Asymmetric six-membered ring pyridine imine complexes containing bulky substituents, methods of making and using the same

Abstract

The present application relates to a kind of asymmetric six-membered ring pyridine imine complex containing big steric hindrance substituent group, which can be applied to ethylene polymerization as catalyst, has high reactivity, and has very strong control performance to polyethylene molecular weight, and can be used to prepare highly linear polyethylene.The structure of the complex of the present application advantageously stabilizes the stronger positive characteristics of the central metal, stronger Lewis acidity, increases the probability of ethylene insertion, making the system have higher catalytic activity and stability.The preparation process of such complex has the advantages of mild reaction conditions, short cycle, simple operation conditions and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyolefin catalysts, and particularly relates to a novel asymmetric six-membered ring pyridine imine metal complex containing a bulky cycloalkane and a benzhydryl substituent, a preparation method and application thereof. BACKGROUND

[0002] Polyethylene (PE) has excellent mechanical properties, good processing performance, stable chemical properties, low price and other advantages, and has become the largest variety of general synthetic resin in production, and is widely used in daily life, packaging industry, automobile, building, agriculture and military fields. At present, China has become the largest PE importer and the second largest consumer in the world. The performance and industrial application of polyethylene materials depend largely on the size and topological structure of the chain, which can range from semi-crystalline plastics to highly branched elastomers to polyethylene waxes. Among them, linear polyethylene refers to a kind of polyethylene with no long side chain on the main chain of macromolecule and only containing short side chains. There are usually high-density polyethylene, ultra-high molecular weight polyethylene, linear low-density polyethylene, very low-density polyethylene, etc. For example, high-density polyethylene can be used as film, fiber and various pipes. Ultra-high molecular weight polyethylene shows broad application prospects in aerospace, processing pipes and other fields.

[0003] Among them, polyethylene wax (PEW) is a low molecular weight polyethylene with a molecular weight of 500-5000 g / mol, a melting point higher than 90℃, and a relative density of 0.92-0.936 g / cm 3 Because of its small toxicity, non-corrosive, high hardness, high softening point, low melt viscosity, wear resistance, heat resistance, and good lubricity, dispersibility and flowability, it can be used as a lubricant, a low-viscosity dispersant, and widely used in various fields. It can also effectively improve the processing efficiency of pipes, films, cables and other plastics and rubbers, and has broad development and utilization prospects.

[0004] Traditional methods for synthesizing linear polyethylene include the use of Ziegler-Natta catalysts (Chem. Rev., 2000, 100, 1169) and Phillips catalysts (Chem. Rev., 1996, 96, 3327) and the like, such as the production of polyethylene wax using high-pressure polymerization technology in 1939; low-pressure Ziegler method can be used for preparation after 1953; since the early 1990s, the latest generation of metallocene catalysts has been used to initiate synthesis. This also illustrates the design and development of olefin polymerization catalysts, which are the key to further development of polyethylene products. However, due to the limitations of the synthesis process, the obtained polyethylene main chain often has some branches, and the related molecular weight distribution of the polymer cannot meet the very narrow demand. Therefore, researchers have turned their attention to post-transition metal iron and cobalt complex catalysts, which are of great interest due to their excellent performance and highly linear characteristics of the obtained polymers.

[0005] Over the years, the inventors' research group has used a simpler, cheaper and more efficient synthesis strategy to regulate the steric hindrance and electronic effect of the complex skeleton structure, and to reasonably regulate and tailor the molecular weight and microstructure of the polymer. Specifically, the inventors' research group found in the study that post-transition metal iron and cobalt-centered metal complexes can catalyze ethylene polymerization (such as A-E in Formula 1) with high activity, obtaining low molecular weight ethylene oligomerization products or highly linear polyethylene with a relatively narrow distribution. For example, iron complex A (R 1 = R 2 = H) shows extremely high ethylene oligomerization activity (up to 4.91 x 10 6 g·mol -1 (Fe)·h -1 ), and the generated α-olefin has high selectivity (> 94%) and meets the Schulz-Flory distribution (Organometallics 2006, 25, 666-677). The catalyst has been used in a medium-sized reaction for the preparation of α-olefins of 500 tons per year.

[0006] The inventors' research group reported different number of alkyl fused ring pyridine diimine iron and cobalt complexes (such as B-E in Formula 1). Among them, the double-sided seven-membered ring structure (Formula 1, B, Eur. J. Inorg. Chem., 2016, 2016, 1748-1755; Polymer, 2018, 149, 45; Appl. Organomet. Chem., 2020, 34) can catalyze ethylene polymerization to obtain a series of different molecular weight, relatively narrow distribution unsaturated linear polyethylene at 70°C or 80°C with MAO or MMAO as cocatalyst, and the activity can reach 10 7 g·mol -1 (Fe / Co)·h-1 2,8-diaryl-imine-5,6,7-trihydroquinoline iron complexes (Formula 1, C, n = 1, Organometallics, 2012, 31, 5039-5048) with pyridine hexacyclic structure, which has the highest activity of 2.4 x 10 7 g mol -1 (Fe) h -1 , with a molecular weight of 1-10 kg mol -1 ; its cobalt complex (Appl. Catal., A. 2012, 447-448, 67-73) also shows very high catalytic activity for ethylene polymerization, and the highest activity of this system can reach 1.09 x 10 7 g mol -1 (Co) h -1 , and the polymer product is a narrow molecular weight distribution polyethylene wax. 2,9-diimine aryl-5,6,7,8-tetrahydrocycloheptapyridine iron complexes C (n = 2) with seven-membered ring fused ring pyridine derivatives, when R is methyl (Dalton Trans., 2014, 43, 16818-16829), show a catalytic activity of up to 1.56 x 10 7 g mol -1 (Fe) h -1 for ethylene polymerization, and the resulting polyethylene product has a narrow molecular weight distribution (PDI ~ 7). When R is phenyl (J. Polym. Sci. Part A. Polym. Chem. 2017, 55, 830-842), it shows high thermal stability and long service life, and the activity can still reach 6.87 x 10 6 g mol -1 (Fe) h -1 at 80°C, the operating temperature of this industrial application. The resulting product is a low molecular weight polyethylene wax. Its cobalt complex, whether R is methyl or phenyl, shows a highly linear polyethylene wax with an end group double bond.

[0007] The introduction of an ortho cycloalkyl group on the N-aryl group also shows high efficiency in catalyzing ethylene polymerization to produce highly linear polyethylene. Among them, cobalt complex E based on a single-sided flexible seven-membered ring diaryl imine pyridine skeleton, when MAO or MMAO is used as a cocatalyst, the optimal experimental temperature is 50°C, and the optimal activity is 4.09 x 10 6 g mol -1 (Co) h -1 , ultimately producing highly linear (T m > 130°C), with narrow dispersion (M w / M nlinear polyethylenes with terminal double bonds (molecular weight range: 9.78-25.6 kg mol –1 )(Molecules, 2019, 24, 1176). While the single-sided fused six-membered ring pyridine cobalt complex D exhibits a catalytic activity of up to 1.71 x 10 6 g mol -1 (Co) h -1 , generating highly linear, low molecular weight (~1.50 kg mol -1 ) and narrow dispersity (M w / M n range: 1.1-2.4) polyethylene waxes; even at a reaction temperature of 90°C, its catalytic activity can reach 6.75 x 10 6 g mol -1 (Co) h -1 (Polymer, 2021, 213, 123294).

[0008]

[0009] Throughout the development of olefin polymerization catalysts, late transition metal complex catalysts as a new type of ethylene polymerization catalyst system still have some difficulties in basic research and constraints in promoting industrialization. At present, how to obtain a high-activity ethylene polymerization catalyst with good thermal stability to adapt to industrial production has become the core content of scholars' research, and is also the key to promoting industrialization as soon as possible. On the basis of the existing research of cycloalkyl fused ring pyridine iron, cobalt and other complexes in the research group, developing new efficient ethylene polymerization catalysts has the research value of promoting research progress and adapting to the needs of industrialization. SUMMARY

[0010] In order to improve the problems of the prior art, the present application provides an asymmetric six-membered ring pyridine imine transition metal complex containing a bulky substituent and a preparation method and application thereof.

[0011] The technical scheme of the present application is: an asymmetric six-membered ring pyridine imine complex containing a bulky substituent, the structural formula of which is shown in the following formula (I):

[0012]

[0013] In formula (I), M is selected from metals, preferably transition metals, such as Fe, Co, Ni;

[0014] R 5 , R 6 , R 7 are the same or different, each independently selected from H, F, Cl, Br, I, NO2, unsubstituted or optionally substituted by one or more R asubstituted lower alkyl, C 1-6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, 3- to 10-membered heterocyclyl, C 3-10 cycloalkyloxy, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl;

[0015] R, R 1 , R 4 are the same or different, each independently selected from the group consisting of H, F, Cl, Br, I, N02, unsubstituted or optionally substituted lower alkyl, C b substituted lower alkyl, C 1-6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, 3- to 10-membered heterocyclyl, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl; and R, R 1 , R 4 are the same or different, each independently selected from the group consisting of H, F, Cl, Br, I, N02, unsubstituted or optionally substituted lower alkyl, C b substituted lower alkyl, C 3-10 cycloalkyl, 3- to 10-membered heterocyclyl, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl;

[0016] R 2 , R 3 are the same or different, each independently selected from the group consisting of H, F, Cl, Br, I, N02, unsubstituted or optionally substituted lower alkyl, C c substituted lower alkyl, C 1-6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, 3- to 10-membered heterocyclyl, C 3-10 cycloalkyloxy;

[0017] each X is the same or different, each independently selected from the group consisting of F, Cl, Br, I;

[0018] R a , R b , Rc identically or differently, each independently selected from the group consisting of H, F, Cl, Br, I, C 1-6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, C 3-10 cycloalkoxy, C 6-20 aryl, C 6-20 aryloxy or C 6-20 aryl C 1-6 alkyl.

[0019] According to an embodiment of the present application, R 2 , R 3 are identical or different and are each independently selected from the group consisting of H, F, Cl, Br, I or C 1-3 alkyl; more preferably each is H.

[0020] According to an embodiment of the present application, R, R 1 , R 4 at least two of which are unsubstituted or optionally substituted by one or more R b alkyl; more preferably each is H. 3-10 cycloalkyl, C 6-20 aryl, C 6-20 aryl C 1-6 alkyl, or di-C 6-20 aryl C 1-6 alkyl.

[0021] According to an embodiment of the present application, R, R 1 , R 4 are identical or different and are each independently unsubstituted or optionally substituted by one or more R b alkyl; more preferably each is H. 3-10 cycloalkyl, 3-10 membered heterocyclyl, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or di-C 6-20 aryl C 1-6 alkyl.

[0022] According to an embodiment of the present application, R, R 1 , R 4 are identical or different and are each independently unsubstituted or optionally substituted by one or more R b alkyl; more preferably each is H. 3-10 cycloalkyl, C 6-20 aryl, C 6-20 aryl C 1-6 alkyl, or di-C 6-20 aryl C 1-6 alkyl.

[0023] According to embodiments of the present application, R, R 1 , R 4 are the same or different, each independently selected from the group consisting of F, Cl, Br, I, N02, OMe, CF3, C 1-6 alkyl, C 3-10 cycloalkyl, C 6-20 aryl C 1-6 alkyl, di C 6-20 aryl C 1-6 alkyl (such as di C 6-20 aryl C 1-3 alkyl);

[0024] According to embodiments of the present application, R, R 1 , R 4 are the same or different, each independently selected from the group consisting of F, Cl, methyl, cyclopentyl, cyclohexyl, cyclooctyl, benzhydryl.

[0025] According to embodiments of the present application, each X can be independently selected from Cl or Br, in particular from Cl.

[0026] According to embodiments of the present application, R 5 , R 6 , R 7 are the same or different, each independently selected from the group consisting of H, F, Cl, Br, I, or C 1-6 alkyl; in particular from H or Cl.

[0027] R a , R b , R c are the same or different, each independently selected from the group consisting of H, F, Cl, C 1-3 alkyl, C 3-10 cycloalkyl, C 6-12 aryl.

[0028] In particular examples of the present application, the complex of formula (I) is the following complex:

[0029] Complex Co-1 : wherein M is Co, R = cyclopentyl (C5H9), R 1 = methyl, R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H;

[0030] Complex Co-2: wherein M is Co, R = benzhydryl (CHPh2), R 1 = methyl, R 4 = cyclopentyl (C5H9), R 2, R 3 , R 5 , R 6 , R 7 = H;

[0031] Complex Co-3: where M is Co, R = cyclopentyl (C5H9), R 1 = diphenylmethyl (CHPh2), R 4 = methyl, R 2 , R 3 , R 5 , R 6 , R 7 = H;

[0032] Complex Co-4: where M is Co, R = cyclopentyl (C5H9), R 1 = R 4 = diphenylmethyl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 = H;

[0033] Complex Co-5: where M is Co, R = cyclohexyl (C6H 11 ), R 1 = R 4 = diphenylmethyl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 = H;

[0034] Complex Co-6: where M is Co, R = cyclooctyl (C8H 15 ), R 1 = R 4 = diphenylmethyl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 = H;

[0035] Complex Co-7: where M is Co, R = methyl, R 1 = R 4 = diphenylmethyl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 = H;

[0036] Complex Co-8: where M is Co, R = F, R1 =R 4 = diphenylmethyl (CHPh2), R 2 R 3 R 5 R 6 R 7 For H;

[0037] Complex Co-9: where M is Co, R = Cl, R 1 =R 4 = diphenylmethyl (CHPh2), R 2 R 3 R 5 R 6 R 7 For H;

[0038] Complex Fe-1: where M is Fe, R = cyclopentyl (C5H9), R 1 =Methyl, R 4 = diphenylmethyl (CHPh2), R 2 R 3 R 5 R 6 R 7 For H;

[0039] Complex Fe-2: where M is Fe, R = diphenylmethyl (CHPh2), R 1 =Methyl, R 4 =cyclopentyl(C5H9), R 2 R 3 R 5 R 6 R 7 For H;

[0040] Complex Fe-3: where M is Fe, R = cyclopentyl (C5H9), R 1 = diphenylmethyl (CHPh2), R 4 =Methyl, R 2 R 3 R 5 R 6 R 7 For H;

[0041] Complex Fe-4: where M is Fe, R = cyclopentyl (C5H9), R 1 =R 4 = diphenylmethyl (CHPh2), R 2 R 3 R 5 R 6 R 7 For H;

[0042] Complex Fe-5: wherein, M is Fe, R = cyclohexyl (C6H 11 ), R 1 = R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H;

[0043] Complex Fe-6: wherein, M is Fe, R = cyclooctyl (C8H 15 ), R 1 = R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H;

[0044] Complex Fe-7: wherein, M is Fe, R = methyl, R 1 = R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H;

[0045] Complex Fe-8: wherein, M is Fe, R = F, R 1 = R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H;

[0046] Complex Fe-9: wherein, M is Fe, R = Cl, R 1 = R 4 = benzhydryl (CHPh2), R 2 , R 3 , R 5 , R 6 , R 7 is H.

[0047] The application further provides a preparation method of the complex shown in the formula (I), comprising: reacting a compound shown in the formula (II), MX2 and an aniline compound shown in the formula (III) to obtain the compound shown in the formula (I),

[0048]

[0049] wherein R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , M, X have the definitions as described above.

[0050] According to the present application, the reaction can be a template reaction.

[0051] According to the preparation method of the present application, the MX2 is selected from one or more of halides containing iron or cobalt, hydrates or other solvates of the halides, for example, can be one or more of FeCl2, FeCl2.4H2O or CoCl2.6H2O.

[0052] According to the preparation method of the present application, the aniline compound represented by formula (III) can also be in the form of its hydrochloride.

[0053] According to the present application, the molar ratio of the compound of formula (II), MX2 or its hydrate, and the aniline compound represented by formula (III) or its hydrochloride is 1.0:(0.5-4.0):(0.9-2.5), for example, 1:1:2.2.

[0054] According to the present application, the temperature of the reaction is 100-160°C, for example, 130°C; the time is 6-12 hours, for example, 8 hours.

[0055] According to the present application, the reaction can be carried out in an organic solvent; for example, the organic solvent can be acetic acid.

[0056] According to the present application, the reaction is preferably carried out in an inert gas atmosphere, for example, under nitrogen atmosphere.

[0057] Preferably, the obtained compound represented by formula (I) can be further purified, and the purification method can comprise the following steps:

[0058] a) concentrating the reaction product containing the compound represented by formula (I), then adding a solvent to produce a precipitate;

[0059] b) solid-liquid separating (for example, filtering) the product of step a), taking the solid phase, washing with a solvent, and drying.

[0060] According to the present application, the solvent can be anhydrous diethyl ether.

[0061] The present application also provides the use of the above-mentioned complex represented by formula (I) in catalyzing the polymerization reaction of olefins.

[0062] The complex represented by the formula (I) can be particularly applied to catalyze the ethylene polymerization.

[0063] The application also provides a catalyst composition comprising a main catalyst and optionally a cocatalyst, wherein the main catalyst is selected from the complex represented by the formula (I) according to the application.

[0064] According to the application, the catalyst composition comprises a main catalyst and a cocatalyst.

[0065] According to the application, when the cocatalyst is present, the cocatalyst can be selected from one or more of aluminoxane, alkylaluminum, chlorinated alkylaluminum. Specifically, the alkyl in the alkylaluminum and chlorinated alkylaluminum is selected from alkyl with 1-3 carbon atoms.

[0066] According to the application, the aluminoxane can be selected from one or both of methylaluminoxane (MAO) or triisobutylaluminum modified methylaluminoxane (MMAO); the chlorinated alkylaluminum can be selected from one or both of diethylaluminum chloride (Et2AlCl) and dimethylaluminum chloride (Me2AlCl).

[0067] In the application, the molar ratio of the metal Al in the cocatalyst to the central metal M of the main catalyst is 500-4000:1. For example, it can be 500:1, 1000:1, 2000:1, 3000:1, 4000:1.

[0068] In the application, the molar ratio of the metal Al in the cocatalyst to the central metal (specifically Co) of the complex represented by the formula (I) is (500-4000):1, preferably the molar ratio is (1000-3000):1, and specifically it can be 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1.

[0069] Preferably, when the cocatalyst is methylaluminoxane (MAO), the molar ratio of the metal Al in the methylaluminoxane (MAO) to the central metal (specifically Co) of the complex represented by the formula (I) can be (1000-3000):1, and more preferably the molar ratio is 1750:1. For example, it can be 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1.

[0070] Preferably, when the co-catalyst is triisobutylaluminum-modified methylaluminoxane (MMAO), the molar ratio of the metal Al in the triisobutylaluminum-modified methylaluminoxane (MMAO) to the central metal (specifically Co) of the complex shown in formula (I) is (1000-3000):1, for example, it can be 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1; more preferably, the molar ratio is 2250:1.

[0071] The application further provides a method for preparing an olefin polymer, comprising the following steps: catalyzing the polymerization of olefin under the action of the above-mentioned complex shown in formula (I) or the above-mentioned catalyst composition to obtain an olefin polymer. Preferably, the temperature of the polymerization reaction is 30-100℃, and specifically can be 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃; preferably, the temperature is 40-90℃.

[0072] According to the application, the time of the polymerization reaction is 5-60 min, and specifically can be 30 min.

[0073] According to the application, the pressure of the polymerization reaction is 0.5-10 atm, and specifically can be 10 atm.

[0074] According to the application, the olefin can be ethylene, that is, the polymerization reaction is carried out in an ethylene atmosphere.

[0075] Beneficial effects

[0076] 1. The application provides a method for preparing a high-thermostable asymmetric six-membered ring pyridine imine-based transition metal complex containing a large steric cycloalkyl group and a benzhydryl group, which can be used for preparing highly linear polyethylene. The preparation process of the compound has the advantages of mild reaction conditions, short cycle, simple operation conditions and the like.

[0077] 2. The application provides the use of an asymmetric six-membered ring pyridine imine-based transition metal complex containing a large steric cycloalkyl group and a benzhydryl group; the complex can be used as a catalyst in an ethylene polymerization reaction, has high reactivity, has extremely strong control performance on the molecular weight of polyethylene, and can be used for preparing highly linear polyethylene. The structure of the complex of the application advantageously stabilizes the strong positive characteristics of the central metal and the strong Lewis acidity, improves the probability of ethylene insertion, and makes the system have higher catalytic activity and stability. The polyethylene prepared by the catalyst has a weight average molecular weight M w In 1.1-101.6 kg·mol -1The molecular weight distribution is between 2-19.8, which can be used for preparing special high-end commercial polyethylene products. By changing the substitution position, steric hindrance and electronic effect of the substituent, the molecular weight of the obtained polyethylene can be greatly regulated.

[0078] 3. The asymmetric six-membered ring pyridine imine transition metal complex provided by the present application has extremely high thermal stability in catalyzing ethylene polymerization. The complex catalyst can still maintain high and persistent activity at a high temperature (80-100℃), meets the operating temperature of industrial production, and has a wide industrial application prospect.

[0079] 4. The method for preparing polyethylene provided by the present application is simple in operation, and the reaction condition is easy to control. The obtained product has adjustable molecular weight and melting point (the melting point is greater than 120℃). Especially for the part of the large steric hindrance iron complex catalyst, the catalytic ethylene polymerization can obtain low molecular weight polyethylene wax with narrow molecular weight distribution (PDI value <2.0), and the molecular weight is about one thousand, and the minimum can be 550 g·mol -1 , which is much lower than the previously synthesized polymer. At the same time, it shows the characteristics of highly linear polyethylene containing end group double bonds, and can be used as a thin film, a fiber and various pipes, and shows potential application in the production of long-chain copolymer, functional polymer and coating material.

[0080] 5. In the complex structure of the present application, the large steric hindrance cycloalkane and the benzhydryl substituent are a new type of flexible six-membered ring pyridine imine catalyst. Due to the steric hindrance effect of the ortho bulky substituent, the dihedral angle formed by the arylimine plane and the coordination plane is close to 90°, and is basically in a vertical position, which can effectively protect the metal active center. Therefore, the complex described in the present application has high activity, and is stable in nature and has long catalytic life.

[0081] Term definition and explanation

[0082] In the present application, the term "C 1-6 alkyl" means a linear or branched alkyl group having 1-6 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl.

[0083] The term "C 1-6 alkyl" means a linear or branched alkyl group having 1-6 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl. 1-6 alkyl" has the above definition, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexyloxy or isomers thereof. In particular, "alkoxy" is "C 1-4 alkoxy", "C 1-3"Alkoxy", preferably methoxy, ethoxy or propoxy. Further preferred is "C 1-2 "Alkoxy", in particular methoxy or ethoxy.

[0084] The term "C 3-10 "Cycloalkyl" is to be understood as meaning a straight-chain or branched, saturated, monovalent monocyclic hydrocarbon ring which contains, for example, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. C 3-8 Cycloalkyl is, for example, a monocyclic hydrocarbon ring, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. In particular, the cycloalkyl group is C 4-6 Cycloalkyl, C 5-6 Cycloalkyl or cyclohexyl. For example, the term "C 3-6 "Cycloalkyl" is to be understood as preferably meaning a saturated, monovalent monocyclic hydrocarbon ring which contains, for example, 3, 4, 5 or 6 carbon atoms. In particular, C 3-6 Cycloalkyl is a monocyclic hydrocarbon ring, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0085] The term "C 3-10 "Cycloalkyloxy" is to be understood as meaning a radical of the formula -O-cycloalkyl, where the term "C 3-10 "Cycloalkyl" has the definition indicated above.

[0086] The term "3-10 membered heterocyclyl" means a saturated, monovalent monocyclic or bicyclic hydrocarbon ring which comprises 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl group can be attached to the remainder of the molecule through any one of the carbon atoms or the nitrogen atom, if present. In particular, the heterocyclyl group can include, but is not limited to: 4-membered rings, such as azetidinyl, oxetanyl; 5-membered rings, such as tetrahydrofuranyl, dioxolanyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or 7-membered rings, such as diazepanyl. Optionally, the heterocyclyl group can be benzo-fused. The heterocyclyl group can be bicyclic, such as, but not limited to, 5,5-membered rings, such as hexahydrocyclopenta[c]pyrrol-2(lH)-yl ring, or 5,6-membered rings, such as hexahydropyrrolo[l,2-a]pyrazin-2(lH)-yl ring. The ring containing a nitrogen atom can be partially unsaturated, i.e. it can contain one or more double bonds, such as, but not limited to, 2,5-dihydro-lH-pyrrolyl, 4H-[l,3,4]thiadiazolyl, 4,5-dihydrooxazolyl or 4H-[l,4]thiazinyl, or it can be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the present application, the heterocyclyl group is non-aromatic.

[0087] The term "C 6-20"Aryl" is to be understood as meaning a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably a "C 6-14 "Aryl". The term "C 6-14 "Aryl" is to be understood as meaning a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms ("C 6-14 "Aryl"), in particular a ring having 6 carbon atoms ("C6-aryl"), for example phenyl; or a ring having 9 carbon atoms ("C9-aryl"), for example indanyl or indenyl; or a ring having 10 carbon atoms ("C 10 "Aryl"), for example tetrahydronaphthyl, dihydronaphthyl or naphthyl; or a ring having 13 carbon atoms ("C 13 "Aryl"), for example fluorenyl; or a ring having 14 carbon atoms ("C 14 "Aryl"), for example anthryl.

[0088] The term "C 6-20 "Aryloxy" is to be understood as meaning of the formula -O-aryl. BRIEF DESCRIPTION OF DRAWINGS

[0089] Figure 1 Reaction scheme for the preparation of the complexes of Examples 1 to 18.

[0090] Figure 2 Schematic representation of the crystal structure of the complex Fe-5 of Example 14.

[0091] Figure 3 Temperature-raising NMR spectra of the polymer obtained in Example 19 i) and NMR carbon spectrum. DETAILED DESCRIPTION

[0092] The technical solutions of the present application will be described in further detail below in connection with specific examples. It should be understood that the following examples are merely illustrative and explanatory of the present application and should not be construed as limiting the scope of protection of the present application. Any technology realized on the basis of the above description of the present application is encompassed within the scope of protection intended by the present application.

[0093] The starting materials and reagents used in the following examples are commercially available or can be prepared by known methods, unless otherwise stated.

[0094] The concentrations in the following examples are molar concentrations, unless otherwise stated.

[0095] Methylaluminoxane (abbreviated as MAO) and triisobutylaluminum modified methylaluminoxane (abbreviated as MMAO) used in Examples 19-47 were purchased from Akzo Nobel Corporation, USA. Al / Fe and Al / Co in the following examples refer to the molar ratio of metal Al in the cocatalyst MAO or MMAO to Fe or Co in the added metal complex catalyst, not the molar ratio of aluminum element to metal Fe or Co.

[0096] The molecular weight (Mn) of the polymer obtained in the ethylene polymerization examples of Examples 19-47 was determined according to the conventional high temperature GPC method, the melting point (Tm) was determined according to the conventional DSC method, and the polymerization activity was calculated according to the following formula: Polymerization activity = polymer yield / (catalyst amount * polymerization time). w m

[0097] All the synthesized compounds were confirmed by infrared and elemental analysis.

[0098] Example 1, Preparation of 2-(1-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino)ethyl)-8-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclopentyl, R 1 is methyl, R 4 is benzhydryl, and R 2 , R 3 is hydrogen), Co-1

[0099]

[0100] A mixture of 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.19 g (0.55 mmol) of 2-cyclopentyl-4-benzhydryl-6-methylaniline, and 0.06 g (0.25 mmol) of CoCl2·6H2O was dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.16 g, 67%) was obtained, which was the Co-1 complex.

[0101] The structural data are as follows:

[0102] FT-IR (KBr cm -1 ): 2949 (w), 2865 (w), 1618 (υ C＝N ​​,w),1489(w),1449(w),1371(w),1263(w),1240(w),1139(w),1032(w),925(w),892(w),827(w),744(w),702(s).

[0103] Elemental analysis: C 61 H 61 Theoretical values ​​for Cl2CoN3 (966.0): C, 75.84%; H, 6.37%; N, 4.35%; Experimental values: C, 75.41%; H, 5.96%; N, 4.17%.

[0104] Example 2: Preparation of 2-(1-(2-diphenylmethyl-4-cyclopentyl-6-methylphenylimino)ethyl)-8-(2-diphenylmethyl-4-cyclopentyl-6-methylphenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is diphenylmethyl, R 1 It is methyl, R 4 It is cyclopentyl, R 2 R 3 (for hydrogen), Co-2

[0105]

[0106] 0.05 g (0.25 mmol) of the 2-acetyl-6,7-dihydroquinoline-8-one compound shown in formula (II-1), 0.19 g (0.55 mmol) of 2-diphenylmethyl-4-cyclopentyl-6-methylaniline, and 0.06 g (0.25 mmol) of CoCl2·6H2O were dissolved in 10 mL of acetic acid. The mixture was stirred and refluxed at 130 °C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate the precipitate. The precipitate was collected by filtration, and the precipitate was then dissolved in dichloromethane. The solution was concentrated, and a large amount of diethyl ether was added to precipitate the precipitate. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying, a brown powder (0.15 g, 63%) was obtained, containing Co-2.

[0107] The structured data is as follows:

[0108] FT-IR (KBr cm) -1 :2947(w),2865(w),1621(υ) C＝N ,w),1574(w),1490(w),1448(w),1373(m),1242(w),1215(w),1032(w),925(w),868(w),825(w),748(w),703(s).

[0109] Elemental analysis: C 61 H 61Cl2CoN3(966.0) Theory: C, 75.84; H, 6.37; N, 4.35 %; Found: C, 75.94; H, 6.14; N, 4.04 %.

[0110] Example 3, Preparation of 2-(l-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)ethyl)-8-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)-5,6,7-trihydroquinoline cobalt complex (R is cyclopentyl, R 1 is benzhydryl, R 4 is methyl, R 2 , R 3 is hydrogen), Co-3

[0111]

[0112] Example 3, Preparation of 2-(l-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)ethyl)-8-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)-5,6,7-trihydroquinoline cobalt complex (R is cyclopentyl, R

[0113] Structural data are as follows:

[0114] FT-IR (KBr cm -1 ): 2949 (w), 2863 (w), 1619 (υ C＝N , 1575 (w), 1496 (w), 1450 (w), 1370 (w), 1267 (w), 1241 (w), 1203 (w), 1033 (w), 993 (w), 934 (w), 861 (w), 821 (w), 750 (w), 703 (w).

[0115] Elemental Analysis: C 61 H 61 Cl2CoN3(966.0) Theory: C, 75.84; H, 6.37; N, 4.35 %; Found: C, 75.94; H, 6.14; N, 4.04 %.

[0116] Example 4: Preparation of 2-(1-(2-cyclopentyl-4,6-di(diphenylmethyl)phenylimino)ethyl)-8-(2-cyclopentyl-4,6-di(diphenylmethyl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclopentyl, R...) 1 =R 4 It is diphenylmethyl, R 2 For hydrogen, R 3 (for hydrogen), Co-4

[0117]

[0118] 0.05 g (0.25 mmol) of the 2-acetyl-6,7-dihydroquinoline-8-one compound shown in formula (II-1), 0.27 g (0.55 mmol) of 2-cyclopentyl-4,6-bis(diphenylmethyl)aniline, and 0.06 g (0.25 mmol) of CoCl2·6H2O were dissolved in 10 mL of acetic acid. The mixture was stirred and refluxed at 130 °C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate the precipitate. The precipitate was collected by filtration, and the precipitate was then dissolved in dichloromethane. The solution was concentrated, and a large amount of diethyl ether was added to precipitate the precipitate. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying, a brown powder (0.17 g, 54%) was obtained, containing Co-4.

[0119] The structured data is as follows:

[0120] FT-IR (KBr cm) -1 :2955(w),2868(w),1606(υ) C＝N ,w),1575(w),1494(w),1448(m),1370(w),1263(w),1241(w),1077(w),1031(w),928(w),920(w),861(w),823(w),748(w),700(s).

[0121] Elemental analysis: C 85 H 77 Theoretical values ​​for Cl2CoN3 (1270.4%): C, 80.36%; H, 6.11%; N, 3.31%; Experimental values: C, 79.79%; H, 5.78%; N, 3.25%.

[0122] Example 5: Preparation of 2-(1-(2-cyclohexyl-4,6-di(diphenylmethyl)phenylimino)ethyl)-8-(2-cyclohexyl-4,6-di(diphenylmethyl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclohexyl, R...) 1 =R 4 It is diphenylmethyl, R 2 For hydrogen, R3 Co-5

[0123]

[0124] A mixture of 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.28 g (0.55 mmol) of 2-cyclohexyl-4,6-bis(benzhydryl) aniline and 0.06 g (0.25 mmol) of CoCl2-6H2O was dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.18 g, 56%) was obtained. Co-5.

[0125] The structural data are as follows:

[0126] FT-IR (KBr cm -1 ): 2930 (w), 2853 (w), 1626 (υ C＝N , 1605 (w), 1575 (w), 1493 (w), 1446 (m), 1369 (w), 1295 (w), 1240 (w), 1076 (w), 1031 (w), 967 (w), 924 (w), 884 (w), 830 (w), 746 (w), 701 (s).

[0127] Elemental analysis: C 87 H 81 Cl2CoN3(1298.5) Calcd: C, 80.48; H, 6.29; N, 3.24%; Found: C, 80.11; H, 6.22; N, 3.22%.

[0128] Example 6, Preparation of 2-(l-(2-cyclooctyl-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-cyclooctyl-4,6-bis(benzhydryl) phenylimino)-5,6,7- trihydroquinoline cobalt complex (R is cyclooctyl, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Co-6

[0129]

[0130] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.29 g (0.55 mmol) of 2-cyclooctyl-4,6-bis(benzhydryl) aniline and 0.06 g (0.25 mmol) of CoCl2-6H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder was obtained (0.18 g, 54%), Co-6.

[0131] Structural data are as follows:

[0132] FT-IR (KBr cm -1 ): 2917 (w), 2859 (w), 1624 (w), 1602 (w), 1576 (w), 1492 (w), 1447 (w), 1371 (w), 1267 (w), 1241 (w), 1075 (w), 1033 (w), 927 (w), 903 (w), 870 (w), 828 (w), 747 (w), 702 (s).

[0133] Elemental analysis: C 91 H 89 Cl2CoN3 (1354.57) Theory: C, 80.69; H, 6.62; N, 3.10%; Experiment: C, 80.22; H, 6.43; N, 3.07%.

[0134] Example 7, Preparation of 2-(l-(2-methyl-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-methyl-4,6-bis(benzhydryl) phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is methyl, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Co-7

[0135]

[0136] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24 g (0.55 mmol) of 2-methyl-4,6-bis(benzhydryl) aniline and 0.06 g (0.25 mmol) of CoCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.16 g, 55%) was obtained, Co-7.

[0137] Structural data are as follows:

[0138] FT-IR (KBr cm -1 ): 2951 (w), 2871 (w), 1624 (υ C＝N , 1593 (w), 1550 (w), 1494 (w), 1449 (w), 1263 (w), 1236 (w), 1121 (w), 1030 (w), 925 (w), 889 (w), 829 (w), 742 (w), 701 (s).

[0139] Elemental analysis: C 77 H 65 Cl2CoN3 (1162.22) Calcd: C, 79.58; H, 5.64; N, 3.62%; Found: C, 79.21; H, 5.51; N, 3.78%.

[0140] Example 8, Preparation of 2-(l-(2-fluoro-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-fluoro-4,6-bis(benzhydryl) phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is fluoro, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Co-8

[0141]

[0142] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24 g (0.55 mmol) of 2-fluoro-4,6-bis(benzhydryl) aniline and 0.06 g (0.25 mmol) of CoCl2-6H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.18 g, 62%) was obtained, Co-8.

[0143] Structural data are as follows:

[0144] FT-IR (KBr cm -1 ): 2950 (w), 2873 (w), 1628 (w), 1602 (w), 1576 (w), 1494 (w), 1427 (w), 1366 (w), 1297 (w), 1241 (w), 1131 (w), 1031 (w), 1000 (w), 925 (w), 830 (w), 745 (w), 701 (s).

[0145] Elemental analysis: C 75 H 59 Cl2CoF2N3 (1170.15) Calcd: C, 76.98; H, 5.08; N, 3.59%; Found: C, 76.49; H, 4.89; N, 3.65%.

[0146] Example 9, Preparation of 2-(l-(2-chloro-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-chloro-4,6-bis(benzhydryl) phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is chloro, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Co-9

[0147]

[0148] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.25 g (0.55 mmol) of 2-chloro-4,6-bis(benzhydryl) aniline and 0.06 g (0.25 mmol) of CoCl2-6H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder was obtained (0.16 g, 53%).

[0149] Structural data are as follows:

[0150] FT-IR (KBr cm -1 ): 2951 (w), 2871 (w), 1624 (υ C＝N , 1593 (w), 1550 (w), 1494 (w), 1449 (w), 1263 (w), 1236 (w), 1121 (w), 1030 (w), 925 (w), 889 (w), 829 (w), 742 (w), 701 (s).

[0151] Elemental analysis: C 75 H 59 Cl4CoN3 (1203.05) Theory: C, 74.88; H, 4.94; N, 3.49%; Experiment: C, 74.62; H, 4.89; N, 3.66%.

[0152] Example 10, Preparation of 2-(l-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino)ethyl)-8-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino)-5,6,7-trihydroquinoline iron complex (R is cyclopentyl, R 1 is methyl, R 4 is benzhydryl, R 2 , R 3 is hydrogen), Fe-1

[0153]

[0154] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.19 g (0.55 mmol) of 2-cyclopentyl-4-benzhydryl-6-methylaniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, and the solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.18 g, 75%) was obtained, Fe-1.

[0155] Structural confirmation data are as follows:

[0156] FT-IR (KBr cm -1 ): 2956.3 (w), 2867.6 (w), 1617.8 (w), 1598.6 (w), 1575.3 (w), 1493.6 (m), 1447.3 (w), 1365.7 (w), 1269.3 (w), 1241.2 (m), 1153.5 (w), 1074.7 (w), 1032.6 (w), 898.5 (w), 862.9 (w), 823.1 (w), 746.6 (m), 698.4 (s).

[0157] Elemental analysis: C 61 H 61 Cl2FeN3(962.9) Calcd: C, 76.09; H, 6.39; N, 4.36 %; Found: C, 76.13; H, 5.93; N, 4.11 %.

[0158] Example 11, Preparation of 2-(l-(2-benzhydryl-4-cyclopentyl-6-methyIphenylimino)ethyl)-8-(2-benzhydryl-4-cyclopentyl-6-methyIphenylimino)-5,6,7-trihydroquinoline iron chloride (R is benzhydryl, R 1 is methyl, R 4 is cyclopentyl, R 2 , R 3 is hydrogen), Fe-2

[0159]

[0160] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by the formula (II-1), 0.19 g (0.55 mmol) of 2-benzhydryl-4-cyclopentyl-6-methylaniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane. The solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.16 g, 67%) was obtained. Fe-2.

[0161] The structural data are as follows:

[0162] FT-IR (KBr cm -1 ): 2948.4 (w), 2865.8 (w), 1619.9 (w), 1574.6 (w), 1490.1 (w), 1449.8 (w), 1374.0 (m), 1266.9 (w), 1243.3 (m), 1214.2 (w), 1153.5 (w), 1078.7 (w), 1033.4 (w), 923.7 (w), 869.1 (w), 824.7 (w), 748.5 (m), 703.0 (s).

[0163] Elemental analysis: C 61 H 61 Cl2FeN3 (962.9) Theory: C, 76.09; H, 6.39; N, 4.36 %; Experiment: C, 75.72; H, 6.28; N, 4.20 %.

[0164] Example 12, Preparation of 2-(l-(2-cyclopentyl-4-methyl-6-benzhydrylphenyl- imino)ethyl)-8-(2-cyclopentyl-4-methyl-6-benzhydrylphenyl-imino)-5,6,7- trihydroquinoline iron chloride (R is cyclopentyl, R 1 is benzhydryl, R 4 is methyl, R 2 , R 3 is hydrogen), Fe-3

[0165]

[0166] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.19 g (0.55 mmol) of 2-cyclopentyl-4-methyl-6- diphenylmethylaniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder was obtained (0.18 g, 75%), Fe-3.

[0167] The structural data are as follows:

[0168] FT-IR (KBr cm -1 ): 2951.2 (w), 2866.1 (w), 1603.3 (w), 1574.5 (w), 1493.2 (w), 1449.8 (w), 1373.2 (w), 1270.4 (w), 1243.0 (w), 1206.5 (w), 1137.0 (w), 1074.5 (w), 1033.1 (w), 931.5 (w), 863.3 (w), 924.2 (w), 747.6 (w), 701.4 (s).

[0169] Elemental analysis: C 61 H 61 Cl2FeN3 (962.9) Theory: C, 76.09; H, 6.39; N, 4.36 %; Experiment: C, 75.88; H, 6.21; N, 4.29 %.

[0170] Example 13, Preparation of 2-(l-(2-cyclopentyl-4,6-di(diphenylmethyI)phenyl- imino)ethyl)-8-(2-cyclopentyl-4,6-di(diphenylmethyl)phenyl-imino)-5,6,7-trihydroquinoline iron chloride (R is cyclopentyl, R 1 = R 4 is diphenylmethyl, R 2 is hydrogen, R 3 is hydrogen), Fe-4

[0171]

[0172] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.27 g (0.55 mmol) of 2-cyclopentyl-4,6-bis(benzhydryl) aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.17 g, 54%) was obtained. Fe-4.

[0173] Structural data are as follows:

[0174] FT-IR (KBr cm -1 ): 2956.3 (w), 2867.6 (w), 1617.8 (w), 1598.6 (w), 1575.3 (w), 1493.6 (m), 1447.3 (w), 1365.7 (w), 1269.3 (w), 1241.2 (m), 1153.5 (w), 1074.7 (w), 1032.6 (w), 898.5 (w), 862.9 (w), 823.1 (w), 746.6 (m), 698.4 (s).

[0175] Elemental analysis: C 85 H 77 Cl2FeN3 (1267.3) Theory: C, 80.56; H, 6.12; N, 3.32%; Experiment: C, 80.08; H, 5.89; N, 3.36%.

[0176] Example 14, Preparation of 2-(l-(2-cyclohexyl-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-cyclohexyl-4,6-bis(benzhydryl) phenylimino)-5,6,7-trihydroquinoline iron chloride (R is cyclohexyl, R 1 = R 4 is benzhydryl, R 2 is hydrogen, R 3 is hydrogen), Fe-5

[0177]

[0178] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.28 g (0.55 mmol) of 2-cyclohexyl-4,6-bis(benzhydryl) aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.18 g, 56%) was obtained. Fe-5.

[0179] Structural confirmation data are as follows:

[0180] FT-IR (KBr cm -1 ): 2924.6 (w), 2857.7 (w), 1623.6 (w), 1599.3 (w), 1569.3 (w), 1493.8 (w), 1446.9 (m), 1368.7 (w), 1271.7 (w), 1241.3 (w), 1075.0 (w), 1032.5 (w), 907.9 (w), 865.4 (w), 824.7 (w), 744.8 (m), 698.7 (s).

[0181] Elemental analysis: C 87 H 81 Cl2FeN3 (1295.4) Theory: C, 80.67; H, 6.30; N, 3.24%; Experiment: C, 80.22; H, 6.11; N, 3.19%.

[0182] A schematic diagram of the crystal structure of Fe-5 is shown in Figure 2 .

[0183] Example 15, Preparation of 2-(l-(2-cyclooctyl-4,6-bis(benzhydryl) phenylimino) ethyl)-8-(2-cyclooctyl-4,6-bis(benzhydryl) phenylimino)-5,6,7- trihydroquinoline iron chloride (R is cyclooctyl, R 1 = R 4 is benzhydryl, and R 2 , R 3 is hydrogen), Fe-6.

[0184]

[0185] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.29 g (0.55 mmol) of 2-cyclooctyl-4,6-bis(benzhydryl)aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, a large amount of diethyl ether was added to precipitate, the precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder was obtained (0.18 g, 53%), Fe-6.

[0186] Structural data are as follows:

[0187] FT-IR (KBr cm -1 ): 2917.7 (w), 2852.0 (w), 1604.7 (w), 1574.8 (w), 1494.2 (w), 1446.3 (w), 1367.4 (w), 1269.3 (w), 1240.5 (w), 1135.4 (w), 1076.6 (w), 1030.7 (w), 924.4 (w), 865.4 (w), 826.5 (w), 745.5 (w), 700.8 (s).

[0188] Elemental analysis: C 91 H 89 Cl2FeN3 (1351.5) Theory: C, 80.87; H, 6.64; N, 3.11%; Experiment: C, 80.39; H, 6.21; N, 3.14%.

[0189] Example 16, Preparation of 2-(l-(2-methyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-methyl-4,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline iron complex (R is methyl, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Fe-7

[0190]

[0191] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24 g (0.55 mmol) of 2-methyl-4,6-bis(benzhydryl) aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.16 g, 55%) was obtained. Fe-7.

[0192] Structural data are as follows:

[0193] FT-IR (KBr cm -1 ): 2951.0 (w), 2861.9 (w), 1622.1 (w), 1597.3 (w), 1491.0 (w), 1452.7 (w), 1363.3 (w), 1261.2 (w), 1244.8 (w), 1202.1 (w), 1139.9 (w), 1031.1 (w), 927.1 (w), 898.3 (w), 745.5 (w), 702.2 (s).

[0194] Elemental analysis: C 77 H 65 Cl2FeN3 (1157.39) Theory: C, 79.79; H, 5.65; N, 3.63%; Experiment: C, 79.51; H, 5.47; N, 3.82%.

[0195] Example 17, Preparation of 2-(l-(2-fluoro-4,6-bis(benzhydryl)phenyl imino)ethyl)-8-(2-fluoro-4,6-bis(benzhydryl)phenyl imino)-5,6,7-trihydroquinoline iron chloride (R is fluoro, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Fe-8

[0196]

[0197] To 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24 g (0.55 mmol) of 2-fluoro-4,6-bis(benzhydryl) aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O were dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.20 g, 69%) was obtained, Fe-8.

[0198] Structural data are as follows:

[0199] FT-IR (KBr cm -1 ): 2974.8 (w), 2908.7 (w), 1623.6 (w), 1602.4 (w), 1573.8 (w), 1494.2 (w), 1427.1 (w), 1297.3 (w), 1243.4 (w), 1125.2 (w), 1031.8 (w), 919.7 (w), 829.9 (w), 744.5 (w), 700.1 (s).

[0200] Elemental analysis: C 75 H 59 Cl2F2FeN3 (1167.1) Theory: C, 77.19; H, 5.10; N, 3.60%; Experiment: C, 74.63; H, 4.55; N, 3.52%.

[0201] Example 18, Preparation of 2-(l-(2-chloro-4,6-bis(benzhydryl)phenyl imino)ethyl)-8-(2-chloro-4,6-bis(benzhydryl)phenyl imino)-5,6,7-trihydroquinoline iron chloride (R is chloro, R 1 = R 4 is benzhydryl, R 2 , R 3 is hydrogen), Fe-9

[0202]

[0203] A mixture of 0.05 g (0.25 mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.25 g (0.55 mmol) of 2-chloro-4,6-bis(benzhydryl) aniline and 0.05 g (0.25 mmol) of FeCl2-4H2O was dissolved in 10 mL of acetic acid, and stirred under reflux at 130°C for 4 h under a nitrogen atmosphere. The reaction solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane. The solution was concentrated, and a large amount of diethyl ether was added to precipitate. The precipitate was collected by filtration, and washed with a large amount of diethyl ether. After drying, a brown powder (0.16 g, 53%) was obtained. Fe-9.

[0204] Structural data are as follows:

[0205] FT-IR (KBr cm -1 ): 2970.3 (w), 2909.2 (w), 1604.7 (w), 1573.8 (w), 1491.3 (w), 1446.8 (w), 1406.3 (w), 1378.0 (w), 1241.3 (w), 1073.5 (w), 900.4 (w), 827.1 (w), 745.9 (w), 701.0 (s).

[0206] Elemental analysis: C 75 H 59 Cl4FeN3 (1200.0) Theory: C, 75.07; H, 4.96; N, 3.50 %; Experiment: C, 74.63; H, 4.55; N, 3.52 %.

[0207] Example 19. Polymerization of ethylene under high pressure using complex Co-1 and cocatalyst MAO

[0208] a) Under a nitrogen atmosphere, 30 ml of a toluene solution of catalyst Co-1 (2 μmol) was injected into a 250 ml stainless steel autoclave equipped with a mechanical stirrer, followed by the addition of 30 ml of toluene, and the addition of the desired amount of cocatalyst MAO (1.46 mol / L in toluene) 3.1 mL, and the addition of toluene to make the total volume of the reaction solution 100 mL. At this time, Al / Co = 2250:1. The mechanical stirring was started, and when the polymerization temperature reached 30°C, ethylene was charged into the reactor, and the polymerization was started. The polymerization was carried out at 30°C under 10 atm of ethylene pressure for 30 min. The reaction solution was neutralized with 10% hydrochloric acid in ethanol, and the polymer precipitate was washed several times with ethanol, and dried in vacuo at 50°C to constant weight. The weight of the polymer was 4.75 g, and the polymerization activity was 4.75 x 10 6 g / mol (Co)h -1 , and the polymer molecular weight Mw was 1.2 x 106.w =1.89kg mol -1 Molecular weight distribution M w / M n 2.7 (M) w M is the weight-average molecular weight of the polymer. n (These are the number-average molecular weights of the polymers, all obtained through GPC testing), polymer T m =122.8℃(T) m (This is the melting temperature of the polymer, obtained through DSC testing).

[0209] b) Basically the same as method a) in this embodiment, except that the polymerization temperature is 40℃. Polymerization activity: 5.32×10 6 g / mol(Co)h -1 Polymer molecular weight M w =1.75kg mol -1 Molecular weight distribution M w / M n The value is 3.6, and the polymer T is... m =122.6℃.

[0210] c) is basically the same as method a) in this embodiment, except that the polymerization temperature is 50℃. Polymerization activity: 8.93×10 6 g / mol(Co)h -1 Polymer molecular weight M w =1.61g mol -1 Molecular weight distribution M w / M n The value is 3.4, and the polymer T is... m =122.4℃.

[0211] d) Basically the same as method a) in this embodiment, except that the polymerization temperature is 60℃. Polymerization activity: 9.18×10 6 g / mol(Co)h -1 Polymer molecular weight M w =1.56kg mol -1 Molecular weight distribution M w / M n The value is 3.3, and the polymer T is... m =122.3℃.

[0212] e) Basically the same as method a) in this embodiment, except that the polymerization temperature is 70℃. Polymerization activity: 5.28 × 10⁻⁶ 6 g / mol(Co)h -1 Polymer molecular weight M w =1.41kg mol -1 Molecular weight distribution M w / Mn = 3.1, polymer T m = 122.1°C.

[0213] f) Essentially as in example a), except that the polymerization temperature was 80°C. Polymerization activity: 2.89 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.37 kg mol -1 , molecular weight distribution M w / M n = 2.9, polymer T m = 121.8°C.

[0214] g) Essentially as in example d), except that the amount of cocatalyst MAO (1.46 mol / L in toluene) was 1.7 mL, giving Al / Co = 1250:1. Polymerization activity: 5.37 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.56 kg mol -1 , molecular weight distribution M w / M n = 3.6, polymer T m = 123.6°C.

[0215] h) Essentially as in example d), except that the amount of cocatalyst MAO (1.46 mol / L in toluene) was 2.1 mL, giving Al / Co = 1500:1. Polymerization activity: 6.47 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.56 kg mol -1 , molecular weight distribution M w / M n = 2.9, polymer T m = 123.3°C.

[0216] i) Essentially as in example d), except that the amount of cocatalyst MAO (1.46 mol / L in toluene) was 2.4 mL, giving Al / Co = 1750:1. Polymerization activity: 13.66 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.63 kg mol -1 , molecular weight distribution M w / M n = 3.2, polymer T m = 123.0°C.

[0217] The resulting polymer 20 mg was dissolved in 2 ml of deuterated 1,1,2,2-tetrachloroethane and tested at 100°C for the presence of the signals of the end groups of the polymer. 1 The H data, as shown in the insert, were collected. The signals were accumulated 64 times and two groups of multiplet signals were obtained at displacements of 5.90 (ppm) and 5.02 (ppm), which proved to be the vinyl groups (-CH=CH2). Figure 3 The H data, as shown in the insert, were collected. The signals were accumulated 64 times and two groups of multiplet signals were obtained at displacements of 5.90 (ppm) and 5.02 (ppm), which proved to be the vinyl groups (-CH=CH2).

[0218] The resulting polymer 20 mg was dissolved in 2 ml of deuterated 1,1,2,2-tetrachloroethane and tested at 100°C for the presence of the signals of the end groups of the polymer. 13 The C data, as shown in the insert, were collected. The signals were accumulated 1024 times and two groups of signals were obtained at displacements of 114.42 (ppm) and 139.57 (ppm), which indicated the ethylene end groups of the long chain of polyethylene, proving that the resulting polymer was highly linear polyethylene, and at 32.23, 22.95 and 14.32 (ppm), which indicated the corresponding n-propyl end groups. Figure 3 The C data, as shown in the insert, were collected. The signals were accumulated 1024 times and two groups of signals were obtained at displacements of 114.42 (ppm) and 139.57 (ppm), which indicated the ethylene end groups of the long chain of polyethylene, proving that the resulting polymer was highly linear polyethylene, and at 32.23, 22.95 and 14.32 (ppm), which indicated the corresponding n-propyl end groups.

[0219] j) Basically the same as method d) in this example, except that the amount of the cocatalyst MAO (1.46 mol / L in toluene) was 2.7 mL, so that Al / Co = 2000:1. Polymerization activity: 10.54 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.58 kg mol -1 , molecular weight distribution M w / M n = 3.3, polymer T m = 123.1°C.

[0220] k) Basically the same as method d) in this example, except that the amount of the cocatalyst MAO (1.46 mol / L in toluene) was 3.4 mL, so that Al / Co = 2500:1. Polymerization activity: 7.81 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.66 kg mol -1 , molecular weight distribution M w / M n = 3.4, polymer T m = 122.8°C.

[0221] Example 20, ethylene polymerization under pressure using the complex Co-2 and MAO as the combined catalyst

[0222] Basically the same as example 19 i), except that the main catalyst was Co-2. Polymerization activity: 2.98 x 106 g / mol(Co)h -1 , the polymerization molecular weight M w = 14.67 kg mol -1 , the molecular weight distribution M w / M n = 5.9, the polymer T m = 129.7°C.

[0223] Example 21, ethylene polymerization under pressure with the complex Co-3 and MAO as combined catalyst

[0224] Essentially as in Example 19 i), with the difference that the procatalyst is Co-3. The polymerization activity: 3.61 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 101.63 kg mol -1 , the molecular weight distribution M w / M n = 3.8, the polymer T m = 134.6°C.

[0225] Example 22, ethylene polymerization under pressure with the complex Co-4 and MAO as combined catalyst

[0226] Essentially as in Example 19 i), with the difference that the procatalyst is Co-4. The polymerization activity: 3.20 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 48.28 kg mol -1 , the molecular weight distribution M w / M n = 3.8, the polymer T m = 134.6°C.

[0227] Example 23, ethylene polymerization under pressure with the complex Co-5 and MAO as combined catalyst

[0228] Essentially as in Example 19 i), with the difference that the procatalyst is Co-5. The polymerization activity: 1.10 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 61.62 g mol -1 , the molecular weight distribution M w / M n = 4.7, the polymer T m = 135.5°C.

[0229] Example 24, ethylene polymerization under pressure with the complex Co-6 and MAO as combined catalyst

[0230] Essentially the same as example 19i), except that the procatalyst is Co-6. Polymerization activity: 0.81 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 92.16 g mol -1 , the molecular weight distribution M w / M n is 6.4, the polymer T m = 134.7°C.

[0231] Example 25, ethylene polymerization under pressure with the complex Co-7 and MAO as combined catalyst

[0232] Essentially the same as example 19i), except that the procatalyst is Co-7. Polymerization activity: 3.65 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 63.91 g mol -1 , the molecular weight distribution M w / M n is 19.8, the polymer T m = 134.3°C.

[0233] Example 26, ethylene polymerization under pressure with the complex Co-8 and MAO as combined catalyst

[0234] Essentially the same as example 19i), except that the procatalyst is Co-8. Polymerization activity: 4.24 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 3.43 g mol -1 , the molecular weight distribution M w / M n is 6.3, the polymer T m = 122.8°C.

[0235] Example 27, ethylene polymerization under pressure with the complex Co-9 and MAO as combined catalyst

[0236] Essentially the same as example 19i), except that the procatalyst is Co-9. Polymerization activity: 3.78 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 24.85 g mol -1 , the molecular weight distribution M w / M n is 9.2, the polymer T m= 131.0 °C.

[0237] Example 28. Ethylene polymerization under pressure using complex Co-1 and MMAO as cocatalyst

[0238] a) Under a nitrogen atmosphere, 30 ml of a toluene solution of catalyst Co-1 (2.0 μmol) was injected into a 250 ml stainless steel autoclave equipped with mechanical stirring, followed by the addition of 30 ml of toluene, the addition of the desired amount of cocatalyst MMAO (2.0 mol / L in toluene) 2.0 ml, and the addition of toluene to bring the total volume of the reaction to 100 ml. At this point, Al / Co = 2000:1. The mechanical stirring was started at 400 rpm, and when the polymerization temperature reached 30 °C, the reaction was started by charging the reactor with ethylene. The polymerization was carried out at 30 °C and 10 atm of ethylene pressure for 30 min. The reaction was neutralized with 10% hydrochloric acid in ethanol, and the polymer was precipitated. The polymer was washed several times with ethanol and dried in a vacuum oven at 50 °C to constant weight. The polymer was weighed and found to be 2.96 g. The polymerization activity was 2.96 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 2.32 kg mol -1 , the molecular weight distribution M w / M n = 4.9 (M w = the weight average molecular weight of the polymer, M n = the number average molecular weight of the polymer, both determined by GPC), the polymer T m = 122.3 °C (T m = the melting temperature of the polymer, determined by DSC).

[0239] b) Essentially as in method a) of this example, except that the polymerization temperature was 40 °C. The polymerization activity was 3.64 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 1.62 kg mol -1 , the molecular weight distribution M w / M n = 3.2, the polymer T m = 122.3 °C.

[0240] c) Essentially as in method a) of this example, except that the polymerization temperature was 50 °C. The polymerization activity was 8.41 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 1.49 kg mol -1 , the molecular weight distribution M w / M n = 3.1, polymer T m = 122.3°C.

[0241] d) Essentially as in example a), except that the polymerization temperature was 60°C. Polymerization activity: 5.27 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 1.38 kg mol -1 , molecular weight distribution M w / M n = 3.1, polymer T m = 122.9°C.

[0242] e) Essentially as in example a), except that the polymerization temperature was 70°C. Polymerization activity: 2.39 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 5.84 kg mol -1 , molecular weight distribution M w / M n = 9.2, polymer T m = 125.3°C.

[0243] f) Essentially as in example a), except that the polymerization temperature was 80°C. Polymerization activity: 2.1539 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 5.54 kg mol -1 , molecular weight distribution M w / M n = 9.2, polymer T m = 124.7°C.

[0244] g) Essentially as in example c), except that the amount of co-catalyst MMAO (2.0 mol / L in toluene) was 1.5 mL to give Al / Co = 1500:1. Polymerization activity: 6.20 x 10 6 g / mol (Co)h -1 , polymerization molecular weight M w = 2.50 kg mol -1 , molecular weight distribution M w / M n = 2.4, polymer T m = 122.3°C.

[0245] h) Essentially as in method c) of this example, with the difference that the amount of co-catalyst MMAO (2.0 mol / L in toluene) is 2.3 mL, giving Al / Co = 2250:1. Polymerisation activity: 11.78 x 10 6 g / mol (Co)h -1 , the polymerisation molecular mass M w = 1.49 kg mol -1 , the molecular mass distribution M w / M n = 4.0, the polymer T m = 121.9°C.

[0246] i) Essentially as in method c) of this example, with the difference that the amount of co-catalyst MMAO (2.0 mol / L in toluene) is 2.5 mL, giving Al / Co = 2500:1. Polymerisation activity: 11.46 x 10 6 g / mol (Co)h -1 , the polymerisation molecular mass M w = 1.30 kg mol -1 , the molecular mass distribution M w / M n = 3.3, the polymer T m = 121.8°C.

[0247] j) Essentially as in method c) of this example, with the difference that the amount of co-catalyst MMAO (2.0 mol / L in toluene) is 2.8 mL, giving Al / Co = 2750:1. Polymerisation activity: 6.87 x 10 6 g / mol (Co)h -1 , the polymerisation molecular mass M w = 2.87 kg mol -1 , the molecular mass distribution M w / M n = 3.2, the polymer T m = 122.5°C.

[0248] k) Essentially as in method c) of this example, with the difference that the amount of co-catalyst MMAO (2.0 mol / L in toluene) is 3.0 mL, giving Al / Co = 3000:1. Polymerisation activity: 5.82 x 10 6 g / mol (Co)h -1 , the polymerisation molecular mass M w = 2.75 kg mol -1 , the molecular mass distribution M w / M n = 3.4, the polymer T m = 122.3°C.

[0249] Example 29, Ethylene polymerization under pressure using the combination of complex Co-2 and MMAO as catalyst

[0250] Essentially the same as example 28h), except that the procatalyst is Co-2. The polymerization activity is 2.80 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 14.06 kg mol -1 , the molecular weight distribution M w / M n is 9.1, the polymer T m = 130.8 °C.

[0251] Example 30, Ethylene polymerization under pressure using the combination of complex Co-3 and MMAO as catalyst

[0252] Essentially the same as example 28h), except that the procatalyst is Co-3. The polymerization activity is 9.56 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 61.79 kg mol -1 , the molecular weight distribution M w / M n is 2.9, the polymer T m = 134.5 °C.

[0253] Example 31, Ethylene polymerization under pressure using the combination of complex Co-4 and MMAO as catalyst

[0254] Essentially the same as example 28h), except that the procatalyst is Co-4. The polymerization activity is 2.50 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 24.23 kg mol -1 , the molecular weight distribution M w / M n is 6.2, the polymer T m = 132.6 °C.

[0255] Example 32, Ethylene polymerization under pressure using the combination of complex Co-5 and MMAO as catalyst

[0256] Essentially the same as example 28h), except that the procatalyst is Co-5. The polymerization activity is 6.31 x 10 6 g / mol (Co)h -1 , the polymerization molecular weight M w = 24.62 kg mol -1 , the molecular weight distribution M w / M n was 3.0, the polymer T m = 133.1°C.

[0257] Example 33, ethylene polymerization under pressure using the combination of complex Co-6 and MMAO as catalyst

[0258] Essentially the same as example 28h), with the difference that the procatalyst was Co-6. The polymerization activity was 3.75 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 31.09 kg mol -1 , the molecular weight distribution M w / M n was 5.3, the polymer T m = 134.6°C.

[0259] Example 34, ethylene polymerization under pressure using the combination of complex Co-7 and MMAO as catalyst

[0260] Essentially the same as example 28h), with the difference that the procatalyst was Co-7. The polymerization activity was 1.80 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 9.01 kg mol -1 , the molecular weight distribution M w / M n was 3.9, the polymer T m = 132.1°C.

[0261] Example 35, ethylene polymerization under pressure using the combination of complex Co-8 and MMAO as catalyst

[0262] Essentially the same as example 28h), with the difference that the procatalyst was Co-8. The polymerization activity was 4.95 x 10 6 g / mol(Co)h -1 , the polymerization molecular weight M w = 1.11 kg mol -1 , the molecular weight distribution M w / M n was 2.1, the polymer T m = 119.5°C.

[0263] Example 36, ethylene polymerization under pressure using the combination of complex Co-9 and MMAO as catalyst

[0264] Essentially the same as example 28h), with the difference that the procatalyst was Co-9. The polymerization activity was 2.35 x 10 6 g / mol(Co)h-1 Polymer molecular weight M w =11.45kg mol -1 Molecular weight distribution M w / M n The value is 9.9, and the polymer T is... m =131.5℃.

[0265] Example 37: Ethylene polymerization under pressure catalyzed by the combined catalysts Fe-5 and MMAO

[0266] a) Under a nitrogen atmosphere, 30 mL of a toluene solution containing Fe-5 catalyst (2.0 μmol) was injected into a 250 mL stainless steel autoclave equipped with a mechanical stirrer. Then, 30 mL of toluene was added, followed by 2.0 mL of the required amount of co-catalyst MMAO (2.0 mol / L in toluene). Toluene was continued to be added until the total volume of the reaction solution was 100 mL. At this point, Al / Fe = 2000:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30°C, ethylene was introduced into the autoclave, and the polymerization reaction began. The ethylene pressure was maintained at 10 atm at 30°C, and the polymerization reaction was carried out with stirring for 30 min. The reaction solution was neutralized with an ethanol solution acidified with 10% hydrochloric acid to obtain a polymer precipitate. This precipitate was washed several times with ethanol, dried under vacuum at 50°C to constant weight, and weighed to obtain 4.47 g of polymer. The polymerization activity was 4.47 × 10⁻⁶. 6 g / mol(Fe)h -1 Polymer molecular weight M w =11.92kg mol -1 Molecular weight distribution M w / M n 2.2 (M) w M is the mass-average molecular weight of the polymer. n (These are the number-average molecular weights of the polymers, all obtained through GPC testing), polymer T m =127.0℃(T) m (This refers to the melting temperature of the polymer, obtained through DSC testing).

[0267] b) Basically the same as method a) in this embodiment, except that the polymerization temperature is 40℃. Polymerization activity: 6.25 × 10 6 g / mol(Fe)h -1 Polymer molecular weight M w = 2.30 kg mol -1 Molecular weight distribution M w / M n The value is 2.0, and the polymer T is... m =126.1℃.

[0268] c) Essentially as in example a) except that the polymerization temperature is 50°C. Polymerization activity: 7.76 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight M w = 1.67 kg mol -1 , the molecular weight distribution M w / M n = 1.7, the polymer T m = 126.0°C.

[0269] d) Essentially as in example a) except that the polymerization temperature is 60°C. Polymerization activity: 9.38 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight M w = 1.47 kg mol -1 , the molecular weight distribution M w / M n = 2.0, the polymer T m = 125.0°C.

[0270] e) Essentially as in example a) except that the polymerization temperature is 70°C. Polymerization activity: 1.62 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight M w = 0.98 kg mol -1 , the molecular weight distribution M w / M n = 1.5, the polymer T m = 123.2°C.

[0271] f) Essentially as in example a) except that the polymerization temperature is 80°C. Polymerization activity: 0.57 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight M w = 0.55 kg mol -1 , the molecular weight distribution M w / M n = 1.7, the polymer T m = 122.5°C.

[0272] g) Essentially as in example d) except that the co-catalyst MMAO (2.0 mol / L in toluene) is used in an amount of 1.5 mL to give Al / Fe = 1500:1. Polymerization activity: 1.39 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight M w = 2.95 kg mol-1 , the molecular weight distribution Mw / Mn w n = 1.5, the polymer Tg m = 129.6°C.

[0273] h) Essentially as in method d) of this example, except that the amount of cocatalyst MMAO (2.0 mol / L in toluene) was 1.8 mL, giving Al / Fe = 1750:1. Polymerization activity: 7.86 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight Mw w = 1.78 kg mol -1 , the molecular weight distribution Mw / Mn w n = 1.8, the polymer Tg m = 128.6°C.

[0274] i) Essentially as in method d) of this example, except that the amount of cocatalyst MMAO (2.0 mol / L in toluene) was 2.3 mL, giving Al / Fe = 2250:1. Polymerization activity: 5.30 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight Mw w = 1.55 kg mol -1 , the molecular weight distribution Mw / Mn w n = 1.8, the polymer Tg m = 123.5°C.

[0275] j) Essentially as in method d) of this example, except that the amount of cocatalyst MMAO (2.0 mol / L in toluene) was 2.5 mL, giving Al / Fe = 2500:1. Polymerization activity: 4.22 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight Mw w = 1.39 kg mol -1 , the molecular weight distribution Mw / Mn w n = 1.9, the polymer Tg m = 124.1°C.

[0276] k) Essentially as in method d) of this example, except that the amount of cocatalyst MMAO (2.0 mol / L in toluene) was 3.0 mL, giving Al / Fe = 3000:1. Polymerization activity: 3.87 x 10 6 g / mol (Fe)h -1 , the polymerization molecular weight Mw w = 1.15 kg mol -1 ​​​​, the molecular weight distribution Mw / Mn w / M n = 1.6, the polymer T m = 123.9°C.

[0277] Example 38, ethylene polymerization under pressure using the combination of complex Fe-1 and MMAO as catalyst

[0278] Essentially the same as example 37d), with the difference that the procatalyst is Fe-1. The polymerization activity: 24.55 x 10 6 g / mol (Fe) h -1 , the molecular weight of the polymer Mw w = 42.32 kg mol -1 , the molecular weight distribution Mw / Mn w / M n = 11.9, the polymer T m = 128.2°C.

[0279] Example 39, ethylene polymerization under pressure using the combination of complex Fe-2 and MMAO as catalyst

[0280] Essentially the same as example 37d), with the difference that the procatalyst is Fe-2. The polymerization activity: 25.20 x 10 6 g / mol (Fe) h -1 , the molecular weight of the polymer Mw w = 62.41 kg mol -1 , the molecular weight distribution Mw / Mn w / M n = 18.3, the polymer T m = 129.0°C.

[0281] Example 40, ethylene polymerization under pressure using the combination of complex Fe-3 and MMAO as catalyst

[0282] Essentially the same as example 37d), with the difference that the procatalyst is Fe-3. The polymerization activity: 13.46 x 10 6 g / mol (Fe) h -1 , the molecular weight of the polymer Mw w = 7.73 kg mol -1 , the molecular weight distribution Mw / Mn w / M n = 2.7, the polymer T m = 128.6°C.

[0283] Example 41, ethylene polymerization under pressure using the combination of complex Fe-4 and MMAO as catalyst

[0284] Essentially the same as example 37d), with the difference that the procatalyst is Fe-4. The polymerization activity: 5.29 x 106 g / mol (Fe) h -1 , the molecular weight Mw w = 1.36 kg mol -1 , the molecular weight distribution Mw w / Mn n = 1.6, the polymer Tm m = 121.6°C.

[0285] Example 42, ethylene polymerization under pressure using the combination of complex Fe-6 and MMAO as catalyst

[0286] Essentially as in Example 37d), with the difference that the procatalyst is Fe-6. The polymerization activity: 1.51 x 10 6 g / mol (Fe) h -1 , the molecular weight Mw w = 2.59 kg mol -1 , the molecular weight distribution Mw w / Mn n = 2.3, the polymer Tm m = 126.5°C.

[0287] Example 43, ethylene polymerization under pressure using the combination of complex Fe-7 and MMAO as catalyst

[0288] Essentially as in Example 37d), with the difference that the procatalyst is Fe-7. The polymerization activity: 11.78 x 10 6 g / mol (Fe) h -1 , the molecular weight Mw w = 1.92 kg mol -1 , the molecular weight distribution Mw w / Mn n = 2.1, the polymer Tm m = 127.2°C.

[0289] Example 44, ethylene polymerization under pressure using the combination of complex Fe-8 and MMAO as catalyst

[0290] Essentially as in Example 37d), with the difference that the procatalyst is Fe-8. The polymerization activity: 21.35 x 10 6 g / mol (Fe) h -1 , the molecular weight Mw w = 9.38 kg mol -1 , the molecular weight distribution Mw w / Mn n = 7.1, the polymer Tm m = 126.5°C.

[0291] Example 45 Polymerization of ethylene under pressure using the combination of complex Fe-9 and MMAO as catalyst

[0292] Example 45 Polymerization of ethylene under pressure using the combination of complex Fe-9 and MMAO as catalyst 6 g / mol (Fe) h -1 , the polymerization molecular weight M w = 25.51 kg mol -1 , the molecular weight distribution M w / M n = 7.4, the polymer T m = 130.3 °C.

[0293] Example 46 Polymerization of ethylene under pressure using the combination of complex Fe-8 and MAO as catalyst

[0294] Example 46 Polymerization of ethylene under pressure using the combination of complex Fe-8 and MAO as catalyst 6 g / mol (Fe) h -1 , the polymerization molecular weight M w = 8.63 kg mol -1 , the molecular weight distribution M w / M n = 6.8, the polymer T m = 126.4 °C.

[0295] Example 47 Polymerization of ethylene under pressure using the combination of complex Fe-8 and MAO as catalyst

[0296] Example 47 Polymerization of ethylene under pressure using the combination of complex Fe-8 and MAO as catalyst 6 g / mol (Fe) h -1 , the polymerization molecular weight M w = 7.06 kg mol -1 , the molecular weight distribution M w / M n = 6.8, the polymer T m = 126.6 °C.

[0297] The above describes embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A complex, having a structure as shown in the following formula (I): Formula (I) wherein, The complex shown in formula (I) is at least one of the following complexes: Complex Co-1 : where M is Co, R = cyclopentyl, R 1 = methyl, R 4 = benzhydryl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Co-2: where M is Co, R = benzhydryl, R 1 = methyl, R 4 = cyclopentyl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Co-3: where M is Co, R = cyclopentyl, R 1 = benzhydryl, R 4 = methyl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Co-4: where M is Co, R = cyclopentyl, R 1 = H, R 4 = H, R 2 = H, R 3 = H, R 5 = H, R 6 = H, R 7 = H. Complex Co-5: where M is Co, R = cyclohexyl, R 1 = H, R 4 = H, R 2 = H, R 3 = H, R 5 = H, R 6 = H, R 7 = H Complex Co-6: where M is Co, R = cyclooctyl, R 1 = H, R 4 = CH3, R 2 = CH3, R 3 = CH3, R 5 = CH3, R 6 = CH3, R 7 = H Complex Co-7: where M is Co, R = methyl, R 1 = H, R 4 = H, R 2 = H, R 3 = H, R 5 = H, R 6 = H, R 7 = H Complex Co-8: wherein M is Co, R = F, R 1 = H 4 = H 2 = H 3 = H 5 = H 6 = H 7 = H Complex Co-9: where M is Co, R = Cl, R 1 = Cl, R 4 = Cl, R 2 = Cl, R 3 = Cl, R 5 = Cl, R 6 = Cl, R 7 = H; Complex Fe-1 : wherein M is Fe, R = cyclopentyl, R 1 = methyl, R 4 = benzhydryl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Fe-2: where M is Fe, R = benzhydryl, R 1 = methyl, R 4 = cyclopentyl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Fe-3: where M is Fe, R = cyclopentyl, R 1 = benzhydryl, R 4 = methyl, R 2 , R 3 , R 5 , R 6 , R 7 is H; Complex Fe-4: where M is Fe, R = cyclopentyl, R 1 = H 4 = H 2 = H 3 = H 5 = H 6 = H 7 = H Complex Fe-5: where M is Fe, R = cyclohexyl, R 1 = H 4 = H 2 = H 3 = H 5 = H 6 = H 7 = H Complex Fe-6: where M is Fe, R = cyclooctyl, R 1 = H 4 = H 2 = H 3 = H 5 = H 6 = H 7 = H Complex Fe-7: where M is Fe, R = methyl, R 1 = H, R 4 = H, R 2 = H, R 3 = H, R 5 = H, R 6 = H, R 7 = H. Complex Fe-8: wherein M is Fe, R = F, R 1 = H 4 = diphenylmethyl, R 2 = H 3 = H 5 = H 6 = H 7 = H Complex Fe-9: where M is Fe, R = CI, R 1 = H, R 4 = H, R 2 = H, R 3 = H, R 5 = H, R 6 = H, R 7 = H.

2. A method of preparing the complex of claim 1 comprising: The compound shown in the following formula (II), MX2 and the aniline compound shown in formula (III) are reacted to obtain the compound shown in formula (I), wherein R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , M, X are as defined in claim 1. 3.The preparation method according to claim 2, wherein the MX2 is selected from one or more of halides containing iron or cobalt, hydrates or other solvates of the halides. 4.The preparation method according to claim 3, wherein the MX2 is one or more of FeCl2, FeCl2•4H2O or CoCl2•6H2O. 5.The preparation method according to claim 3, wherein the temperature of the reaction is 100-160℃. 6.The preparation method according to claim 3, wherein the reaction is carried out in an inert gas atmosphere.

7. Use of the complex according to claim 1, characterized in that, It is used for catalyzing olefin polymerization reaction.

8. Use according to claim 7, characterized in that, It is used for catalyzing ethylene polymerization reaction.

9. A catalyst composition characterized in that, It comprises a main catalyst and optionally a cocatalyst, wherein the main catalyst is selected from the complex according to claim 1.

10. The catalyst composition of claim 9, wherein, The cocatalyst is selected from one or more of aluminoxane, alkylaluminum, chlorinated alkylaluminum.

11. The catalyst composition of claim 10, wherein, The aluminoxane is selected from one or both of methylaluminoxane or triisobutylaluminum modified methylaluminoxane; the chlorinated alkylaluminum is selected from one or both of chlorinated diethylaluminum or chlorinated dimethylaluminum. 12.A preparation method of olefin polymer, comprising the following step: catalyzing olefin to carry out polymerization reaction under the action of the complex according to claim 1 or the catalyst composition according to any one of claims 9-11 to obtain olefin polymer.

13. The production method according to claim 12, wherein the temperature of the polymerization reaction is 30 ~ 100 o C; The time of the polymerization reaction is 5-60 min; The pressure of the polymerization reaction is 0.5-10 atm. 14.The preparation method according to claim 12, wherein the olefin is ethylene.

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