.12 mmol) of N-methyl-2-cyclopentadienyl-ethylamine was added dropwise with stirring. After 8 hours at room temperature, the reaction was worked up and the intermediate compound was obtained by distillation under reduced pressure. N-methyl-3-(cyclopentadienyl)propylamine. After 8 hours at room temperature, the reaction was worked up and the intermediate compound was obtained by distillation under reduced pressure.

[0267] 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. To this, 17.11 mg (0.10 mmol) of N,N'-dimethylformamide was added dropwise with stirring. After 8 hours at room temperature, the reaction was worked up and the target product was obtained by distillation under reduced pressure. N,N"-dimethyl-N'-trifluoromethyl-dimethylidene-triamine. After 8 hours at room temperature, the reaction was worked up and the target product was obtained by distillation under reduced pressure.

[0268] Example 10: Preparation of (CpCH2CH2NMe)Hf(AllylNCH2CH2NHCH2CH2CH2NCF3)

[0269] Under an argon atmosphere, 35.62 mg (0.10 mmol) of tetra(dimethylamino)hafnium was dispersed in 100 ml of n-hexane and cooled to -15°C. To this, 14.78 mg (0.12 mmol) of N-methyl-2-cyclopentadienyl-ethylamine was added dropwise with stirring. After 8 hours at room temperature, the reaction was worked up and the intermediate compound was obtained by distillation under reduced pressure.

[0270] 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. To this, 24.77 mg (0.11 mmol) of N,N'-dimethylformamide was added dropwise with stirring. After 8 hours at room temperature, the reaction was worked up and the target product was obtained by distillation under reduced pressure. N-trifluoromethyl-N"-allyl-propylidene-ethyltriamine. After 8 hours at room temperature, the reaction was worked up and the target product was obtained by distillation under reduced pressure.

[0271] Example 11: Preparation of (2-allylCpCH2CH2CH2CH2NMe)Ti(HNCH2CH2CH2NHCH2CH2CH2N i Bu)

[0272] Under argon atmosphere, 22.42 mg (0.1 mmol) of tetra(dimethylamino) titanium was dispersed in 100 ml of n-hexane and cooled to -15°C. To this, 22.94 mg (0.12 mmol) of N-methyl-4-(2-allyl-cyclopentadienyl)butylamine was added dropwise under stirring. N-methyl-4-(2-allyl-cyclopentadienyl)butylamine. After 8 hours of reaction at room temperature, desolventization was performed and the intermediate compound was obtained by distillation under reduced pressure.

[0273] 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, 20.59 mg (0.11 mmol) of N,N'-diallylformamidine was added dropwise under stirring. N'-isobutyl-dipropyltriamine. After 8 hours of reaction at room temperature, desolventization was performed and the target product was obtained by distillation under reduced pressure.

[0274] Example 12: Preparation of (CpCH2CH2CH2CH2NMe)Zr(HNCHAllylNHCHMeNCycloAm)

[0275] Under argon atmosphere, 35.62 mg, (0.10 mmol) of tetra(dimethylamino) zirconium was dispersed in 100 ml of n-hexane and cooled to -15°C. To this, 18.14 mg (0.12 mmol) of N-methyl-4-(cyclopentadienyl)butylamine was added dropwise under stirring. N-methyl-4-(cyclopentadienyl)butylamine. After 8 hours of reaction at room temperature, desolventization was performed and the intermediate compound was obtained by distillation under reduced pressure.

[0276] 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, 21.69 mg (0.11 mmol) of N,N'-diallylformamidine was added dropwise under stirring. N-(allyl-methylidene)-N'-cyclopentyl-(1-methyl-methylidene)triamine. After 8 hours of reaction at room temperature, desolventization was performed and the target product was obtained by distillation under reduced pressure.

[0277] Application Example 1: Experiment of catalytic polymerization of ethylene

[0278] 6.25 μmol of the Group IVB metal compound prepared in Example 2 The main catalyst, 0.25 mmol methylaluminoxane as cocatalyst, 200 ml toluene as reaction solvent were placed in a stainless steel reactor, then 13 g of 1,3-butadiene monomer was added into the reactor, and heated to 75°C for polymerization. After 1 hour of reaction, the polybutadiene was separated by filtration and dried under vacuum for analysis. The weight average molecular weight (Mw) of the obtained polymer was 157000 g / mol, and the molecular weight distribution (PDI) was 1.95, determined by gel chromatography.

[0279] In order to evaluate the catalytic performance of the Group IVB metal compound of the present application, the following comparative experiments were carried out on the commonly used olefin polymerization catalysts.

[0280] Polymerization Comparative Example 1: 6.25 μmol of cyclopentadiene tris(dimethylamino)zirconium was used as the main catalyst, and the polymerization reaction was carried out in the same way as described above. The weight average molecular weight (Mw) of the obtained polymer was 126000 g / mol, and the molecular weight distribution (PDI) was 2.28, determined by gel chromatography.

[0281] Polymerization Comparative Example 2: 6.25 μmol of commercial dichlorobis-cyclopentadienyl zirconium compound Cp2ZrCl2 was used as the main catalyst, and the polymerization reaction was carried out in the same way as described above. The weight average molecular weight (Mw) of the obtained polymer was 159000 g / mol, and the molecular weight distribution (DPI) was 2.05, determined by gel chromatography.

[0282] It can be seen that the Group IVB metal compound prepared in Example 2 has good catalytic performance for olefin polymerization reaction, and the synthesized polymer has high molecular weight and uniform molecular weight distribution, and its effect can match that of the commercial cyclopentadienyl zirconium catalyst. This is related to the high thermal stability of the Group IVB metal compound of the present application, which can maintain catalytic activity at high temperature when used as an organic catalyst for olefin polymerization, thereby improving the polymerization reaction efficiency at high temperature.

[0283] Application Example 2: Thin film preparation experiment

[0284] A clean silicon substrate was selected and transferred to the reaction chamber of a thin film deposition device. The substrate was heated to 350°C. The Group IVB metal compound prepared in Example 2 was introduced into the reaction chamber under 50 sccm argon as carrier gas, pulsed for 5 seconds, then 500 sccm argon was introduced for purging, and the purging time was 10 seconds. Then, 100 sccm ozone was introduced as reaction gas, pulsed for 3 seconds, and then stopped. Finally, 500 sccm argon was introduced for purging, and the purging time was 10 seconds to ensure that the ozone and by-products not involved in the reaction were removed, and thus a cycle of thin film deposition was completed. The above process was repeated 200 times to obtain a zirconia thin film.

[0285] The zirconium oxide film prepared above was subjected to X-ray photoelectron spectroscopy analysis, and the X-ray photoelectron spectrum obtained is shown in Fig. 5. As shown in Fig. 5, the two peaks presented therein are consistent with the characteristics of Zr02, confirming that the zirconium oxide film has been successfully prepared in the experiment.

[0286] It can be seen from the above that the Group IVB metal compound of the present application can be used as a precursor for preparing a functional material containing a Group IVB metal element, particularly as a precursor for preparing a film containing a Group IVB metal element.

[0287] The foregoing description of specific exemplary embodiments of the application has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the principles of the application and its practical application, to thereby enable others skilled in the art to implement and utilize the application in various different exemplary embodiments and various different selections and combinations of elements.

Claims

1. A Group IVB metal compound characterized in that, having the general formula 1: [Formula 1] wherein M is Ti, Zr or Hf; R1to R 10 each independently selected from H, a C1to C6group, and R8is not H; m, n, k are each independently selected from 1, 2, 3; said Ci to C6 group is a saturated or unsaturated straight chain, branched or cyclic group, optionally substituted with a fluorine atom.

2. The Group IVB metal compound of claim 1, wherein, R9, R 10 each H, having the general formula 2: [Formula 2] 3. The Group IVB metal compound of claim 2, wherein, k is 1; when m, n are both 2, it has the general formula 3: [Formula 3] when m, n are both 3, it has the general formula 4: [Formula 4] 4. The Group IVB metal compound of claim 1, wherein, R9, R 10 each is CH3, k is 1, and when m, n are both 2, it has the following general formula 5: [Formula 5] when m, n are both 3, it has the general formula 6: [Formula 6] 5. The Group IVB metal compound of claim 1, wherein, said compound is selected from: (CpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe), (CpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe), (CpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe), (CpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe), (MeCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe), (MeCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe), (MeCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe), (MeCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe), (EtCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe), (EtCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe), (EtCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe), (EtCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe), ( n PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe), ( n PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe), ( n PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe), ( n PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe), ( i PrCpCH2CH2NMe)M(MeNCH2CH2NHCH2CH2NMe), ( i PrCpCH2CH2NEt)M(MeNCH2CH2NHCH2CH2NMe), ( i PrCpCH2CH2N n Pr)M(MeNCH2CH2NHCH2CH2NMe), ( i PrCpCH2CH2N i Pr)M(MeNCH2CH2NHCH2CH2NMe), (CpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe), (CpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe), (CpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe), (CpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe), (MeCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe), (MeCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe), (MeCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe), (MeCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe), (EtCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe), (EtCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe), (EtCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe), (EtCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe), ( n PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe), ( n PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe), n PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),​ n PrCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),​ ( i PrCpCH2CH2NMe)M(MeNCH2CH2NMeCH2CH2NMe),​ i PrCpCH2CH2NEt)M(MeNCH2CH2NMeCH2CH2NMe),​ i PrCpCH2CH2N n Pr)M(MeNCH2CH2NMeCH2CH2NMe),​ i PrCpCH2CH2N i Pr)M(MeNCH2CH2NMeCH2CH2NMe),​ (CpCH2CH2NMe)M(EtNCH2CH2NHCH2CH2NEt), (CpCH2CH2NEt)M(EtNCH2CH2NHCH2CH2NEt), (CpCH2CH2N n Pr)M(EtNCH2CH2NHCH2CH2NEt), (CpCH2CH2N i Pr)M(EtNCH2CH2NHCH2CH2NEt), (CpCH2CH2NMe)M(EtNCH2CH2NMeCH2CH2NEt), (CpCH2CH2NEt)M(EtNCH2CH2NMeCH2CH2NEt), (CpCH2CH2N n Pr)M(EtNCH2CH2NMeCH2CH2NEt), (CpCH2CH2N i Pr)M(EtNCH2CH2NMeCH2CH2NEt), (CpCH2CH2NMe)M i PrNCH2CH2NHCH2CH2N i Pr), (CpCH2CH2NEt)M i PrNCH2CH2NHCH2CH2N i Pr), (CpCH2CH2N n Pr)M( i PrNCH2CH2NHCH2CH2N i Pr), (CpCH2CH2N i Pr)M( i PrNCH2CH2NHCH2CH2N i Pr), (CpCH2CH2NMe)M i PrNCH2CH2NMeCH2CH2N i Pr), (CpCH2CH2NEt)M i PrNCH2CH2NMeCH2CH2N i Pr), (CpCH2CH2N n Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr), (CpCH2CH2N i Pr)M( i PrNCH2CH2NMeCH2CH2N i Pr) ; (CpCH2CH2CH2CH2NMe)M(HNCHAllylNHCHMeNCycloAm); (2-allylCpCH2CH2CH2CH2NMe)M(HNCH2CH2CH2NHCH2CH2CH2N i Bu); (CpCH2CH2NMe)M(AllylNCH2CH2NHCH2CH2CH2NCF3); (CpCH2CH2CH2NMe)M(MeNCH2NCF3CH2NMe); (2,3,4,5-4MeCpCH2CH2CH2CH2NCF3)M(CycloAmNCH2CH2CHMeNMeCHMeCH2CH2NMe); (2,4-2MeCpCH2CH2CH2NAllyl)M(MeNCHMeCH2NHCH2CHMeNMe); (MeCpCH2CH2NMe)M(MeNCH2CHMeCH2NMeCH2CHMeCH2NMe); (CpCH2CH2NMe)M(MeNCH2CH2CH2NHCH2CH2CH2NMe); or (CpCH2CH2NMe)M(MeNCH2CHMeNHCHMeCH2NMe); 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, i Bu represents i-butyl.

6. A process for the preparation of a Group IVB metal compound, characterized in that, comprising: reacting a compound of Formula 7 with a compound of Formula 8 to obtain an intermediate; reacting the intermediate with a compound of Formula 9 to obtain a Group IVB metal compound of Formula 1; [Formula 7] [Formula 8] [Formula 9] [Formula 1] wherein M is Ti, Zr or Hf; R1to R 10 each is independently selected from H, a C1to C6group, and R8is not H; R 11 to R 12 each independently selected from C1to C6groups; m, n, k are each independently selected from: 1, 2, 3; C1 to C6 groups are saturated or unsaturated linear, branched or cyclic groups, optionally substituted with fluorine atoms.

7. The production method according to claim 6, characterized by, The step of reacting a compound of Formula 7 with a compound of Formula 8 to obtain an intermediate is: The compound of Formula 7 is dispersed in an organic solvent, the compound of Formula 8 is added dropwise to the organic solvent under cooling stirring, then the reaction is carried out by warming to the reaction temperature, and the intermediate is obtained by distillation after the reaction is completed.

8. The preparation method according to claim 6, characterized in that, The step of reacting the intermediate with a compound of Formula 9 to obtain a Group IVB metal compound is: The intermediate is dispersed in an organic solvent, the compound of Formula 9 is added dropwise to the organic solvent under cooling stirring, then the reaction is carried out by warming to the reaction temperature, and the Group IVB metal compound is obtained by distillation after the reaction is completed.

9. The production method according to claim 7 or 8, characterized by, The organic solvent is selected from hydrocarbons or ethers.

10. The production method according to any one of claims 6 to 9, characterized by, The molar ratio of the compound of Formula 7, the compound of Formula 8 and the compound of Formula 9 is 1:(1-1.2):(1-1.1).

11. A composition comprising 0.1 wt% to 99.9 wt% of the compound of Formula 1 and a balance of one or more organic compounds selected from hydrocarbons, ethers, esters, alcohols, amines, sulfides, phosphines; [Formula 1] wherein M is Ti, Zr or Hf; R1to R 10 each independently selected from H, a C1to C6group, and R8is not H; m, n, k are each independently selected from 1, 2, 3; C1 to C6 groups are saturated or unsaturated linear, branched or cyclic groups, optionally substituted with fluorine atoms.

12. An olefin polymerization method comprising using the Group IVB metal compound of any one of claims 1 to 5 or the Group IVB metal compound prepared by the method of 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 the Group IVB metal compound of any one of claims 1 to 5 or the Group IVB metal compound prepared by the method of any one of claims 6 to 10 as a precursor, preferably in a form in which a film of the functional material is formed.

14. The method of claim 13, wherein, The film containing the Group IVB metal element is prepared by a chemical vapor deposition process or an atomic layer deposition process.

15. The method of claim 14, wherein, Films containing Group IVB metal elements include compounds of the formula: (M 1 a O b M 2 1-a )N c C d ; wherein 0 < a ≤ 1, 0 ≤ b < 3, 0 ≤ c < 2, 0 ≤ d < 1, and b + c ≠ 0. M 1 represents Ti, Zr or Hf; M 2 represents Mg, Al, In, Ga, Si, Ge, Sn, Ti, Zr, Hf, Nb, Ta, La or Ce; And M 1 and M 2 are different.

Images