Aminophenol oxygroup transition metal complex as well as preparation method and application thereof

Abstract

The invention discloses an aminophenol oxygroup transition metal complex, which is characterized in that lewis acidity of a transition metal center and steric hindrance around the metal center are adjusted by changing pendent coordinatable substituent groups and phenoxy ortho-and para substituent groups in a ligand, so that a catalyst has good thermal stability under a high-temperature solution polymerization condition; and high-activity preparation of polyolefin and polyolefin plastomer is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin polymerization catalysts, in particular to a class of aminophenoloxy transition metal complexes and a preparation method thereof, and application of the complexes in olefin polymerization. Background Art

[0002] Vinyl polymers are one of the most widely used polymers today. They are widely used in various fields of social production and life due to their low price, excellent performance, and easy production and processing. Copolymerization of ethylene with various α-olefins is the basis for achieving the diversification of the structure and performance of vinyl polymers. By selecting different α-olefins and achieving different α-olefin insertion rates, the molecular weight and distribution, the composition distribution of branches in the interchain, etc. can be further precisely controlled, and even polyethylene products with a full range of structure-performance relationships can be obtained: hard plastics, soft plastics, plastomers, and elastomers. In order to achieve efficient regulation of the chain structure of vinyl polymers, the design and synthesis of structure-controllable single-active center olefin catalysts is the most critical factor.

[0003] Pre-transition metal catalysts (IVB family) in non-metallocene catalysts are similar to metallocene catalysts, have the characteristics of a single active center, and use heteroatom ligands, and the ligand structure design is more diversified, which can be applied to the copolymerization of ethylene and α-olefins. In 1995, Cozzi's group used imine bisphenol ligands to synthesize a series of pre-transition metal (Ti, Zr, V) complexes to catalyze ethylene polymerization, but the activity was low (Inorg. Chem., 1995, 34, 2921-2930). Subsequently, Fujita et al. synthesized pre-transition metal (Ti, Zr, V) complexes (i.e. FI catalysts) by changing the ligand substituents to adjust the electronic effect and steric effect. This type of catalyst has a high catalytic activity, but when catalyzing the copolymerization of ethylene and α-olefins, the thermal stability and activity are poor (Euro. Patent Appl. EP0874005, 1998). In 2001, Fujita et al. replaced the ortho hydrogen atoms on aniline in the FI catalyst with fluorine atoms, and the fluorinated FI catalyst showed excellent active coordination polymerization characteristics of ethylene and propylene at room temperature (Angew. Chem. Int. Ed., 2001, 40, 2918-2920. Chem. Lett., 2001, 30, 576-577). In 2004, Tang Yong et al. designed a tridentate coordination single active center non-metallocene catalyst based on the imine bisphenol ligand, but only the complex with oxygen atoms as the side arm group was active (Organometallics, 2004, 23, 1684-1688). In 2005, Waymouth et al. used aminophenol ligands to synthesize pre-transition metal (Ti, Zr) complexes, and the comonomer insertion rate was significantly improved at room temperature, but the effect was still poor under high temperature conditions (Macromolecules, 2005, 38, 2552-2558). In addition, Exxon-Mobil disclosed a class of metal complexes of Salan ligands in patent WO2017058388A1, which have high catalytic activity for ethylene homopolymerization and copolymerization of ethylene with various α-olefins, but generally have poor temperature resistance, and their activity is significantly reduced or even directly deactivated under high-temperature polymerization conditions. Symax disclosed metal complexes of bisphenol ligands with bisether structure bridged in patent US2004010103A1 and Dow disclosed metal complexes of bisphenol ligands with bisether structure bridged in patent US20120108770A1, which have high catalytic performance for copolymerization of ethylene with various α-olefins and good temperature resistance, but their ligand structures are very complex and difficult to synthesize.

[0004] As can be seen from the above, non-metallocene early transition metal catalysts are commonly used in ethylene and propylene homopolymerization, but are rarely used in ethylene and α-olefin copolymerization, and generally have poor high temperature resistance. Therefore, it is of great significance to develop transition metal catalysts that can catalyze the copolymerization of ethylene and α-olefins with high activity under high temperature conditions and obtain copolymers with good performance. Summary of the invention

[0005] One of the objects of the present invention is to provide an aminophenoloxy transition metal complex.

[0006] The second object of the present invention is to provide a method for preparing an aminophenoloxy transition metal complex.

[0007] The third object of the present invention is to provide an application of an aminophenoloxy transition metal complex in olefin polymerization, which is particularly suitable for ethylene polymerization and copolymerization of ethylene and α-olefins such as 1-octene, and exhibits good catalytic activity and thermal stability.

[0008] Under high-temperature solution polymerization conditions, the thermal stability of the catalyst becomes one of the important parameters for measuring its catalytic performance. Currently reported aminophenol ligands are usually tetradentate ligands, which provide significantly fewer electrons for coordination with the metal center than cyclopentadienyl ligands, resulting in poor thermal stability of this type of complex. The present invention provides a class of aminophenoloxy transition metal complexes, which adjust the Lewis acidity of the transition metal center and the steric hindrance around the metal center by changing the pendant coordinating substituents and the ortho- and para-substituents of the phenoloxy groups in the ligands, so that the catalyst has good thermal stability under high-temperature solution polymerization conditions, and achieves high activity in the preparation of polyolefins and polyolefin plastomers.

[0009] The technical solution of the present invention is as follows:

[0010] The aminophenoloxy transition metal complex provided by the present invention has the following general formula (I):

[0011]

[0012] In formula (I):

[0013] R 1 , R 2 Each independently represents hydrogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C1~C 20 Straight chain, branched chain or cyclic alkoxy, C7~C 30 Mono- or poly-aryl-substituted alkyl, C6~C 30 aryl, or halogen;

[0014] A is a group having a structure represented by formula (II), (III), (IV), (V) or (VI):

[0015]

[0016] wherein A may coordinate with the metal center M through its nitrogen atom, or may not coordinate with the metal center M; or only one of A in formula (I) coordinates with the metal center M through its nitrogen atom;

[0017] X is halogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C7~C 30 A mono- or poly-aryl-substituted alkyl group;

[0018] M is selected from Group IVB metals, preferably Ti, Zr, Hf;

[0019] As a preferred embodiment, in formula (I):

[0020] R 1 , R 2 Preferably, hydrogen, C1~C 12 Straight chain, branched chain or cyclic alkyl group, C1~C 12 Straight chain, branched chain or cyclic alkoxy, C7~C 20 Alkyl, mono- or poly-aryl-substituted, C6~C 18 aryl, or halogen;

[0021] A is preferably:

[0022]

[0023] X is preferably halogen, C1~C 12 Straight chain, branched chain or cyclic alkyl group, C7~C 20 A mono- or poly-aryl-substituted alkyl group;

[0024] As a more preferred embodiment, in formula (I):

[0025] R 1 , R 2 Preferred are hydrogen, methyl, methoxy, isopropyl, tert-butyl, cumyl, 1,1-diphenylethyl, trityl, phenyl, naphthyl, anthracenyl, 3,5-di-tert-butyl-1-phenyl, halogen;

[0026] X is preferably chlorine, methyl or benzyl.

[0027] As some specific embodiments, the aminophenoloxy transition metal complex structure is:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] The invention also provides a method for preparing the aminophenoloxy transition metal complex.

[0034] The preparation method of the aminophenoloxy transition metal complex (I) of the present invention comprises the following steps:

[0035] (1) preparing aminophenol ligand compound (IX); using Path A or Path B;

[0036]

[0037] As shown in Path A, ethylenediamine is reacted with an aldehyde-substituted nitrogen-containing heterocyclic compound represented by formula (VII), and then reduced with a reducing agent to generate a corresponding di-secondary amine, and then 2-bromomethyl-4,6-disubstituted phenol (VIII) is added to react at a temperature of 0 to 150° C. (e.g., 10° C., 20° C., 30° C., 50° C., 60° C., 80° C., 100° C., 120° C., etc.), and a reaction time of 2 to 96 hours, and then an aminophenol ligand compound (IX) is collected from the reaction product;

[0038] Alternatively, as shown in Path B, diethyl oxalate is subjected to a reductive amination reaction with a primary amine represented by formula (X) to generate a corresponding di-secondary amine, and 2-bromomethyl-4,6-disubstituted phenol (VIII) is added for reaction at a temperature of 0 to 150° C. (e.g., 10° C., 20° C., 30° C., 50° C., 60° C., 80° C., 100° C., 120° C., etc.), and a reaction time of 2 to 96 hours, and then an aminophenol ligand compound (IX) is collected from the reaction product;

[0039] (2) preparing aminophenoloxy transition metal complex (I) using Path C or Path D;

[0040]

[0041] As shown in Path C, the aminophenol ligand compound represented by formula (IX) is reacted with a main group metal organic reagent in an organic medium at a reaction temperature of -70 to 120°C (e.g., -50°C, -20°C, 0°C, 20°C, 40°C, 80°C, 100°C, 120°C, etc.) for a reaction time of 2 to 96 hours; then a transition metal raw material compound MX is added n (THF) mContinue the reaction at a temperature of -70 to 120° C. (e.g., -50° C., -20° C., 0° C., 20° C., 40° C., 80° C., 100° C., 120° C., etc.) for 2 to 96 hours, and collect the target aminophenoloxy transition metal complex (I) from the reaction product;

[0042]

[0043] Alternatively, as shown in Path D, the aminophenol ligand compound represented by formula (IX) is reacted with the transition metal raw material compound MX n (THF) m reacting at a temperature of -70 to 180° C. (e.g., -50° C., -20° C., 0° C., 20° C., 40° C., 80° C., 100° C., 120° C., 150° C., etc.), for a reaction time of 2 to 96 hours, and collecting the target aminophenoloxy transition metal complex (I) from the reaction product;

[0044] (3) Optionally, perform Path E;

[0045]

[0046] As shown in Path E, optionally, the aminophenoloxy transition metal complex represented by formula (I) is further reacted with twice the amount of a main group metal organic reagent in an organic medium, the reaction temperature is -70 to 120°C (e.g., -50°C, -20°C, 0°C, 20°C, 40°C, 80°C, 100°C, 120°C, etc.), the reaction time is 2 to 96 hours, and the target aminophenoloxy transition metal complex (I*) is collected from the reaction product; the aminophenoloxy transition metal complex represented by formula (I*) is consistent with the aminophenoloxy transition metal complex (I) that meets the requirements of the present invention.

[0047] In the above preparation method:

[0048] Substituent R 1 ~R 2 , A and X are consistent with the corresponding groups satisfying the aminophenoloxy transition metal complex (I) of the present invention; the substituent X' is consistent with the X group satisfying the aminophenoloxy transition metal complex (I) of the present invention (ie, X' is also selected from halogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C7~C 30 (a) a mono- or poly-aryl-substituted alkyl group, X' is different from X;

[0049] The reducing agent is a common reducing agent in organic reactions, preferably sodium borohydride or lithium aluminum hydride;

[0050] The main group metal organic reagent is an alkyl lithium reagent, Grignard reagent, sodium hydride, potassium hydride commonly used in metal organic reactions; preferably sodium hydride, potassium hydride, methyl lithium, n-butyl lithium, benzyl lithium, CH3MgBr, BnMgBr;

[0051] The transition metal raw material compound MX n (THF) m In: X is halogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C7~C 30 A single or multiple aromatic substituted alkyl group; n is 3 or 4; m is 0, 1, 2 or 3; M is selected from Group IVB metals, preferably Ti, Zr, Hf; more preferably, the transition metal raw material compound MX n (THF) m Preferred are TiCl4, [TiCl4(THF)2], ZrCl4, [ZrCl4(THF)2], HfCl4, [HfCl4(THF)2], TiBn4, ZrBn4, HfBn4;

[0052] The molar ratio of the aminophenol ligand compound (IX) to the main group metal organic reagent is 1:2.0 to 3.0, preferably 1:2.2 to 2.5;

[0053] Aminophenol ligand compound (IX) and transition metal raw material compound MX n (THF) m The amount ratio of the substance is 1:0.8 to 1.5, preferably 1:0.9 to 1.2;

[0054] The organic medium is selected from one or more of dichloromethane, tetrahydrofuran, ether, toluene, benzene, petroleum ether and n-hexane.

[0055] The present invention provides application of the aminophenoloxy transition metal complex (I) in olefin polymerization.

[0056] A method for olefin polymerization uses the aminophenoloxy transition metal complex of the formula (I) as a catalyst to catalyze olefin polymerization under the action of a co-catalyst.

[0057] Olefin polymerization (homopolymerization and copolymerization) is a technique known in the art, and those skilled in the art can select appropriate conditions according to actual needs.

[0058] Preferably, the olefin polymerization of the present invention comprises ethylene homopolymerization and ethylene and α-olefin copolymerization; the α-olefin is selected from one or more of propylene, 1-butene, 2-butene, 3-methyl-1-ene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene and styrene.

[0059] Preferably, in the method for olefin polymerization of the present invention, the cocatalyst is selected from one or more of alkylaluminoxane, alkylaluminum, tri(perfluoroaryl)boron compound or borate;

[0060] Preferably, the alkylaluminoxane is preferably methylaluminoxane or modified methylaluminoxane; the molar ratio of the alkylaluminoxane to the aminophenoloxy transition metal complex represented by formula (I) is 10 to 5000:1, preferably 50 to 2000:1, and most preferably 200 to 1000:1;

[0061] Preferably, the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-octylaluminum; the molar ratio of the alkyl aluminum to the aminophenoloxy transition metal complex represented by formula (I) is 1 to 1000:1, preferably 5 to 500:1, and most preferably 10 to 100:1.

[0062] Preferably, the tri(perfluoroaryl)boron compound is tri(pentafluorophenyl)boron; the molar ratio of the tri(perfluoroaryl)boron compound to the aminophenoloxy transition metal complex represented by formula (I) is 0 to 15:1, preferably 0.1 to 5:1, and most preferably 0.5 to 1.5:1.

[0063] Preferably, the borate is preferably [(C6F5)4B] - [CPh3] + The molar ratio of borate to aminophenoloxy transition metal complex represented by formula (I) is 0 to 15:1, preferably 0.8 to 5:1, and most preferably 1.0 to 1.5:1.

[0064] In the method for olefin polymerization of the present invention, the polymerization reaction temperature is 80-200°C, preferably 100-180°C, most preferably 120-160°C; the reaction time is 5-120 min, preferably 10-60 min, most preferably 10-30 min; the pressure is 0.1-5 MPa, preferably 1-3 MPa, most preferably 1-2 MPa, and the pressure described in the present invention is absolute pressure.

[0065] The beneficial effects of the present invention are:

[0066] The invention uses hexadentate aminophenol as a basic skeleton, and can conveniently regulate the electronic effect and steric effect of the ligand by changing the substituent groups on the phenoloxy group and the skeleton nitrogen, thereby achieving the performance of the aminophenoloxy transition metal complex shown in formula (I) in catalyzing olefin polymerization.

[0067] The aminophenoloxy transition metal complex represented by formula (I) of the present invention has the advantages of simple preparation, high catalytic activity, good thermal stability, etc., and is suitable for ethylene polymerization, copolymerization of ethylene and α-olefins such as 1-octene, and preparation of polyolefins and polyolefin plastomers by high-temperature solution polymerization. DETAILED DESCRIPTION

[0068] The present invention is further described below by means of specific implementation modes, but the present invention is not limited thereto.

[0069] The raw materials used in the examples are all commercially available conventional raw materials.

[0070] Experimental instruments: Bruker AVANCE-400 nuclear magnetic resonance instrument from Germany; Carlo-Erba EA-1106 elemental analyzer from Italy.

[0071] Example 1

[0072] Synthesis of ligand L1:

[0073] Prepared with reference to Example 1 of CN116874414A:

[0074] (1) Synthesis of N,N'-di[(pyridin-2-yl)-methyl]ethylenediamine

[0075]

[0076] (2) Synthesis of ligand L1

[0077]

[0078] Example 2

[0079] Synthesis of ligand L2:

[0080]

[0081] To a 50 mL eggplant-shaped bottle containing N, N'-di[(pyridin-2-yl)-methyl]ethylenediamine (about 9.57 mmol, 2.32 g), 20 mL of dichloromethane, triethylamine (57.4 mmol, 5.81 g) and 2-bromomethyl-4,6-dicumylphenol (19.1 mmol, 8.08 g) were added. The mixture was reacted at room temperature for 12 h, quenched with water, extracted with dichloromethane, dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and 30 mL of alcohol was added. After stirring for 12 h, the mother liquor was poured off and the residue was drained to obtain a yellow foamy powder (4.67 g, 52.6%). 1 H NMR (400MHz, CDCl3, 298K): δ10.00 (br s, 2H, OH), 8.33 (d, 3 J=4.8Hz,2H,ArH),7.34(td, 3 J=7.7,1.6Hz,2H,ArH),7.19–7.26(m,7H,ArH),7.01–7.08(m,12H,ArH),7.09–7.01(m,5H,ArH),6.67(s,2H,ArH),6.56(d, 3 J=7.8Hz,2H,ArH),3.48(s,4H,NCH2Ar),3.38(s,4H,NCH2Ar),2.45(s,4H,NCH2CH2N),1.66(s,12H,C(CH3)2Ph),1.63(s,12H,C(CH3)2Ph). 13 C NMR (101MHz, CDCl3): δ157.28,153.40,151.60,151.40,148.75,140.22,136.79,135.33,128.00,127.75,126.82,126.15,1 25.78,125.52,125.06,124.79,123.97,122.26,121.39,58.99,58.87,49.87,42.55,42.09,31.18,29.55.Anal.Calcd.for C 64 H 70 N4O2: C, 82.90; H, 7.61; N, 6.04. Found: C, 82.87; H, 7.38; N, 5.70%.

[0082] Example 3

[0083] Synthesis of ligand L3:

[0084] Reference CN116874414A Example 2:

[0085]

[0086] Example 4

[0087] Synthesis of ligand L4

[0088] (1) Synthesis of 2-bromomethyl-4-methoxy-6-tert-butylphenol

[0089]

[0090] Under argon protection, 100 mL of anhydrous tetrahydrofuran solution of 2-tert-butylhydroquinone (16.6 g, 100 mmol) was slowly added to 100 mL of tetrahydrofuran solution of potassium tert-butoxide (10.2 g, 90 mmol) (cooled with an ice-salt bath). After the resulting mixture was stirred for 30 minutes, iodomethane (12.8 g, 90 mmol) was added dropwise and stirred overnight under ice-salt bath cooling. Saturated ammonium chloride solution was added to quench the reaction. The reaction product was extracted with ethyl acetate, washed with saturated brine, and after drying, the crude product was purified by column chromatography to obtain the product 2-tert-butyl-4-methoxyphenol (15.3 g, 66%).

[0091] Add 2-tert-butyl-4-methoxyphenol (10.0 g, 55.5 mmol), paraformaldehyde (2.5 g, 83.8 mmol), 50 mL glacial acetic acid and 33 wt% hydrogen bromide acetic acid solution (19.5 mL, 111 mmol) to a 250 mL three-necked flask and react in a 70 ° C oil bath. After TLC detection of the reaction of the raw materials, cool to room temperature, pour into 150 mL ice water, extract with dichloromethane, wash the organic phase with ice water until pH = 7, and dry the organic phase with anhydrous magnesium sulfate. Filter, evaporate the filtrate under reduced pressure to remove the solvent to obtain the target product, which is directly used in the next step.

[0092] (2) Synthesis of ligand L4

[0093]

[0094] Except that the raw materials used were N,N'-di[(pyridin-2-yl)-methyl]ethylenediamine (about 10 mmol, 2.42 g), triethylamine (60 mmol, 6.07 g) and 2-bromomethyl-4-methoxy-6-tert-butylphenol (20.0 mmol, 5.44 g), the other operations were the same as those in Example 1 to obtain a light yellow solid (2.62 g, 45.5%).

[0095] Example 5

[0096] Synthesis of ligand L5

[0097] Reference CN116874414A Example 3:

[0098]

[0099] Example 6

[0100] Synthesis of ligand L6

[0101] Reference CN116874414A Example 4:

[0102] (1) Synthesis of N,N'-di[(quinolin-2-yl)-methyl]ethylenediamine

[0103]

[0104] Example 7

[0105] Synthesis of ligand L7

[0106] Reference CN116874414A Example 5:

[0107] (1) Synthesis of N,N'-di[(N-methylbenzimidazol-2-yl)-methyl]ethylenediamine

[0108]

[0109] (2) Synthesis of ligand L7

[0110]

[0111] Example 8

[0112] Synthesis of ligand L8:

[0113] (1)N 1 ,N 2 -Bis(2-(dimethylamino)ethyl)oxalamide

[0114]

[0115] Under argon protection, add N 1 ,N 1 -dimethylethylenediamine (113.4mmol, 10.0g) and ethanol (50mL), add diethyl oxalate (56.7mmol, 8.2g), heat to 90℃ for reaction, the reaction liquid changes from light yellow to orange-red, react for 8 hours. After cooling to room temperature, add ether for recrystallization to obtain pure compound (10.5g, 80.38%).

[0116] (2)N 1 ,N 1 -1,2-Diethyl-N 2 ,N 2 -Dimethylethane-1,2-amine

[0117]

[0118] Under argon protection, N 1 ,N 2 -bis(2-(dimethylamino)ethyl)oxalamide (20.0mmol, 4.6g) and tetrahydrofuran (80mL), lithium aluminum hydride (90.0mmol, 3.4g) were weighed and added into a three-necked flask at 0°C, stirred at room temperature for 1 hour after the addition, and refluxed for 6h. Cooled to room temperature, quenched with 5mL of saturated sodium sulfate solution under cooling, the solid was filtered out, the solution was spin-dried, and vacuum dried to obtain a colorless liquid (3.6g, 89%).

[0119] (3) Synthesis of ligand L8

[0120]

[0121] 2-Bromomethyl-4,6-dichlorophenol (43.3 mmol, 11.1 g) and dichloromethane (40 mL) were added to a 250 mL eggplant-shaped bottle, and N 1 ,N 1 -1,2-Diethyl-N 2 ,N 2 -Dimethylethane-1,2-amine (17.3mmol, 3.5g) in dichloromethane (70mL), a white solid gradually precipitated from the light yellow solution, and triethylamine (69.2mmol, 6.9g) was added after the addition was complete, the solid gradually dissolved, the solution turned dark yellow and a white solid was produced, and the reaction was carried out at 25°C for 24h. After the reaction was completed, a saturated sodium chloride aqueous solution was added for washing, and the organic phase was concentrated and recrystallized twice from dichloromethane / methanol to obtain a white solid (6.0g, 62.8%).

[0122] Example 9

[0123] Synthesis of ligand L9:

[0124]

[0125] In addition to the raw materials, 2-bromomethyl-4,6-di(2-phenyl-2-propyl)phenol (14.5mmol, 6.2g), N 1 ,N 1 -1,2-Diethyl-N 2 ,N 2 -dimethylethane-1,2-amine (6.9 mmol, 1.4 g) and triethylamine (20.7 mmol, 2.1 g), other operations were the same as in Example 8 to obtain a white solid (4.2 g, 68.6%).

[0126] Example 10

[0127] Synthesis of ligand L10

[0128]

[0129] In addition to the raw materials using 2-bromomethyl-4-chloro-6-tert-butylphenol (14.8mmol, 4.1g), N 1 ,N 1 -1,2-Diethyl-N 2 ,N 2 -dimethylethane-1,2-amine (7.4mmol, 1.5g) and triethylamine (22.2mmol, 2.2g), other operations were the same as in Example 8. After the reaction was completed, a saturated sodium chloride aqueous solution was added for washing, the organic phase was concentrated, and concentrated hydrochloric acid was added to precipitate a large amount of white solids, the solid was washed with petroleum ether, the solid was adjusted to pH=5-6 by adding 15% sodium hydroxide, EA was extracted, the organic phase was washed with water three times, the organic phases were combined and dried, and concentrated to precipitate a large amount of white solids, the mother liquor was purple, the solid was washed with EA, dissolved in water, and the pH was readjusted to 12, extracted with DCM, the organic phase was dried, and concentrated to dryness to obtain a yellow solid (2.1g, 47.7%).

[0130] Embodiment 11

[0131] Synthesis of ligand L11

[0132]

[0133] Except for the raw materials N 1 ,N 1 '-(Ethane-1,2-diyl)bis(N 2 ,N 2 -dimethylethane-1,2-amine) (about 10 mmol, 2.02 g), triethylamine (60 mmol, 6.07 g) and 2-bromomethyl-4-tert-butyl-6-phenylphenol (20 mmol, 6.38 g), other operations were the same as those in Example 10 to obtain a yellow foamy powder.

[0134] Example 12

[0135] Synthesis of Complex Zr1

[0136]

[0137] Under argon protection, ligand L1 (0.500mmol, 340mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (261mg, 62.3%).

[0138] 1 H NMR (400MHz,CDCl3):δ9.43(d, 3 J=5.7Hz,2H,ArH),7.61(td, 3 J=7.6Hz,1.7Hz,2H,ArH),7.45(d, 3 J=5.6Hz,2H,ArH),7.34(t,2H, 3 J=7.6Hz,2H,ArH),7.03(m,4H,ArH),4.34(d, 2 J=15.5Hz,2H,ArCH2N),4.00(d, 2 J = 12.9 Hz, 2H, ArCH2N), 3.90 (d, 2 J = 15.5 Hz, 2H, ArCH2N), 3.45 (d, 2 J = 12.8 Hz, 2H, ArCH2N), 3.02 (d, 2 J=10.5Hz,2H,NCH2CH2N),2.69(d, 2 J=10.5Hz,2H,NCH2CH2N),2.02(s,18H,C(CH3)3),1.50(s,18H,C(CH3)3).Anal.Calcd.for C 44 H 60 Cl2N4O2Zr: C, 62.98; H, 7.21; N, 6.68. Found: C, 63.20; H, 7.70; N, 6.24%.

[0139] Example 13

[0140] Synthesis of Complex Zr2

[0141]

[0142] Under argon protection, ligand L2 (0.500mmol, 464mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were removed by filtration. The filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (273mg, 50.3%).

[0143] 1 H NMR (400MHz,CDCl3):δ9.43(d, 3 J=5.6Hz,2H,ArH),7.61(d, 4 J=2.7Hz,2H,ArH),7.58–7.51(m,4H,ArH),7.48(dd, 3 J=7.7,1.6Hz,4H,ArH),7.06(t, 3 J=7.2Hz,6H,ArH),6.98(d, 3 J=7.6Hz,2H,ArH),6.79(td, 3 J=7.8,2.0Hz,2H,ArH),6.39(d, 3 J=7.7Hz,2H,ArH),6.28(dd, 3 J=7.6,4.9Hz,2H,ArH),4.52(d, 2 J=10.6Hz,2H,NCH2Ar),4.05(d, 2 J=13.5Hz,2H,NCH2Ar),3.54(d, 2 J=8.3Hz,2H,NCH2CH2N),3.38(s,6H,(CPh(CH3)2),2.85(d, 2 J=13.5Hz,2H,NCH2Ar),1.86(s,12H,CPh(CH3)2),1.79(s,12H,CPh(CH3)2),1.25(d, 2 J=8.3Hz,2H,NCH2CH2N).Anal.Calcd.for C 64 H 68 Cl2N4O2Zr: C, 70.69; H, 6.30; N, 5.15. Found: C, 70.26; H, 6.80; N, 5.48%.

[0144] Embodiment 14

[0145] Synthesis of Complex Zr3

[0146]

[0147] Under argon protection, ligand L3 (0.500mmol, 318mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (251mg, 63.3%).

[0148] 1 H NMR (400MHz,CDCl3):δ9.39(d, 3 J=5.6Hz,2H,ArH),7.64(dd, 3 J=5.2,1.8Hz,2H,ArH),7.58(d, 4 J=2.9Hz,2H,ArH),6.84(td, 3 J=7.4,1.9Hz,2H,ArH),6.45(d, 3 J=7.7Hz,2H,ArH),6.32(dd, 3 J=7.6,4.9Hz,2H,ArH),3.96(d, 2 J=10.9Hz,2H,NCH2Ar),3.85(d, 2 J=13.9Hz,2H,NCH2Ar),2.70(d, 2 J=9.0Hz,2H,NCH2CH2N),2.24(d, 2 J=13.9Hz,2H,NCH2Ar),1.96(d, 2 J=10.9Hz,2H,NCH2Ar),1.36(d, 2 J=9.0Hz,2H,NCH2CH2N),1.79(s,18H,C(CH3)3).Anal.Calcd.for C 36 H 42 Cl4N4O2Zr: C, 54.34; H, 5.32; N, 7.04. Found: C, 54.66; H, 5.02; N, 6.89%.

[0149] Embodiment 15

[0150] Synthesis of Complex Zr4

[0151]

[0152] Under argon protection, ligand L4 (0.500mmol, 313mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (211mg, 53.89%).

[0153] 1 H NMR (400MHz,CDCl3):δ9.41(d, 3 J=5.6Hz,2H,ArH),7.69(dd, 3 J=5.2,1.8Hz,2H,ArH),7.63(d, 4 J=2.9Hz,2H,ArH),6.87(td, 3 J=7.4,1.9Hz,2H,ArH),6.51(d, 3 J=7.7Hz,2H,ArH),6.37(dd, 3 J=7.6,4.9Hz,2H,ArH),4.13(d, 2 J=10.9Hz,2H,NCH2Ar),3.95(d, 2 J=13.9Hz,2H,NCH2Ar),2.72(d, 2 J=9.0Hz,2H,NCH2CH2N),2.54(s,6H,OCH3),2.34(d, 2 J=13.9Hz,2H,NCH2Ar),1.96(d, 2 J=10.9Hz,2H,NCH2Ar), 1.44(d, 2 J=9.0Hz,2H,NCH2CH2N),1.82(s,18H,C(CH3)3).Anal.Calcd.for C 38 H 48 Cl2N4O4Zr: C, 58.00; H, 6.15; N, 7.12. Found: C, 58.06; H, 6.09; N, 6.89%.

[0154] Example 16

[0155] Synthesis of Complex Zr5

[0156]

[0157] Under argon protection, ligand L5 (0.500mmol, 359mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (295mg, 67.4%).

[0158] 1 H NMR (400MHz,CDCl3):δ9.56(d, 3 J=5.6Hz,2H,ArH),7.97(d, 3 J=4.5Hz,2H,ArH),7.60(d, 3 J=7.5Hz,4H,ArH),7.22(t, 3 J=7.5Hz,4H,ArH),7.10–7.05(m,4H,ArH),6.90(s,2H,ArH),6.31(d, 3 J=7.8Hz,2H,ArH),6.24–6.16(m,2H,ArH),4.01(d, 2 J=11.6Hz,2H,NCH2Ar),3.20(s,4H,NCH2Ar),2.52(d, 2 J=11.6Hz,4H,NCH2Ar,NCH2CH2N),2.37(s,2H,NCH2CH2N),1.46(s,18H,C(CH3)3).Anal.Calcd.for C 48 H 52 Cl2N4O2Zr: C, 65.58; H, 5.96; N, 6.37. Found: C, 65.45; H, 5.45; N, 6.65%.

[0159] Embodiment 17

[0160] Synthesis of Complex Zr6

[0161]

[0162] Under argon protection, ligand L6 (0.500mmol, 390mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were removed by filtration. The filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (204mg, 43.6%).

[0163] 1 H NMR (400MHz,CDCl3):δ7.99(d, 3 J=8.4Hz,2H,ArH),7.75(d, 4 J=2.8Hz,2H,ArH),7.34(d, 3 J=8.5Hz,2H,ArH),7.19(dd, 3 J=8.4,1.4Hz,2H,ArH),7.16(d, 4 J=2.7Hz,2H,ArH),7.02(ddd, 3 J=8.5,6.9,1.5Hz,2H,ArH),6.96–6.87(ddd, 3 J=8.0,6.9,1.2Hz,2H,ArH),6.52(d, 3 J=8.4Hz,2H,ArH),4.77(d, 2 J=10.7Hz,2H,NCH2Ar),4.32(d, 2 J=15.2Hz,2H,NCH2Ar),3.14(d, 2 J=8.9Hz,2H,NCH2CH2N),2.69(d, 2 J=15.2Hz,2H,NCH2Ar),2.34(d, 2 J=10.7Hz,2H,NCH2Ar)2.15(s,18H,C(CH3)3),1.59(s,18H,C(CH3)3).Anal.Calcd.forC 52 H 64 Cl2N4O2Zr: C, 66.50; H, 6.87; N, 5.97. Found: C, 66.98; H, 6.04; N, 5.67%.

[0164] Embodiment 18

[0165] Synthesis of Complex Zr7

[0166]

[0167] Under argon protection, ligand L7 (0.500mmol, 394mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were removed by filtration. The filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (236mg, 50.2%).

[0168] 1 H NMR (400MHz,CDCl3):δ7.95(d, 4 J=2.8Hz,2H,ArH),7.36(d, 3 J=8.5Hz,2H,ArH),7.30(dd, 3 J=8.4,1.4Hz,2H,ArH),7.26(d, 4 J=2.7Hz,2H,ArH),7.13(ddd, 3 J=8.5,6.9,1.5Hz,2H,ArH),6.35(d, 3 J=8.4Hz,2H,ArH),4.54(d, 2 J=10.7Hz,2H,NCH2Ar),4.40(d, 2 J=15.2Hz,2H,NCH2Ar),3.21(d, 2 J=8.9Hz,2H,NCH2CH2N),2.69(d, 2 J=15.2Hz,2H,NCH2Ar),2.53(s,6H,NCH3),2.43(d, 2 J=10.7Hz,2H,NCH2Ar),2.13(s,18H,C(CH3)3),1.53(s,18H,C(CH3)3).Anal.Calcd.for C 50 H 66 Cl2N6O2Zr: C, 63.53; H, 7.04; N, 8.89. Found: C, 64.02; H, 7.54; N, 8.79%.

[0169] Embodiment 19

[0170] Synthesis of Complex Zr8

[0171]

[0172] Under argon protection, ligand L8 (1.000mmol, 550mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (3.0mmol, 72mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (1.000mmol, 377mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (385mg, 54.1%).

[0173] 1 H NMR (400MHz, CDCl3): δ7.28 (d, J=2.8Hz, 2H, ArH), 6.84 (d, J=2.4Hz, 2H, ArH), 4.48 (d, J=13.6Hz, 2H, ArCH2), 3.52 (d, J=13.6Hz, 2H, ArCH2), 3.27–3.16 ( m,2H,NCH2CH2N),2.94–2.85(m,2H,NCH2CH2N),2.71(d,J=10.3Hz,2H,NCH2CH2N),2.62–2.38(m,6H,NCH2CH2N),2.15(s,12H,N(CH3)2).Anal.Calcd.for C 24 H 32 Cl6N4O2Zr: C, 40.46; H, 4.53; N, 7.86. Found: C, 40.12; H, 4.23; N, 7.55%.

[0174] Embodiment 20

[0175] Synthesis of Complex Zr9

[0176]

[0177] Under argon protection, ligand L9 (0.500mmol, 443mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were removed by filtration. The filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (225mg, 43.2%).

[0178] 1 H NMR (400MHz, CDCl3): δ7.25–7.19(m,11H,ArH),7.18–7.12(m,7H,ArH),7.08–7.00(m,4H,ArH),6.67(d,J=2.4Hz, 2H, ArH), 3.99 (d, J=13.1Hz, 2H, ArCH2), 3.42 (d, J=13.2Hz, 2H,), 2.76 (dd, J=13.9, 7.2Hz, 2H, ArCH2), 2.67 (d, J= 10.0Hz,2H,NCH2CH2N),2.60(dd,J=13.0,7.6Hz,2H,NCH2CH2N),2.43–2.32(m,4H,NCH2CH2N),2.05(dd,J=12.1,6 .5Hz,2H,NCH2CH2N),1.94(s,12H,N(CH3)2),1.76(s,12H,CPh(CH3)2),1.60(s,12H,CPh(CH3)2).Anal.Calcd.for C 60 H 76 Cl2N4O2Zr: C, 68.80; H, 7.31; N, 5.35. Found: C, 68.48; H, 7.17; N, 4.96%.

[0179] Embodiment 20

[0180] Synthesis of Complex Zr10

[0181]

[0182] Under argon protection, ligand L10 (0.500mmol, 297mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (362mg, 48.2%).

[0183] 1 H NMR (400MHz, CDCl3): δ7.15 (d, J=2.6Hz, 2H, ArH), 6.85 (d, J=2.5Hz, 2H, ArH), 4.18 (d,J=13.1Hz,2H,ArCH2),3.58(d,J=13.3Hz,2H,ArCH2),3.18–3.05(m,4H,NCH2CH 2N),2.80(d,J=10.2Hz,2H,NCH2CH2N),2.54–2.41(m,4H,NCH2CH2N),2.34–2.30(m ,2H,NCH2CH2N),2.03(s,12H,N(CH3)2),1.46(s,18H,C(CH3)3).Anal.Calcd.forC 32 H 50 Cl4N4O2Zr: C, 50.85; H, 6.67; N, 7.41. Found: C, 50.52; H, 6.42; N, 7.15%.

[0184] Embodiment 21

[0185] Synthesis of Complex Zr11

[0186]

[0187] Under argon protection, ligand L11 (0.500mmol, 339mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.5mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then zirconium tetrachloride tetrahydrofuran complex (0.500mmol, 188mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were removed by filtration. The filtrate was vacuum-decompressed to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (153mg, 42.36%).

[0188] 1 H NMR (400MHz, CDCl3): δ7.62-7.56(d,J=7.2Hz,4H,ArH),7.38(s,2H,ArH),7.13–6.99(m,6H,ArH),3.62(s,2H,NCH2Ar),2.8 5–2.45(m,6H,NCH2CH2N),2.42-2.12(m,4H,NCH2Ar,NCH2CH2N),1.76(s,12H,N(CH3)2),1.50(s,18H,C(CH3)3).Calcd.forC 44 H 60 Cl2N4O2Zr: C, 62.98; H, 7.21; N, 6.68. Found: C, 62.43; H, 7.67; N, 6.18%.

[0189] Embodiment 22

[0190] Synthesis of Complex Ti1

[0191]

[0192] Under argon protection, ligand L1 (0.500mmol, 340mg) was added to a 50mL Schlenk bottle, dissolved with 15mL anhydrous tetrahydrofuran, then NaH (1.500mmol, 36mg) was slowly added, reacted at room temperature for 12h, and then titanium tetrachloride tetrahydrofuran complex (0.500mmol, 167mg) was added, and reacted at room temperature for 12h. The solvent was removed in vacuo, and dry dichloromethane was added to dissolve, and the excess sodium hydride and sodium chloride were filtered out, and the filtrate was vacuum-dry to obtain a yellow foamy solid. Dichloromethane and n-hexane were added for recrystallization to obtain a light yellow solid (248mg, 62.3%).

[0193] 1 H NMR (400MHz,CDCl3):δ9.76(d, 3 J=5.7Hz,2H,ArH),7.56(td, 3 J=7.6Hz,1.7Hz,2H,ArH),7.34(d, 3 J=5.6Hz,2H,ArH),7.23(t,2H, 3 J=7.6Hz,2H,ArH),7.05(m,4H,ArH),4.45(d, 2 J=15.5Hz,2H,ArCH2N),4.13(d, 2 J = 12.9 Hz, 2H, ArCH2N), 3.89 (d, 2J = 15.5 Hz, 2H, ArCH2N), 3.34 (d, 2 J = 12.8 Hz, 2H, ArCH2N), 3.02 (d, 2 J=10.5Hz,2H,NCH2CH2N),2.69(d, 2 J=10.5Hz,2H,NCH2CH2N),2.13(s,18H,C(CH3)3),1.45(s,18H,C(CH3)3).Anal.Calcd.for C 44 H 60 Cl2N4O2Ti: C, 66.41; H, 7.60; N, 7.04. Found: C, 66.90; H, 7.95; N, 6.65%.

[0194] Embodiment 23

[0195] Synthesis of Complex Ti8

[0196]

[0197] Under argon protection, add ligand L8 (0.500mmol, 276mg) to a 50mL Schlenk bottle, dissolve it with 15mL anhydrous tetrahydrofuran, then slowly add NaH (1.500mmol, 36mg), react at room temperature for 12h, then add titanium tetrachloride tetrahydrofuran complex (0.500mmol, 167mg), and react at room temperature for 12h. Remove the solvent in vacuo, add dry dichloromethane to dissolve, filter to remove excess sodium hydride and sodium chloride, and vacuum dry the filtrate to obtain a yellow foamy solid. Add dichloromethane and n-hexane for recrystallization to obtain a light yellow solid (123mg, 37.3%).

[0198] 1 H NMR (400MHz, CDCl3): δ7.26 (d, J=2.8Hz, 2H, ArH), 6.88 (d, J=2.4Hz, 2H, ArH), 4.41 (d, J=13.6Hz, 2H, ArCH2), 3.52 (d, J=13.6Hz, 2H, ArCH2), 3.25–3.12 (m ,2H,NCH2CH2N),2.90–2.80(m,2H,NCH2CH2N),2.71(d,J=10.3Hz,2H,NCH2CH2N),2.62–2.38(m,6H,NCH2CH2N),2.17(s,12H,2N(CH3)2).Anal.Calcd.for C 24 H 32Cl6N4O2Ti: C, 43.08; H, 4.82; N, 8.37. Found: C, 42.73; H, 4.44; N, 8.12%.

[0199] Embodiment 24

[0200] Synthesis of complex Hf1

[0201]

[0202] Under argon protection, add ligand L1 (0.500mmol, 340mg) to a 50mL Schlenk bottle, dissolve it with 15mL anhydrous tetrahydrofuran, then slowly add NaH (1.500mmol, 36mg), react at room temperature for 12h, then add hafnium tetrachloride (0.500mmol, 160mg), and react at room temperature for 12h. Remove the solvent in vacuo, add dry dichloromethane to dissolve, filter to remove excess sodium hydride and sodium chloride, and vacuum dry the filtrate to obtain a yellow foamy solid. Add dichloromethane and n-hexane for recrystallization to obtain a light yellow solid (238mg, 51.3%).

[0203] 1 H NMR (400MHz,CDCl3):δ9.32(d, 3 J=5.7Hz,2H,ArH),7.32(td, 3 J=7.6Hz,1.7Hz,2H,ArH),7.23(d, 3 J=5.6Hz,2H,ArH),7.04(t,2H, 3 J=7.6Hz,2H,ArH),6.89(m,4H,ArH),4.35(d, 2 J = 15.5 Hz, 2H, ArCH2N), 4.07 (d, 2 J=12.9Hz,2H,ArCH2N),3.79(d, 2 J=15.5Hz,2H,ArCH2N),3.24(d, 2 J=12.8Hz,2H,ArCH2N),3.00(d, 2 J=10.5Hz,2H,NCH2CH2N),2.65(d, 2 J=10.5Hz,2H,NCH2CH2N),2.10(s,18H,C(CH3)3),1.41(s,18H,C(CH3)3).Anal.Calcd.for C 44 H 60Cl2N4O2Hf: C, 57.05; H, 6.53; N, 6.05. Found: C, 56.65; H, 6.45; N, 6.04%.

[0204] Embodiment 26

[0205] Synthesis of Complex Hf8

[0206]

[0207] Under argon protection, add ligand L8 (0.500mmol, 276mg) to a 50mL Schlenk bottle, dissolve it with 15mL anhydrous tetrahydrofuran, then slowly add NaH (1.500mmol, 36mg), react at room temperature for 12h, then add hafnium tetrachloride (0.500mmol, 160mg), and react at room temperature for 12h. Remove the solvent in vacuo, add dry dichloromethane to dissolve, filter to remove excess sodium hydride and sodium chloride, and vacuum dry the filtrate to obtain a yellow foamy solid. Add dichloromethane and n-hexane for recrystallization to obtain a light yellow solid (123mg, 37.3%).

[0208] 1 H NMR (400MHz, CDCl3): δ7.26 (d, J=2.8Hz, 2H, ArH), 6.88 (d, J=2.4Hz, 2H, ArH), 4.41 (d, J=13.6Hz, 2H, ArCH2), 3.52 (d, J=13.6Hz, 2H, ArCH2), 3.25–3.12 (m ,2H,NCH2CH2N),2.90–2.80(m,2H,NCH2CH2N),2.71(d,J=10.3Hz,2H,NCH2CH2N),2.62–2.38(m,6H,NCH2CH2N),2.17(s,12H,2N(CH3)2).Anal.Calcd.for C 24 H 32 Cl6N4O2Hf: C, 43.08; H, 4.82; N, 8.37. Found: C, 42.73; H, 4.44; N, 8.12%.

[0209] Embodiment 27

[0210] Synthesis of Complex Hf9

[0211]

[0212] Under argon protection, add ligand L9 (0.500mmol, 443mg) to a 50mL Schlenk bottle, dissolve it with 15mL anhydrous tetrahydrofuran, then slowly add NaH (1.500mmol, 36mg), react at room temperature for 12h, then add hafnium tetrachloride (0.500mmol, 160mg), and react at room temperature for 12h. Remove the solvent in vacuo, add dry dichloromethane to dissolve, filter to remove excess sodium hydride and sodium chloride, and vacuum dry the filtrate to obtain a yellow foamy solid. Add dichloromethane and n-hexane for recrystallization to obtain a light yellow solid (237mg, 41.9%).

[0213] 1 H NMR (400MHz, CDCl3) δ7.25–7.19(m,11H,ArH),7.17-1.12(m,7H,ArH),7.05(dd,J=9.4,4.8Hz,4H,ArH),6. 67(d,J=2.3Hz,2H,ArH),3.97(d,J=13.1Hz,2H,ArCH2),3.44(d,J=13.3Hz,2H,ArCH2),2.77–2.66(m,4H,NC H2CH2N),2.57–2.46(m,4H,NCH2CH2N),2.34(dd,J=11.7,5.9Hz,2H,NCH2CH2N),2.02(dd,J=13.2,5.1Hz,2H ,NCH2CH2N),1.93(s,12H,N(CH3)2),1.76(s,12H,CPh(CH3)2),1.60(s,12H,CPh(CH3)2).Anal.Calcd.forC 60 H 76 Cl2N4O2Hf·0.2CH2Cl2: C, 62.78; H, 6.69; N, 4.86. Found: C, 62.87; H, 5.98; N, 4.86%.

[0214] Embodiment 28

[0215] Synthesis of Complex Zr12

[0216]

[0217] Under argon protection, the complex Zr10 (0.500mmol, 378mg) was added to a 50mL Schlenk bottle, dissolved with 15mL tetrahydrofuran, and then slowly added with CH3Li ether solution (1.0mmol, 1.0mL, 1.0mol / L) at -70°C, and then heated to 0°C for 12h. Rapidly filter at room temperature, remove the solvent in vacuo, add n-hexane to dissolve, and place at low temperature for crystallization to obtain a yellow solid (114mg, 31.9%).

[0218] 1 H NMR (400MHz, CDCl3): δ7.13 (d, J=2.5Hz, 2H, ArH), 6.80 (d, J=2.5Hz, 2H, ArH), 4.15 (d, J=13.1Hz,2H,ArCH2),3.55(d,J=13.3Hz,2H,ArCH2),3.10–3.00(m,4H,NCH2CH2N),2.8 5(d,J=10.2Hz,2H,NCH2CH2N),2.50–2.38(m,4H,NCH2CH2N),2.31–2.28(m,2H,NCH2CH 2N),2.05(s,12H,N(CH3)2),1.49(s,18H,C(CH3)3),0.55(s,6H,CH3).Anal.Calcd.for C 34 H 56 Cl2N4O2Zr: C, 57.12; H, 7.89; N, 7.84. Found: C, 56.73; H, 7.51; N, 7.26%.

[0219] Embodiment 29

[0220] Synthesis of Complex Zr13

[0221]

[0222] Under argon protection, ligand L10 (0.500mmol, 297mg) was added to a 50mL Schlenk bottle, dissolved in 15mL toluene, and then tetrabenzyl zirconium (0.500mmol, 228mg) was slowly added, and reacted at room temperature for 12h. Filtered, the solvent was removed in vacuo, n-hexane was added to dissolve, and placed at low temperature for crystallization to obtain a yellow solid (205mg, 47.3%).

[0223] 1H NMR (400MHz, CDCl3): δ7.13-6.90(m,12H,ArH&PhH),6.85(d,J=2.5Hz,2H,ArH),5.23(s ,4H,PhCH2),4.21(d,J=13.1Hz,2H,ArCH2),3.54(d,J=13.3Hz,2H,ArCH2),3.12–2.95(m ,4H,NCH2CH2N),2.85(d,J=10.2Hz,2H,NCH2CH2N),2.54–2.41(m,4H,NCH2CH2N),2.34– 2.30(m,2H,NCH2CH2N),2.07(s,12H,N(CH3)2),1.45(s,18H,C(CH3)3).Anal.Calcd.for C 46 H 64 Cl2N4O2Zr: C, 63.71; H, 7.44; N, 6.46. Found: C, 63.34; H, 7.31; N, 6.26%.

[0224] Examples 30-52

[0225] The aminophenoloxy transition metal complex of the present invention is used to catalyze ethylene polymerization.

[0226] Take the complex Zr1 as an example: the ampoule bottle containing the transition metal complex Zr1 (3μmo1), the temperature sensor and the mechanically stirred 500mL high-pressure reactor were dried continuously at 120℃ for 1 hour, vacuumed and gradually cooled to 25℃. 200mL of xylene and 0.6mL MMAO (1.0mo1 / L) were added in sequence, and then the temperature was raised to 120℃, 3.0MPa of ethylene monomer was introduced, the ampoule bottle was broken, and the polymerization reaction began. During the entire polymerization process, the stirring rate, polymerization temperature and ethylene pressure remained unchanged. After 30 minutes, the gas in the kettle was emptied and the reaction liquid was neutralized with 5wt% hydrochloric acid-acidified ethanol solution to obtain a polymer precipitate and washed several times, and then vacuum dried to constant weight. The molecular weight and distribution were determined by high-temperature GPC, the test temperature was 135℃, and the mobile phase was 1,3,5-trichlorobenzene. The specific data results are shown in Table 1.

[0227] Table 1. Ethylene polymerization results a

[0228]

[0229] Polymerization conditions: a The dosage of the main catalyst was 3 μmol, the co-catalyst was modified methylaluminoxane MMAO, and the polymerization time was 30 min; b Catalytic activity, unit: g / (mol-M·h -1 );c The co-catalyst is Al i Bu3 and [(C6F5)4B] - [CPh3] + , [Al] / [M] / [B]=10:1:1.2.

[0230] Examples 53-60

[0231] Ethylene / 1-octene copolymerization catalyzed by the aminophenoloxy transition metal complex of the present invention

[0232] Take the complex Zr1 as an example: the ampoule bottle containing the complex Zr1 (3μmo1), the temperature sensor and the 500mL high-pressure reactor with mechanical stirring were dried continuously at 120℃ for 1 hour, vacuumed and gradually cooled to 25℃. 200ml xylene, 0.6mL MMAO (1.0mo1 / L) and 10mL 1-octene were added in sequence, and then the temperature was raised to 120℃, 3.0MPa ethylene monomer was introduced, the ampoule bottle was broken, and the polymerization reaction began. During the entire polymerization process, the stirring rate, polymerization temperature and ethylene pressure remained unchanged. After 30min, the gas in the reactor was evacuated, and the reaction solution was neutralized with 5wt% hydrochloric acid acidified ethanol solution to obtain a polymer precipitate and washed several times, and then vacuum dried to constant weight. The molecular weight and distribution were determined by high-temperature GPC, the test temperature was 135℃, and the mobile phase was 1,3,5-trichlorobenzene. The insertion rate of 1-octene in the copolymer was analyzed by online infrared. The specific data results are shown in Table 2.

[0233] Table 2. Results of copolymerization of ethylene and 1-octene a

[0234]

[0235] Polymerization conditions: a The dosage of the main catalyst was 3 μmol, the co-catalyst was modified methylaluminoxane MMAO, Al / M=200, and the polymerization time was 30 min; b Catalytic activity, unit: g / (mol-M·h -1 ); c The co-catalyst is Al i Bu3 and [(C6F5)4B] - [CPh3] + , [Al] / [M] / [B]=10:1:1.2.

[0236] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An aminophenoloxy transition metal complex, characterized in that: It has the following general formula (I): In formula (I): R 1 ~R 2 Each independently represents hydrogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C1~C 20 Straight chain, branched chain or cyclic alkoxy, C7~C 30 Mono- or poly-aryl-substituted alkyl, C6~C 18 aryl, or halogen; A is a group having a structure represented by formula (II), (III), (IV), (V) or (VI): A is coordinated to the metal center M via its nitrogen atom, or is not coordinated to the metal center M, or only one of A in formula (I) is coordinated to the metal center M via its nitrogen atom; X is halogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C7~C 30 A mono- or poly-aryl-substituted alkyl group; M is selected from Group IVB metals, preferably Ti, Zr, Hf.

2. The aminophenoloxy transition metal complex according to claim 1, characterized in that R 1 ~R 2 are independently hydrogen, C1~C 12 Straight chain, branched chain or cyclic alkyl group, C1~C 12 Straight chain, branched chain or cyclic alkoxy, C7~C 20 Mono- or poly-aryl-substituted alkyl, C6~C 18 aryl, or halogen; A is a group having a structure represented by formula (II), (III), (V) or (VI): X is halogen, C1~C 12 Straight chain, branched chain or cyclic alkyl group, C7~C 20 A mono- or poly-aryl-substituted alkyl group.

3. The aminophenoloxy transition metal complex according to claim 1, characterized in that R 1 ~R 2 are independently hydrogen, methyl, methoxy, isopropyl, tert-butyl, cumyl, 1,1-diphenylethyl, trityl, phenyl, naphthyl, anthracenyl, 3,5-di-tert-butyl-1-phenyl, halogen; X is chlorine, methyl, benzyl.

4. A method for preparing the aminophenoloxy transition metal complex according to any one of claims 1 to 3, comprising the following steps: (1) Preparation of aminophenol ligand compound (IX); using Path A or Path B: Path A: reacting ethylenediamine with an aldehyde-substituted nitrogen-containing heterocyclic compound represented by formula (VII), reducing the compound with a reducing agent to generate a corresponding di-secondary amine, and then adding 2-bromomethyl-4,6-disubstituted phenol (VIII) to react to obtain an aminophenol ligand compound (IX); Path B: Reductive amination of diethyl oxalate with the primary amine represented by formula (X) to generate the corresponding di-secondary amine, and adding 2-bromomethyl-4,6-disubstituted phenol (VIII) to react to obtain an aminophenol ligand compound (IX); (2) Preparation of aminophenoloxy transition metal complex (I) using Path C or Path D: Path C: react the aminophenol ligand compound represented by formula (IX) with the main group metal organic reagent in an organic medium; then add the transition metal raw material compound MX n (THF) m Continue the reaction to obtain an aminophenoloxy transition metal complex (I); Path D: The aminophenol ligand compound represented by formula (IX) is reacted with the transition metal raw material compound MX n (THF) m Reaction to obtain an aminophenoloxy transition metal complex (I); (3) optionally perform Path E; Path E: Optionally, the aminophenoloxy transition metal complex represented by formula (I) is reacted with twice the amount of a main group metal organic reagent in an organic medium to obtain an aminophenoloxy transition metal complex (I*); the selection range of the X' group in formula (I*) is consistent with the X group in the aminophenoloxy transition metal complex (I), and X' is different from X.

5. The preparation method according to claim 4, characterized in that: In Path A and Path B, the reaction temperature is 0 to 150° C. and the reaction time is 2 to 96 hours. In Path C, the reaction temperature of the aminophenol ligand compound represented by formula (IX) and the main group metal organic reagent is -70 to 120° C. and the reaction time is 2 to 96 hours. The transition metal raw material compound MX is added. n (THF) m In Path D, the reaction temperature is -70 to 120°C, and the reaction time is 2 to 96 hours; in Path D, the reaction temperature is -70 to 180°C, and the reaction time is 2 to 96 hours.

6. The preparation method according to claim 4, characterized in that: The reducing agent is selected from sodium borohydride and lithium aluminum hydride; The main group metal organic reagent is selected from alkyl lithium reagents, Grignard reagents, sodium hydride, potassium hydride, preferably sodium hydride, potassium hydride, methyl lithium, n-butyl lithium, benzyl lithium, CH3MgBr, BnMgBr; The transition metal raw material compound MX n (THF) m In the above formula, X is halogen, C1~C 20 Straight chain, branched chain or cyclic alkyl group, C7~C 30 a mono- or poly-aryl-substituted alkyl group; n is 3 or 4; m is 0, 1, 2 or 3; M is selected from Group IVB metals, preferably Ti, Zr, Hf; a transition metal raw material compound MX n (THF) m Preferred are TiCl4, [TiCl4(THF)2], ZrCl4, [ZrCl4(THF)2], HfCl4, [HfCl4(THF)2], TiBn4, ZrBn4, HfBn4; Preferably, the molar ratio of the aminophenol ligand compound (IX) to the main group metal organic reagent is 1:2.0 to 3.0, more preferably 1:2.2 to 2.5; Preferably, the aminophenol ligand compound (IX) and the transition metal raw material compound MX n (THF) m The amount ratio of the substance is 1:0.8 to 1.5, and more preferably 1:0.9 to 1.

2.

7. Use of the aminophenoloxy transition metal complex according to any one of claims 1 to 3, characterized in that: Used for ethylene polymerization and copolymerization of ethylene and α-olefins; Preferably, the α-olefin is selected from propylene, 1-butene, 2-butene, 3-methyl-1-ene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene and styrene.

8. The use according to claim 7, characterized in that: The aminophenoloxy transition metal complex of formula (I) is used as a catalyst to catalyze olefin polymerization under the action of a co-catalyst; the co-catalyst is selected from one or more of alkylaluminoxane, alkylaluminum, tri(perfluoroaryl)boron compound or borate.

9. The use according to claim 8, characterized in that: The alkylaluminoxane is selected from methylaluminoxane and modified methylaluminoxane; the alkylaluminum is selected from trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-octylaluminum; the tri(perfluoroaryl)boron compound is tri(pentafluorophenyl)boron; the borate is [(C6F5)4B] - [CPh3] + .

10. The use according to any one of claims 7 to 9, characterized in that: The polymerization reaction temperature is 80-200°C, preferably 100-180°C, most preferably 120-160°C; the reaction time is 5-120 min, preferably 10-60 min, most preferably 10-30 min; the pressure is 0.1-5 MPa, preferably 1-3 MPa, most preferably 1-2 MPa.

Images