CN108794545B - Tert-butyl-containing asymmetric α -diimine nickel complex for preparing ultra-high molecular weight polyethylene elastomer, preparation method and application - Google Patents

Abstract

The invention provides an asymmetric α -diimine nickel complex containing tert-butyl, an intermediate, a preparation method and application thereof, wherein the prepared nickel complex has a single catalytic activity center, can realize the regulation and control of polymer molecular weight and branching degree by changing a ligand structure and polymerization conditions, and has the advantages of high catalytic activity, low cost, stable performance and the like⁷g·mol^‑1(Ni)·h^‑1The weight average molecular weight M of the polyethylene obtained_wIn the range of 1.0-30.8X 10⁵g·mol^‑1The molecular weight distribution is between 1.9 and 5.0, the regulation and control performance on the molecular weight of the polyethylene is shown, the polyethylene can be used for preparing the ultra-high molecular weight polyethylene, and the obtained polyethylene has high branching degree and is a potential polyolefin elastomer.

Description

Tert-butyl-containing asymmetric α -diimine nickel complex for preparing ultra-high molecular weight polyethylene elastomer, preparation method and application

Technical Field

The invention relates to the field of polyolefin catalysts, in particular to a tert-butyl-containing asymmetric α -diimine nickel complex for preparing an ultrahigh molecular weight polyethylene elastomer, an intermediate, a preparation method and application thereof.

Background

Polyethylene, which is the fastest-developing, largest-yield and most-versatile synthetic resin, is widely applied to many fields such as industry, agriculture, military, medical health and daily life. The extensive development and application of polyethylene products is not independent of the development of olefin polymerization catalysts. Polyethylene Catalysts which have been commercialized at present mainly include Ziegler-Natta type Catalysts (DEPat 889229 (1953); IT Pat 536899(1955) and IT Pat545332 (1956); chem.Rev.,2000,100,1169 and the related references of the specialty), Phillips type Catalysts (Belg.Pat.530617 (1955); chem.Rev.1996,96,3327) and metallocene type Catalysts (W.Kaminsky, Metaorganic Catalysts for Synthesis and polymerization, Berin: Springer, rl1999), as well as highly efficient ethylene oligomerization and polymerization Catalysts of the late transition metal complex type which have been developed in recent years.

In 1995, the Brookhart group reported that α -diimine coordinated nickel, palladium complexes catalyzed ethylene polymerization (j.am.chem.soc.,1995,117,6414) to yield high molecular weight, highly branched polyethylene having the structure shown in formula 1 and formula 2:

the subject group of the inventor has been devoted to research on ethylene oligomerization and polymerization catalysts and catalytic processes in the past years, and research and development on various types of nickel complex ethylene polymerization catalysts. Wherein, the 4, 5-diazafluorene-9-ketone benzoyl hydrazone nickel compound can better catalyze the oligomerization and polymerization of ethylene (Applied Catalysis A: general.2003,246,11), and the structural formula is shown as formula 3:

then, mononuclear and binuclear nickel pyridinimine complexes are designed and synthesized, ethylene polymerization catalytic reaction is carried out, branched polyethylene is obtained, nuclear magnetic studies prove that a branched chain is butyl (J.Organomet. chem.,2005,690,1570 and J.Organomet. chem.,2005,690,1739), and by utilizing the characteristics, novel polyethylene resin (shown in formula 4 and formula 5) is developed and designed.

However, the catalytic performance of the above catalysts, as well as the conditions and efficiency of the preparation process thereof, still need to be further improved.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a tertiary butyl-containing asymmetric α -diimine nickel complex shown as the following formula (I):

wherein R is¹The same or different, each independently selected from H, F, Cl, Br, I or optionally substituted by one or more R³Substituted of the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group;

R²selected from H, halogen, C_1-6Alkyl-or C_1-6An alkoxy group;

x, which are identical or different, are each independently selected from halogen;

each R³Can be the same or different and are respectively and independently selected from H, F, Cl, Br, I and C_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group.

Preferably, R¹The same or different, each is independently selected from H, F, Cl, Br, I, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group;

x is the same or different and is independently selected from F, Cl and Br.

More preferably, R¹Are the same or different and are each independently selected from C_1-6Alkyl or C_1-6An alkoxy group; r²Is selected from H or C_1-6An alkyl group; x is the same or different and is independently selected from Cl and Br.

Also preferably, R¹Are the same or different and are each independently selected from C_1-3An alkyl group; r²Is selected from H or C_1-3An alkyl group.

Still more preferably, R¹Identical or different, each independently selected from methyl, ethyl or isopropyl; r²Selected from hydrogen or methyl.

Most preferably, the nickel complex has a structure represented by the following formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):

wherein X is the same or different and is independently selected from Cl and Br.

By way of example, the complex of formula (I) may be selected from complexes having the following group definitions:

C1:R¹＝Me；R²h; x is Br;

C2:R¹＝Et；R²h; x is Br;

C3:R¹＝i-Pr；R²h; x is Br;

C4:R¹＝Me；R²me; x is Br;

C5:R¹＝Et；R²me; x is Br;

C6:R¹＝Me；R²h; x is Cl;

C7:R¹＝Et；R²h; x is Cl;

C8:R¹＝i-Pr；R²h; x is Cl;

C9:R¹＝Me；R²me; x is Cl;

C10:R¹＝Et；R²me; and X is Cl.

The present invention also provides an intermediate of a tert-butyl group-containing asymmetric α -diimine nickel complex represented by the following formula (II):

wherein, in the formula (II), R¹Are the same or different and are each independently selected from H, F,Cl, Br, I or optionally unsubstituted or substituted by one or more R³Substituted of the following groups: c_1-6Alkyl radical, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group;

R²selected from H, halogen, C_1-6Alkyl or C_1-6An alkoxy group;

R³having the definitions as described above.

Preferably, R¹The same or different, each is independently selected from H, F, Cl, Br, I, C_1-6Alkyl-, C_1-6Alkoxy radical, C_3-10Cycloalkyl radical, C_3-10Cycloalkyl oxy, C_6-14Aryl radical, C_6-14An aryloxy group.

More preferably, R¹Are the same or different and are each independently selected from C_1-6Alkyl or C_1-6An alkoxy group; r²Is selected from H or C_1-6An alkyl group.

Also preferably, R¹Are the same or different and are each independently selected from C_1-3An alkyl group; r²Is selected from H or C_1-3An alkyl group.

Still more preferably, R¹Identical or different, each independently selected from methyl, ethyl or isopropyl; r²Selected from hydrogen or methyl.

Most preferably, the nickel complex intermediate has a structure represented by the following formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):

namely, the nickel complex intermediate represented by the formula (II) is selected from complex intermediates defined by the following groups:

L1:R¹＝Me；R²＝H；

L2:R¹＝Et；R²＝H；

L3:R¹＝i-Pr；R²＝H；

L4:R¹＝Me；R²＝Me；

L5:R¹＝Et；R²＝Me。

the invention also provides a catalyst composition which comprises a main catalyst and an optional cocatalyst, wherein the main catalyst is selected from the nickel complex shown in the formula (I).

According to the present invention, the cocatalyst may be selected from one or more of aluminoxane, alkylaluminum, and alkylaluminum chloride.

According to the present invention, the aluminoxane may be selected from one or both of Methylaluminoxane (MAO) or triisobutylaluminum-Modified Methylaluminoxane (MMAO).

According to the invention, the alkylaluminum chloride may be chosen from diethylaluminum chloride (Et)₂AlCl), dimethylaluminum chloride (Me)₂AlCl), preferably diethylaluminum chloride (Et)₂AlCl)。

According to the invention, when the catalyst composition further comprises a cocatalyst, the molar ratio of the metal Al in the cocatalyst to the central metal Ni of the nickel complex represented by formula (I) is (200-4000): 1, preferably (300-2000): 1, and may be, for example, 200:1, 500:1, 1000:1, 1500:1, 2000:1 or 3000: 1.

When the cocatalyst is Methylaluminoxane (MAO), the molar ratio of metal Al in the Methylaluminoxane (MAO) to the central metal Ni of the nickel complex shown in the formula (I) is (1000-3000): 1, and the preferred molar ratio is 1000: 1.

Wherein the cocatalyst is dimethyl aluminum chloride (Me)₂AlCl), dimethylaluminum chloride (Me)₂The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (100-1000: 1), and the preferred molar ratio is 200: 1.

Wherein, when the cocatalyst is triisobutylaluminum-Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutylaluminum-Modified Methylaluminoxane (MMAO) to the central metal Ni of the nickel complex shown in the formula (I) is (500-4000): 1, preferably (1000-4000): 1, for example, 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 3500:1 or 4000: 1;

wherein the cocatalyst is diethylaluminum chloride (Et)₂AlCl), diethylaluminum chloride (Et)₂The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex represented by the formula (I) is (200-1000): 1, preferably (200-800): 1, and may be, for example, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1 or 800: 1.

According to an embodiment of the present invention, when the cocatalyst is diethylaluminum chloride, the molar ratio of the metal Al in diethylaluminum chloride to the central metal Ni of the nickel complex represented by formula (I) may be (200 to 800):1, preferably the molar ratio is (500 to 700):1, and more preferably 600: 1; when the cocatalyst is triisobutylaluminum-modified methylaluminoxane, the molar ratio of the metal Al in the triisobutylaluminum-modified methylaluminoxane to the central metal Ni of the nickel complex represented by formula (I) may be (1000 to 4000):1, preferably (2000 to 4000):1, and more preferably 3000: 1.

The invention also provides a preparation method of the asymmetric α -diimine nickel complex containing the tert-butyl group, which is shown in the formula (I), and comprises the following steps:

and (2) reacting (such as a complexation reaction) the compound shown in the formula (II) with a nickel-containing compound to obtain the nickel complex shown in the formula (I).

According to the invention, the nickel-containing compound may be selected from nickel-containing halides, which may be (DME) NiBr, for example₂、NiCl₂·6H₂O or NiBr₂Such as (DME) NiBr₂Or NiCl₂·6H₂O。

According to the invention, the reaction is preferably carried out in the absence of oxygen, for example under the protection of an inert gas such as nitrogen.

According to the invention, the molar ratio of the nickel-containing compound to the compound shown in the formula (II) can be 1: 1-2, preferably 1: 1-1.5; further preferably 1: 1.1.

According to the invention, the temperature of the reaction may be in the range of from 0 to 35 ℃, for example from 10 to 30 ℃, such as from 20 to 25 ℃; the reaction time may be 8 to 16 hours, preferably 12 to 16 hours, more preferably 14 to 16 hours.

According to the present invention, the reaction may be carried out in an organic solvent, which may be selected from one or more of halogenated alkanes or alcoholic solvents, such as one or both of dichloromethane or ethanol.

Preferably, the resulting nickel complex of formula (I) can be further purified. The purification method may comprise the steps of:

a) the solvent of the compound shown in the formula (I) is pumped by a vacuum pump, and then the compound is dissolved in an organic solvent (such as anhydrous ether);

b) after precipitation, the solid was separated from the liquid, washed with anhydrous ether and dried.

The invention also provides a preparation method of an intermediate of the asymmetric α -diimine nickel complex containing the tertiary butyl group shown in the formula (II), which comprises the following steps:

1) performing substitution reaction on acenaphthenone shown in a formula (III) and aniline shown in a formula (IV) to obtain 2-aniline acenaphthenone shown in a formula (V);

2) carrying out condensation reaction on the 2-phenylamine acenaphthenone shown in the formula (V) obtained in the step 1) and a compound shown in the formula (VI) to obtain a compound shown in the formula (II);

according to the invention, in step 1), the substitution reaction can be carried out under catalysis of p-toluenesulfonic acid.

According to the invention, in step 1), the substitution reaction can be carried out in a solvent, for example in an aromatic hydrocarbon solvent, such as toluene.

According to the present invention, in step 1), the substitution reaction is preferably carried out under heating under reflux for 3 to 8 hours, more preferably 5 to 8 hours.

According to the invention, in the step 1), the molar charge ratio of the acenaphthylene dione shown in the formula (III) and the aniline shown in the formula (IV) can be 1-2: 1, and is preferably 1.1: 1.

According to the present invention, preferably, the obtained 2-anilinoacenaphthenone represented by formula (V) can be further purified. The purification method may comprise the steps of:

a) dissolving 2-phenylamine acenaphthenone shown in a formula (V) obtained in the step 1) in dichloromethane;

b) loading with silica gel, performing column chromatography with silica gel column, eluting with mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether and ethyl acetate is preferably 50:1) as eluent, detecting the eluate by thin layer chromatography (the developer is mixed solvent of petroleum ether and ethyl acetate at volume ratio of 10:1, and collecting the third fraction);

c) removing the solvent to obtain the purified 2-phenylalanenaphthenone represented by the formula (V).

According to the invention, in step 2), the condensation reaction can be carried out under catalysis of p-toluenesulfonic acid.

According to the invention, in step 2), the condensation reaction can be carried out in a solvent, for example in an aromatic hydrocarbon solvent, such as toluene.

According to the present invention, in step 2), the condensation reaction may be performed under heating reflux for 6 to 10 hours, preferably 8 to 10 hours.

According to the invention, in the step 2), the molar charge ratio of the 2-phenylaniline acenaphthenone represented by the formula (V) to the compound represented by the formula (VI) can be 1: 1-2, and the preferred molar ratio is 1: 1.1.

According to the present invention, preferably, the compound represented by formula (II) obtained may be further purified. The purification method may comprise the steps of:

a') dissolving the compound of formula (II) obtained in step 2) in dichloromethane;

b') carrying by using alkaline alumina, carrying out column chromatography by using an alkaline alumina column, eluting by using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of the petroleum ether to the ethyl acetate is preferably 50:1) as an eluent, detecting an eluted fraction by using thin-layer chromatography, and collecting a second fraction;

c') removing the solvent to obtain a purified compound represented by the formula (II).

The invention also provides a process for preparing polyethylene, which comprises polymerizing ethylene in the presence of the catalyst composition as described above.

Preferably, the temperature of the polymerization reaction is 20-100 ℃, for example, 20 ℃, 30 ℃ or 80 ℃; the polymerization reaction time is 5-120 min, for example, 5min, 10min, 15min, 45min, 60min or 120 min; the pressure of the polymerization reaction is 0.5 to 10atm, and may be, for example, 5atm or 10 atm.

According to the present invention, the solvent for the polymerization reaction may be one or more selected from toluene, dichloromethane, ethanol, tetrahydrofuran, hexane, or cyclohexane.

According to the invention, the polymerization is preferably carried out under an ethylene atmosphere.

The invention also provides application of the asymmetric α -diimine nickel complex containing the tertiary butyl group shown in the formula (I) in catalysis of olefin polymerization reaction, preferably ethylene polymerization reaction.

The invention also provides the use of the catalyst composition in catalysing the polymerisation of olefins, in particular ethylene.

The invention also provides application of the tert-butyl-containing asymmetric α -diimine nickel complex intermediate shown in the formula (II) in preparation of the nitro-containing asymmetric α -diimine nickel complex shown in the formula (I).

Term definition and interpretation

The term "C_1-6Alkyl "is understood to mean a linear or branched, saturated monovalent hydrocarbon radical having 1,2, 3, 4,5 or 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl or isomers thereof. In particular, the radicals have 1,2, 3 or 4 carbon atoms ("C)_1-4Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)_1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.

The term "C_3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4,5, 6,7, 8, 9 or 10 carbon atoms. Said C is_3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.

The term "C_6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6,7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C_6-14Aryl group "), in particular a ring having 6 carbon atoms (" C₆Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C₉Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C₁₀Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C₁₃Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)₁₄Aryl), such as anthracenyl.

The term "halogen" includes F, Cl, Br, I.

The invention has the beneficial effects that:

1. the asymmetric α -diimine nickel complex containing tert-butyl and the intermediate thereof have a single catalytic activity center, can realize the regulation and control of the molecular weight and the branching degree of a polymer by changing the ligand structure and the polymerization conditions, and have the advantages of high catalytic activity, low cost, stable performance and the like.

2. The invention provides asymmetric α -diimine nickel complex containing tert-butyl and a preparation method of an intermediate thereof.

3. The asymmetric α -diimine nickel complex containing tert-butyl and the application of the intermediate thereof, the nickel complex is used as a catalyst for ethylene polymerization, and for example, the activity of the nickel complex for ethylene polymerization can be as high as 1.26 multiplied by 10 under the condition of 20-25 DEG, and the nickel complex is used for catalyzing the ethylene polymerization⁷g·mol^-1(Ni)·h^-1The weight average molecular weight M of the prepared polyethylene_wIn the range of 1.0-30.8X 10⁵g·mol^-1The molecular weight distribution is between 1.9 and 5.0, the polyethylene has extremely strong regulation and control performance on the molecular weight of polyethylene, can be used for preparing ultrahigh molecular weight polyethylene, has high branching degree of the obtained polyethylene, reaches the branching degree of 173 plus chains with each 1000 carbon atoms, and is a potential polyolefin elastomer, and the polyethylene prepared by catalyzing ethylene polymerization by the asymmetric α -diimine nickel complex containing tert-butyl has extremely great industrial application potential.

4. The method for preparing the polyethylene provided by the invention is simple to operate, the reaction conditions are mild, and the obtained product is an elastomer with ultrahigh molecular weight and is a potential polyolefin elastomer. Its weight average molecular weight M_wCan be as high as 32.8 multiplied by 10⁵g·mol^-1The molecular weight distribution is between 1.8 and 2.8, and the application prospect is wide.

Drawings

FIG. 1 is a schematic diagram of the crystal structure of complex C1.

FIG. 2 is a schematic diagram of the crystal structure of complex C2.

FIG. 3 is a schematic diagram of the crystal structure of complex C6.

FIG. 4 shows a thermogram of a polymer obtained in example 19 d.

FIG. 5 shows a thermogram of a polymer obtained in example 29 e.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The concentrations in the following examples are molar concentrations unless otherwise specified.

The molecular weight and molecular weight distribution of the polymer obtained in the following ethylene polymerization examples were measured by a conventional high-temperature GPC method, the melting point was measured by a conventional DSC method, and the polymerization activity of the polymer was calculated according to the following formula: polymerization activity ═ polymer yield/(catalyst amount. polymerization time). Reference is made to the method for calculating the degree of branching (Macromolecules,1999,32, 1620-738; Polym., J.1984,16, 731-738).

All of the synthesized compounds described below were confirmed by nuclear magnetic, infrared and elemental analysis.

As a preferred embodiment, the synthesis of the complex in the following examples is carried out according to the following reaction equation:

example 1

Preparing 2- (2, 6-di (benzhydryl) -4-tert-butyl aniline) acenaphthenone shown as a formula (V).

To a solution of 2, 6-bis (benzhydryl) -4-tert-butylaniline (9.63g,20mmol) and acenaphthylene dione (4.00g,22mmol) in toluene (150mL) was added a catalytic amount (1.25g) of p-toluenesulfonic acid and reacted under reflux for 5 h. Removing the solvent, performing silica gel column chromatography on the residue with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:50, detecting the eluted fraction with a thin-layer silica gel plate, collecting a third fraction, and removing the solvent to obtain an orange-yellow solid, wherein the developing solvent is a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 10: 1. Yield: 70 percent. Melting point 186-188 ℃.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3059(w),2958(w),1727(ν(C＝O)m),1657(ν(C＝N)m),1598(s),1582(s),1492(s),1456(m),1332(s),1182(w),1028(m),911(w),825(s).

¹H NMR(400MHz,CDCl₃.TMS):δ8.01(t,J＝8.0Hz,2H,Ph-H),7.71-7.68(m,2H,Ph-H),7.24-7.21(m,4H,Ph-H),7.16(d,J＝6.8Hz,2H,Ph-H),7.04-7.01(m,5H,Ph-H),6.99(s,2H,Ph-H)6.84(d,J＝7.6Hz,4H,Ph-H),6.59(t,J＝7.2Hz,4H,Ph-H),6.40(t,J＝76Hz,2H,Ph-H),6.00(d,J＝7.2Hz,1H,Ph-H),5.44(s,2H,2×CH),1.16(m,9H,C(CH₃)₃).

¹³C NMR(100MHz,CDCl₃.TMS):δ189.7(C＝O),162.3(C＝N),146.6,145.9,143.1,142.4,141.9,131.7,131.1,130.1,129.9,129.6,129.3,128.3,128.0,127.7,127.4,127.2,127.1,126.1,125.4,125.0,123.8,121.4,52.4,34.4,31.4.

elemental analysis C₄₈H₃₉Theoretical NO (645.85) C, 89.27; h, 6.09; n,2.17 Experimental value C, 89.10; h, 6.00; and N,2.14.

Example 2

Preparation of 1- (2, 6-dimethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene [ L1 ] shown in formula (II)]Wherein R is¹Is methyl, R²Is hydrogen.

2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthenone (1.00g,1.55mmol) and 2, 6-dimethylaniline (0.2g,1.65mmol) in toluene (100mL) were added with a catalytic amount of p-toluenesulfonic acid and heated under reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 50. Detecting the eluted fraction by a thin-layer silica gel plate, collecting the second fraction, and removing the solvent to obtain an orange yellow solid. Yield: 32 percent. Melting point 146-148 ℃.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3026(w),2953(w),1659(ν(C＝N)m),1631(ν(C＝N)m),1593(s),1446(s),1361(w),1255(w),1110(w),1031(m),924(s),831(s),775(m),696(s).

¹H NMR(400MHz,CDCl₃.TMS):δ7.70(d,J＝8.0Hz,1H,Ph-H),7.56(d,J＝8.0Hz,1H,Ph-H),7.24-7.21(m,5H,Ph-H),7.18-7.15(m,4H,Ph-H),7.09-7.07(m,5H,Ph-H),6.98-6.91(m,7H,Ph-H),6.59(t,J＝8.0Hz,4H,Ph-H),6.51(d,J＝7.2Hz,1H,Ph-H),6.40(t,J＝7.2Hz,2H,Ph-H),5.95(d,J＝7.2Hz,1H,Ph-H),5.63(s,2H,2×CH),2.21(s,6H,2×CH₃),1.17(m,9H,C(CH₃)₃).

¹³C NMR(100MHz,CDCl₃.TMS):δ163.4(C＝N),161.3(C＝N),149.3,146.7,146.0,143.5,142.0,139.9,131.6,129.8,129.8,129.5,128.9,128.7,128.6,128.3,128.0,127.9,127.6,127.4,126.9,126.0,125.3,125.1,124.8,124.1,123.6,121.6,52.5,34.4,31.5,14.1.

elemental analysis C₅₆H₄₈N₂(749.01) theoretical value C, 89.80; h, 6.46; n,3.74. experimental values: c, 89.71; h, 6.41; and N,2.50.

Example 3

Preparation of 1- (2, 6-diethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene [ L2 ] shown in formula (II)]Wherein R is¹Is ethyl, R²Is hydrogen.

2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthenone (1.00g,1.55mmol) and 2, 6-diethylaniline (0.21g,1.65mmol) in toluene (100mL) were added with a catalytic amount of p-toluenesulfonic acid and heated under reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 50. Detecting the eluted fraction by a thin-layer silica gel plate, collecting the second fraction, and removing the solvent to obtain an orange yellow solid. Yield: 35 percent. Melting point 197-.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3026(w),2959(w),1659(ν(C＝N)m),1632(ν(C＝N)m),1593(m),1447(s),1361(w),1257(m),1111(m),1073(m),923(s),777(w),830(m),695(s).

¹H NMR(400MHz,CDCl₃.TMS):δ7.68(d,J＝8.0Hz,1H),7.52(d,J＝8.0Hz,1H),7.25-7.14(m,10H),7.08(d,J＝7.6Hz,4H),6.99(s,2H),6.92-6.88(m,5H),6.57(t,J＝7.6Hz,4H),6.50(d,J＝7.2Hz,1H),6.39(d,J＝7.6Hz,2H),5.86(d,J＝8.0Hz,1H),5.64(s,2H),2.7-2.65(m,2H),2.54-2.49(m,2H),1.18-1.15(m,15H).

¹³C NMR(100MHz,CDCl₃.TMS):δ163.5,161.6,148.4,146.8,146.0,143.7,142.0,139.9,131.6,130.7,129.7,129.5,128.9,128.6,128.5,127.9,127.7,127.6,127.1,126.9,126.1,126.0,125.4,125.2,124.1,124.0,122.2,52.4,34.4,31.5,24.4,14.1.

elemental analysis C₅₈H₅₂N₂(777.07) theoretical value C, 89.65; h, 6.75; n,3.61 Experimental value C, 89.71; h, 6.97; and N,3.63.

Example 4 production of 1- (2, 6-diisopropylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene [ L3 ] represented by the formula (II)]Wherein R is¹Is isopropyl, R²Is hydrogen.

2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthenone (1.00g,1.55mmol) and 2, 6-diisopropylaniline (0.22g,1.65mmol) in toluene (100mL) were added with a catalytic amount of p-toluenesulfonic acid and heated under reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 50. Detecting the eluted fractions by a thin-layer silica gel plate, collecting a third fraction, and removing the solvent to obtain a light yellow solid. Yield: 28% melting point 211-213 ℃.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3027(w),2959(w)1657(ν(C＝N)m),1635(ν(C＝N)m),1594(m),1453(s),1361(m),1254(m),1110(w),1075(w),923(m),829(w),780(w),695(s).

¹H NMR(400MHz,CDCl₃.TMS):δ7.66(d,J＝8.4Hz,1H),7.48(d,J＝8.0Hz,1H),7.30-7.15(m,10H),7.08(d,J＝7.6Hz,4H),7.00(s,2H),6.90(d,J＝7.2Hz,4H),6.85(t,J＝8.0Hz,1H),6.55(t,J＝7.6Hz,4H),6.43(d,J＝7.2Hz,1H),6.37(t,J＝7.6Hz,2H),5.78(d,J＝7.2Hz,1H),5.65(s,2H),3.17-312(m,2H),1.28(d,J＝6.8Hz,6H),1.18(s,9H),1.01(d,J＝6.8Hz,6H).

¹³C NMR(100MHz,CDCl₃.TMS):δ163.6,162.0,147.1,146.8,146.0,143.8,141.9,140.0,135.7,131.6,129.7,129.5,128.7,128.5,127.9,127.7,127.6,126.9,126.8,125.9,125.4,125.2,124.4,124.2,123.5,122.8,52.3,34.4,31.4,28.4,24.1,23.7.

elemental analysis C₆₀H₅₆N₂(805.12) theoretical value C, 89.51; h, 7.01; n,3.48, the experimental value is C, 89.39; h, 7.43; and N,3.18.

Example 5

Preparation of 1- (2,4, 6-trimethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene [ L4 ] shown as formula (II)]Wherein R is¹Is methyl, R²Is methyl.

2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthenone (1.00g,1.55mmol) and 2,4, 6-trimethylaniline (0.21g,1.65mmol) in toluene (100mL) were added with a catalytic amount of p-toluenesulfonic acid and heated under reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 50. Detecting the eluted fractions by a thin-layer silica gel plate, collecting a third fraction, and removing the solvent to obtain a light yellow solid. Yield: melting point 138 ℃ and 140 ℃.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3028(w),2957(w),1666(ν(C＝N)m),1640(ν(C＝N)m),1595(m),1447(m),1361(w),1269(m),1154(w),1076(w),923(m),823(w),730(s),697(s).

¹H NMR(400MHz,CDCl₃.TMS):δ7.70(d,J＝7.2Hz,1H),7.56(d,J＝8.0Hz,1H),7.27-7.21(m,6H),7.16(t,J＝7.2Hz,2H),7.08(d,J＝7.6Hz,4H),6.97(d,J＝4.8Hz,4H),6.92(s,2H),6.90(s,2H),6.60-6.56(m,5H),6.40(t,J＝7.2Hz,2H),5.94(d,J＝7.2Hz,1H),5.62(s,2H),2.38(s,3H),2.17(s,6H),1.17(s,9H).

¹³C NMR(100MHz,CDCl₃.TMS):δ163.4,161.5,146.8,145.9,143.4,142.0,139.9,132.8,131.5,129.8,129.4,128.9,128.7,128.4,127.9,127.8,127.6,127.3,126.8,126.0,125.3,125.1,124.6,124.0,121.6,53.3,52.4,34.4,31.4,18.0,14.0.

elemental analysis C₅₇H₅₀N₂(763.04) theoretical C, 89.72; h, 6.61; n,3.67, experimental value C, 89.51; h, 6.63; and N,3.56.

Example 6

Preparation of 1- (2, 6-diethyl-4-methylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthylene [ L5 ] shown as formula (II)]Wherein R is¹Is ethyl, R²Is methyl.

To a solution of 2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthenone (1.00g,1.55mmol) and 2, 6-diethyl-4-methylaniline (0.22g,1.65mmol) in toluene (80mL) was added a catalytic amount of p-toluenesulfonic acid and heated under reflux for 8 h. Removing the solvent toluene, and using ethyl acetate and petroleum ether to make the residue have a volume ratio of 1:50 of the mixed solvent is subjected to basic alumina column chromatography. Detecting the eluted fractions by a thin-layer silica gel plate, collecting a third fraction, and removing the solvent to obtain an orange yellow solid. Yield: 42% melting point 186-.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3028(w),2960(w),1667(ν(C＝N)m),1641(ν(C＝N)m),1596(m),1448(m),1361(w),1268(m),1182(w),1076(w),919(m),829(w),732(s),698(s).

¹H NMR(400MHz,CDCl₃.TMS):δ7.67(d,J＝8.4Hz,1H),7.52(d,J＝8.4Hz,1H),7.25-7.21(m,6H),7.17(d,J＝7.2Hz,2H),7.08(d,J＝7.2Hz,4H),7.00(s,2H),6.99(s,2H),6.92(s,2H),6.90(s,2H),6.57(t,J＝6.8Hz,5H),6.38(t,J＝7.2Hz,2H),5.85(d,J＝7.2Hz,1H),5.63(s,2H),2.68-2.59(m,2H),2.53-2.45(m,2H),2.42(s,3H),1.18-1.12(m,15H).

¹³C NMR(100MHz,CDCl₃.TMS):δ163.5,161.7,146.8,145.9,145.8,143.6,141.9,139.9,133.1,131.4,129.7,129.4,128.9,128.6,128.3,127.9,127.6,127.6,127.1,126.8,126.8,125.9,125.3,125.1,124.0,122.2,52.3,34.4,31.4,24.4,14.0,13.9.

elemental analysis C₅₉H₅₄N₂(791.10) theoretical value C, 89.58; h, 6.88; n,3.54, the experimental value is C, 89.32; h, 7.01; n,3.34.

Example 7

Preparing [1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) bromides [ complexes C1]Wherein R is¹Is methyl, R²Is hydrogen and X is bromine.

Reacting (DME) NiBr at room temperature₂(0.055g,0.18mmol) and 1- (2, 6-dimethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene prepared in example 2 (0.15g,0.20mmol) were mixed and dissolved in dichloromethane, stirred under nitrogen for 16h, dichloromethane was removed under reduced pressure, and then diethyl ether was added to precipitate a red solid, which was filtered, washed with diethyl ether and dried to obtain a red solid. Yield: 85 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3026(w),2958(w),1648(ν(C＝N),w),1622(ν(C＝N),m),1583(m),1493(m),1445(s),1291(m),1242(s),1185(m),1078(m),1033(s),920(m),828(m),770(s),699(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-16.62(s,1H,Ar–H_p),3.71(s,9H,–C(CH₃)₃),4.80(s,1H,An–H),5.13(s,3H,Ar–H),5.50(s,5H,Ar–H),6.07(s,1H,An–H),7.03-7.33(m,8H,Ar–H),8.31(s,4H,Ar–H),11.94(broad,1.3H,Ar–CH(Ph)₂),16.01(s,1H,An–H),16.81(s,1H,An–H),20.44(s,1H,An–H),23.16(s,2H,Ar–H),25.14(s,1H,An–H),26.27(s,2H,Ar–H),29.39(s,6H,2×CH₃).

elemental analysis C₅₆H₄₈Br₂N₂Theoretical Ni (967.52) C, 69.52; h, 5.00; n,2.90, Experimental value C, 69.71; h, 5.25; and N,2.95.

Example 8

Preparing [1- (2, 6-diethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) bromides [ complexes C2]Wherein R is¹Is ethyl, R²Is hydrogen and X is bromine.

Reacting (DME) NiBr at room temperature₂(0.055g,0.18mmol) and 1- (2, 6-diethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene prepared in example 3 (0.15g,0.20mmol) is dissolved in dichloromethane, stirred for 16h under the protection of nitrogen, the dichloromethane is removed under reduced pressure, diethyl ether is added to precipitate a red solid, and the red solid is obtained after filtration, washing with diethyl ether and drying. Yield: 87 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3024(w),2958(w),1650(ν(C＝N),w),1624(ν(C＝N),m),1583(m),1494(m),1444(s),1292(m),1262(s),1187(m),1076(m),1029(s),943(m),823(m),767(s),699(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-16.28(s,1H,Ar–H_p),0.73(s,6H,2×CH₃),3.71(s,9H,–C(CH₃)₃),4.81(s,1H,An–H),5.01(s,1H,Ar–H),5.16(s,3H,Ar–H),5.58(s,5H,Ar–H),6.05(s,1H,An–H),7.01-7.30(m,7H,Ar–H),8.28(s,4H,Ar–H),11.75(s,1.25H,Ar–CH(Ph)₂),16.02(s,1H,An–H),16.75(s,1H,An–H),20.45(s,1H,An–H),23.18(s,2H,Ar–H),25.23(s,1H,An–H),25.94(s,2H,Ar–H),26.95(s,2H,–CH₂),28.89(s,2H,–CH₂).

elemental analysis C₅₈H₅₂Br₂N₂Theoretical Ni (995.57) value of C, 69.97; h, 5.26; n,2.81, experimental value C, 69.51; h, 5.29; n,2.77.

Example 9

Preparing [1- (2, 6-diisopropylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) bromides [ complexes C3]Wherein R is¹Is isopropyl, R²Is hydrogen and X is bromine.

Reacting (DME) NiBr at room temperature₂(0.055g,0.18mmol) and 1- (2, 6-diisopropylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene prepared in example 4 (0.16g,0.20mmol) were mixed and dissolved in dichloromethane, and stirred under nitrogen for 16h, after dichloromethane was removed under reduced pressure, diethyl ether was added to precipitate a red solid, which was filtered, washed with diethyl ether and dried to obtain a red solid. Yield: 81 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3022(w),2968(w),1638(ν(C＝N),w),1616(ν(C＝N),m),1577(m),1494(m),1447(s),1292(m),1259(w),1181(m),1075(w),1027(s),938(m),844(w),808(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-15.77(s,1H,Ar–H_p),1.67(s,6H,2×CH₃),1.84(s,6H,2×CH₃),3.85(s,9H,–C(CH₃)₃),4.88(s,1H:An–H),5.25(s,5H,Ar–H),5.57(s,1H,An–H),5.78(s,3H,Ar–H),7.02(s,3H,Ar–H),7.24(5H,Ar–H),8.24(s,4H,Ar–H),12.51(broad,1.28H,Ar–CH(Ph)₂),16.24(s,1H,An–H),17.25(s,1H,An–H),21.31(s,1H,An–H),23.80(s,2H,Ar–H),25.58(s,1H:An–H；2H:Ar–H).

elemental analysis C₆₀H₅₆Br₂N₂Theoretical Ni (1023.62) value of C, 70.40; h, 5.51; n,2.74, experimental value C, 70.23; h, 5.94; and N,2.62.

Example 10

Preparing [1- (2,4, 6-trimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) bromides [ complexes C4]Wherein R is¹Is methyl, R²Is methyl and X is bromine.

Reacting (DME) NiBr at room temperature₂(0.055g,0.18mmol) and 1- (2,4, 6-trimethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene prepared in example 5 (0.16g,0.20mmol) were mixed and dissolved in dichloromethane, stirred under nitrogen for 16h, after dichloromethane was removed under reduced pressure, diethyl ether was added to precipitate a red solid, which was filtered, washed with diethyl ether and dried to obtain a red solid. Yield: 85 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3027(w),2961(w),1648(ν(C＝N),w),1621(ν(C＝N),m),1583(m),1492(m),1360(w),1292(m),1262(w),1183(m),1079(w),1031(s),917(w),864(m),828(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ3.69(s,9H,–C(CH₃)₃),4.75(s,1H,An–H),5.13(s,6H,Ar–H),5.56(s,4H,Ar–H),6.17(s,1H,An–H),7.07(s,2H,Ar–H),7.35(s,4H,Ar–H),8.37(s,4H,Ar–H),11.75(broad,1.19H,Ar–CH(Ph)₂),15.99(s,1H,An–H),16.75(s,1H,An–H),20.19(s,1H,An–H),23.10(s,2H,Ar–H),25.67(s,1H,An–H),25.93(s,2H,Ar–H),29.43(s,6H,2×CH₃),34.90(s,3H,–CH₃).

elemental analysis C₅₇H₅₀Br₂N₂Theoretical Ni (981.54) value of C, 69.75; h, 5.13; n,2.85, the experimental value is C, 69.61; h, 5.04; and N,2.70.

Example 11

Preparing [1- (2, 6-diethyl-4-methylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) bromides [ complexes C5]Wherein R is¹Is ethyl, R²Is methyl and X is bromine.

Reacting (DME) NiBr at room temperature₂(0.055g,0.18mmol) and 1- (2, 6-diethyl-4-methylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene prepared in example 6 (0.16g,0.20mmol) were mixed and dissolved in dichloromethane, stirred under nitrogen for 16h, after dichloromethane was removed under reduced pressure, diethyl ether was added to precipitate a red solid, which was filtered, washed with diethyl ether and dried to obtain a red solid. Yield: 88 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3025(w),2962(w),1651(ν(C＝N),w),1622(ν(C＝N),m),1583(m),1494(m),1452(s),1363(w),1293(m),1261(w),1186(m),1075(w),1048(w),1032(m),962(w),897(m),866(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ3.73(s,9H,–C(CH₃)₃),4.77(s,1H,An–H),5.16(s,3H,Ar–H),5.59(s,5H,Ar–H),6.16(s,1H,An–H),7.07(s,3H,Ar–H),7.35(s,5H,Ar–H),8.36(s,4H,Ar–H),11.47(broad,1.27H,Ar–CH(Ph)₂),16.10(s,1H,An–H),16.79(s,1H,An–H),20.34(s,1H,An–H),23.28(s,2H,Ar–H),25.76(s,2H,An–H),25.96(s,1H,Ar–H),27.13(s,2H,CH₂),28.98(s,2H,CH₂)35.03(s,3H,–CH₃).

elemental analysis C₅₉H₅₄Br₂N₂Theoretical Ni (1009.60) value of C, 70.19; h, 5.39; n,2.77, Experimental value C, 70.03; h, 5.42; and N,2.75.

Example 12

Preparing [1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) chloride [ complex C6]Wherein R is¹Is methyl, R²Is hydrogen and X is chlorine.

At room temperature, adding NiCl₂·6H₂Mixing O (0.043g,0.18mmol) and 1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene (0.15g,0.20mmol), dissolving in a mixed solution of dichloromethane and ethanol (volume ratio 15:5), stirring for 16h under the protection of nitrogen, removing the solvent under reduced pressure, adding diethyl ether to precipitate a red solid, filtering, washing with diethyl ether, and drying to obtain the red solid. Yield: 88 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3020(w),2961(s),1652(ν(C＝N),w),1624(ν(C＝N),m),1584(m),1491(w),1445(m),1291(w),1222(w),1118(m),1079(m),1034(s),920(w),829(s),772(s),744(m).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-14.83(s,1H,Ar–H_p),-0.80(s,3H,Ar–H),4.50(s,9H,–C(CH₃)₃),4.74-4.76(m,1H,An–H；2H,Ar–H),5.00(s,5H,Ar–H),5.89(s,1H,An–H),7.02-7.05(m,2H,Ar–H),7.31(s,4H,Ar–H),8.60(s,4H,Ar–H),10.94(broad,1.39H,Ar–CH(Ph)₂),15.96(s,1H,An–H),16.72(s,1H,An–H),21.15(s,1H,An–H),24.79(s,2H,Ar–H),25.42(s,1H,An–H),27.58(s,2H,Ar–H),27.98(s,6H,2×CH₃).

elemental analysis C₅₆H₄₈Cl₂N₂Theoretical Ni (878.61) C, 76.55; h, 5.51; n,3.19 Experimental value C, 75.28; h, 5.50; and N,2.98.

Example 13

Preparing [1- (2, 6-diethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) chloride [ complex C7]Wherein R is¹Is ethyl, R²Is hydrogen and X is chlorine.

At room temperature, adding NiCl₂·6H₂O (0.043g,0.18mmol) and 1- (2, 6-diethylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthylene (0.15g,0.20mmol) is mixed and dissolved in a mixed solution of dichloromethane and ethanol (volume ratio is 15:5), stirred for 16 hours under the protection of nitrogen, the solvent is removed under reduced pressure, then ether is added to precipitate red solid, the red solid is filtered, washed by ether and dried to obtain the red solid. Yield: 86 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3236(w),2965(s),1653(ν(C＝N),w),1628(ν(C＝N),m),1586(s),1494(s),1444(s),1292(m),1264(w),1188(s),1077(m),1032(m),944(w),869(w),823(m).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-14.19(s,1H,Ar–H_p),-0.38(s,3H,Ar–H),0.56(s,6H,2×CH₃),4.51(s,9H,–C(CH₃)₃),4.85(s,1H,An–H；2H,Ar–H),5.12(s,5H,Ar–H),5.92(s,1H,An–H),6.99-7.02(m,2H,Ar–H),7.25(s,4H,Ar–H),8.52(s,4H,Ar–H),10.94(broad,0.6H,Ar–CH(Ph)₂),15.92(s,1H,An–H),16.59(s,1H,An–H),21.16(s,1H,An–H),24.03(s,2H,CH₂),24.70(s,2H,Ar–H),25.30(s,1H,An–H),26.76(s,2H,CH₂),27.05(s,2H,Ar–H).

elemental analysis C₅₈H₅₂Cl₂N₂Theoretical Ni (906.66) values C, 76.84; h, 5.78; n,3.09. experimental value C, 75.13; h, 5.78; and N,3.04.

Example 14

Preparing [1- (2, 6-diisopropylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) chloride [ complex C8]Wherein R is¹Is isopropyl, R²Is hydrogen and X is chlorine.

At room temperature, adding NiCl₂·6H₂Mixing O (0.043g,0.18mmol) and 1- (2, 6-diisopropylaniline) -2- (2, 6-bis (benzhydryl) -4-tert-butylaniline) acenaphthene (0.16g,0.20mmol), dissolving in a mixed solution of dichloromethane and ethanol (volume ratio 15:5), stirring for 16h under the protection of nitrogen, removing the solvent under reduced pressure, adding diethyl ether to precipitate a red solid, filtering, washing with diethyl ether, and drying to obtain the red solid. Yield: 81 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3368(b),2966(m),1646(ν(C＝N),w),1620(ν(C＝N),m),1582(s),1446(m),1362(w),1291(m),1261(m),1114(s),1076(m),1031(s),769(m),742(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-13.91(s,1H,Ar–H_p),-0.02(s,3H,Ar–H),1.13(s,6H,2×CH₃),1.55(s,6H,2×CH₃),4.68(s,9H,–C(CH₃)₃),4.88(s,1H,An–H；2H,Ar–H),5.29(s,5H,Ar–H),5.55(s,1H,An–H),6.98(s,2H,Ar–H),7.20(s,4H,Ar–H),8.47(4H,Ar–H),11.21(broad,1.41H,Ar–CH(Ph)₂),16.16(s,1H,An–H),17.09(s,1H,An–H),22.06(s,1H,An–H),25.45(s,2H,CH₂),25.81(s,1H,An–H),26.92(s,2H,Ar–H).

elemental analysis C₆₀H₅₆Cl₂N₂Theoretical Ni (934.72) C, 77.10; h, 6.04; n,3.00. Experimental value C, 76.13; h, 6.54; and N,2.89.

Example 15

Preparing [1- (2,4, 6-trimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) chloride [ complex C9]Wherein R is¹Is methyl, R²Is methyl and X is chlorine.

At room temperature, adding NiCl₂·6H₂Mixing O (0.043g,0.18mmol) and 1- (2,4, 6-trimethylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene (0.16g,0.20mmol), dissolving in a mixed solution of dichloromethane and ethanol (volume ratio 15:5), stirring for 16h under the protection of nitrogen, removing the solvent under reduced pressure, adding diethyl ether to precipitate a red solid, filtering, washing with diethyl ether, and drying to obtain the red solid. Yield: 88 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3425(b)2970(m),1652(ν(C＝N),w),1623(ν(C＝N),m),1585(s),1521(s),1493(m),1438(m),1339(s),1289(m),1082(m),1032(s),912(m),822(m),771(m),699(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-0.87(s,3H,Ar–H),4.46(s,9H,–C(CH₃)₃),4.69(s,1H,An–H)4.76(s,2H,Ar–H),4.99(s,5H,Ar–H),6.00(s,1H,An–H),7.05(s,2H,Ar–H),7.32(s,4H,Ar–H),8.64(s,4H,Ar–H),10.51(broad,1.31H,Ar–CH(Ph)₂),15.93(s,1H,An–H),16.66(s,1H,An–H),20.85(s,1H,An–H),24.67(s,2H,Ar–H),25.97(s,1H,An–H),27.22(s,2H,Ar–H),28.00(s,6H,2×CH₃),35.50(s,3H,CH₃).

elemental analysis C₅₇H₅₀Cl₂N₂Theoretical Ni (892.63) C, 76.70; h, 5.65; n,3.14, the experimental value is C, 75.00; h, 5.65; and N,2.92.

Example 16

Preparing [1- (2, 6-diethyl-4-methylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene shown as formula (I)]Nickel (II) chloride [ complex C10]Wherein R is¹Is ethyl, R²Is methyl and X is chlorine.

At room temperature, adding NiCl₂·6H₂Mixing O (0.043g,0.18mmol) and 1- (2, 6-diethyl-4-methylaniline) -2- (2, 6-di (benzhydryl) -4-tert-butylaniline) acenaphthene (0.16g,0.20mmol), dissolving in a mixed solution of dichloromethane and ethanol (volume ratio 15:5), stirring for 16h under the protection of nitrogen, removing the solvent under reduced pressure, adding diethyl ether to precipitate a red solid, filtering, washing with diethyl ether, and drying to obtain the red solid. Yield: 84 percent.

The structure validation data is as follows:

FT-IR(KBr,cm^-1):3237(b)2964(m),1655(ν(C＝N),w),1628(ν(C＝N),m),1586(s),1494(s),1445(s),1291m(m),1076(w),1035(w),945(w),867(m),826(m),769(s).

¹H NMR(400MHz,CD₂Cl₂.TMS):δ-0.50(s,3H,Ar–H),0.59(s,6H,2×CH₃),4.53(s,9H,–C(CH₃)₃),4.79-4.82(m,1H,An–H；2H,Ar–H),5.07(s,5H,Ar–H),5.94(s,1H,An–H),7.03(m,2H,Ar–H),7.28(s,4H,Ar–H),8.61(s,4H,Ar–H),10.52(broad,0.6H,Ar–CH(Ph)₂),15.97(s,1H,An–H),16.60(s,1H,An–H),21.07(s,1H,An–H),24.33(s,2H,CH₂),24.86(s,0.12H,Ar–H),25.95(s,1H,An–H),26.93(s,2H,CH₂；2H,Ar–H),35.28(s,3H,CH₃).

elemental analysis C₅₉H₅₄Cl₂N₂Ni(920.69) theoretical value C, 76.97; h, 5.91; n,3.04. Experimental value C, 75.53; h, 5.74; n,3.33.

Example 17

Ethylene polymerization under pressure with Complex C1 and MAO cocatalyst:

under an ethylene atmosphere, 20mL of toluene, 30mL of a toluene solution of catalyst C1 (2. mu. mol), 1.34mL of co-catalyst MAO (1.46mol/L of the toluene solution), and 50mL of toluene were sequentially charged into a 250mL stainless steel autoclave, at which time Al/Ni was 1000: 1. Mechanical stirring is started, 400 rpm is maintained, and when the polymerization temperature reaches 30 ℃, ethylene is charged into the reaction kettle, and the polymerization reaction starts. The mixture was stirred at 30 ℃ for 30min while maintaining the ethylene pressure at 10 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing.

Polymerization Activity: 0.55X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝114.9℃。(T_mMelting temperature of the polymer, obtained by DSC measurement), molecular weight M of the polymer_w＝6.0×10⁵g·mol^-1，PDI＝6.1(M_wMass average molecular weight of the polymer, obtained by elevated temperature GPC test).

Example 18

By means of complexes C1 and Me₂Ethylene polymerization under pressure with AlCl cocatalyst:

under an ethylene atmosphere, 20mL of toluene, 30mL of a toluene solution of catalyst C1 (2. mu. mol), and 0.4mL of co-catalyst Me₂AlCl (1.00mol/L toluene solution) and 50mL of toluene were sequentially added to a 250mL stainless steel autoclave, at which point Al/Ni was 200: 1. Mechanical stirring is started, 400 rpm is maintained, and when the polymerization temperature reaches 30 ℃, ethylene is charged into the reaction kettle, and the polymerization reaction starts. The mixture was stirred at 30 ℃ for 30min while maintaining the ethylene pressure at 10 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing.

Polymerization Activity: 0.31X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝98.0℃。(T_mMelting temperature of the polymer, obtained by DSC measurement), molecular weight M of the polymer_w＝0.5×10⁶g·mol^-1，PDI＝4.0(M_wMass average molecular weight of the polymer, obtained by elevated temperature GPC test).

Example 19

Using complexes C1 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

a) 20mL of toluene, 30mL of a solution of catalyst C1 (2. mu. mol) in toluene, 0.47mL of cocatalyst Et₂AlCl (1.17mol/L toluene solution) and 50mL of toluene were sequentially charged into a 250mL stainless steel autoclave. At this point, Al/Ni is 200: 1. Mechanical stirring is started, 400 rpm is maintained, and when the polymerization temperature reaches 30 ℃, ethylene is charged into the reaction kettle, and the polymerization reaction starts. The mixture was stirred at 30 ℃ for 30min while maintaining the ethylene pressure at 10 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing.

Polymerization Activity: 8.58X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝58.1℃。(T_mMelting temperature of the polymer, obtained by DSC measurement), molecular weight M of the polymer_w＝2.1×10⁵g·mol^-1，PDI＝3.7(M_wMass average molecular weight of the polymer, obtained by elevated temperature GPC test).

b) Essentially the same as a), except that: cocatalyst Et with the dosage of 0.94mL₂AlCl (1.17mol/L toluene solution) so that Al/Ni becomes 400: 1. Polymerization Activity: 9.15X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝53.8℃，M_w＝2.8×10⁵g·mol^-1，PDI＝3.3。

c) Essentially the same as a), except that: cocatalyst Et with 1.17mL of cocatalyst₂AlCl (1.17mol/L toluene solution) so that Al/Ni becomes 500: 1. Polymerization Activity: 10.29X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝55.1℃，M_w＝2.8×10⁵g·mol^-1，PDI＝3.3。

d) Essentially the same as a), except that: cocatalyst Et with 1.4mL of cocatalyst₂AlCl (1.17mol/L toluene solution) so that Al/Ni becomes 600: 1. Polymerization Activity: 10.62X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝52.5℃，M_w＝5.0×10⁵g·mol^-1，PDI＝3.1。

The obtained polymer (100 mg) was dissolved in 5mL of deuterium tetrachloroethane and the polymer was tested at 100 ℃ for¹³And C, data. The signal was accumulated 2000 times to give a signal peak shift between 20 and 40(ppm), indicating a shift in the methyl, methylene and methine groups, confirming that the resulting polymer is branched polyethylene (see FIG. 4 for specific information).

e) Essentially the same as a), except that: cocatalyst Et with 1.64mL of cocatalyst₂AlCl (1.17mol/L toluene solution) so that Al/Ni becomes 700: 1. Polymerization Activity: 9.75X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝56.7℃，M_w＝2.3×10⁵g·mol^-1，PDI＝3.8。

f) Essentially the same as a), except that: cocatalyst Et with 1.87mL of cocatalyst₂AlCl (1.17mol/L toluene solution) so that Al/Ni becomes 800: 1. Polymerization Activity: 9.08X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝53.4℃，M_w＝2.3×10⁵g·mol^-1，PDI＝3.5。

g) Substantially the same as d), except that: the polymerization temperature was 20 ℃. Polymerization Activity: 5.27X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝87.1℃，M_w＝5.0×10⁵g·mol^-1，PDI＝3.7。

h) Substantially the same as d), except that: the polymerization temperature was 40 ℃. Polymerization Activity: 5.72X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝58.2℃，M_w＝2.3×10⁵g·mol^-1，PDI＝4.9。

i) Substantially the same as d), except that: the polymerization temperature was 50 ℃. Polymerization Activity: 3.90X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝29.1℃，M_w＝1.0×10⁵g·mol^-1，PDI＝4.6。

j) Substantially the same as d), except that: the polymerization time was 5 min. Polymerization Activity: 13.97X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝70.0℃，M_w＝7.8×10⁵g·mol^-1，PDI＝2.2。

k) Substantially the same as d), except that: the polymerization time was 10 min. Polymerization Activity: 16.32X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝68.1℃，M_w＝8.0×10⁵g·mol^-1，PDI＝2.0。

l) is substantially the same as d), except that: the polymerization time was 15 min. Polymerization Activity: 16.36X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝48.9℃，M_w＝1.9×10⁵g·mol^-1，PDI＝4.9。

m) is substantially the same as d), except that: the polymerization time was 45 min. Polymerization Activity: 8.34X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝56.3℃，M_w＝1.8×10⁵g·mol^-1，PDI＝4.9。

n) is substantially the same as d), except that: the polymerization time was 60 min. Polymerization Activity: 6.30X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝61.6℃，M_w＝2.1×10⁵g·mol^-1，PDI＝5.0。

Example 20

Using complexes C2 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C2. Polymerization Activity: 10.37X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝50.7℃，M_w＝6.0×10⁵g·mol^-1，PDI＝2.5。

Example 21

By means of complexes C3 andEt₂ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C3. Polymerization Activity: 10.45X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝51.5℃，M_w＝9.0×10⁵g·mol^-1，PDI＝2.4。

Example 22

Using complexes C4 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C4. Polymerization Activity: 12.57X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝52.7℃，M_w＝4.0×10⁵g·mol^-1，PDI＝2.7。

Example 23

Using complexes C5 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C5. Polymerization Activity: 9.5X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝43.1℃，M_w＝5.8×10⁵g·mol^-1，PDI＝2.5。

Example 24

Using complexes C6 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C6. Polymerization Activity: 5.43X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝62.6℃，M_w＝7.3×10⁵g·mol^-1，PDI＝2.4。

Example 25

Using complexes C7 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C7. Polymerization Activity: 4.42X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝67.4℃，M_w＝9.9×10⁵g·mol^-1，PDI＝2.3。

Example 26

Using complexes C8 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C8. Polymerization Activity: 4.31X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝58.8℃，M_w＝10.8×10⁵g·mol^-1，PDI＝2.4。

Example 27

Using complexes C9 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C9. Polymerization Activity: 4.63X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝54.0℃，M_w＝7.2×10⁵g·mol^-1，PDI＝2.4。

Example 28

Using complexes C10 and Et₂Ethylene polymerization under pressure with AlCl cocatalyst:

essentially the same as example 19d), except that: the main catalyst is C10. Polymerization Activity: 4.52X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝67.1℃，M_w＝10.5×10⁵g·mol^-1，PDI＝2.3。

Example 29

Ethylene polymerization under pressure with Complex C1 and MMAO cocatalyst:

a) 20mL of toluene, 30mL of a toluene solution of catalyst C1 (2. mu. mol), 1.04mL of co-catalyst MMAO (1.93mol/L of the toluene solution), and 50mL of toluene were sequentially charged into a 250mL stainless steel autoclave under an ethylene atmosphere. In this case, Al/Ni is 1000: 1. Mechanical stirring is started, 400 rpm is maintained, and when the polymerization temperature reaches 30 ℃, ethylene is charged into the reaction kettle, and the polymerization reaction starts. The mixture was stirred at 30 ℃ for 30min while maintaining the ethylene pressure at 10 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing.

Polymerization Activity: 2.26X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝76.7℃。(T_mMelting temperature of the polymer, obtained by DSC measurement), molecular weight M of the polymer_w＝9.2×10⁵g·mol^-1，PDI＝3.0(M_wMass average molecular weight of the polymer, obtained by elevated temperature GPC test).

b) Essentially the same as a), except that: the cocatalyst amount was 1.56mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni became 1500: 1. Polymerization Activity: 4.47X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝74.5℃，M_w＝12.7×10⁵g·mol^-1，PDI＝2.3。

c) Essentially the same as a), except that: the cocatalyst amount was 2.08mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni became 2000: 1. Polymerization Activity: 5.58X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝75.2℃，M_w＝4.0×10⁵g·mol^-1，PDI＝2.9。

d) Essentially the same as a), except that: the amount of cocatalyst used was 2.60mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni became 2500: 1. Polymerization Activity: 6.22X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝68.8℃，M_w＝8.3×10⁵g·mol^-1，PDI＝2.1。

e) Essentially the same as a), except that: the cocatalyst amount was 3.12mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni would be 3000: 1. Polymerization Activity: 8.3X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝63.2℃，M_w＝6.4×10⁵g·mol^-1，PDI＝2.6。

The obtained polymer (100 mg) was dissolved in 5mL of deuterated tetrachloroethane, and the polymer was tested at 100 deg.C¹³And C, data. The signal is accumulated 2000 times, and the peak shift of the signal is obtained to be between 20 and 40(ppm), which shows that the signal is methyl and methyleneAnd displacement of methine groups, confirming that the resulting polymer is branched polyethylene (see FIG. 5 for specific information).

f) Essentially the same as a), except that: the cocatalyst amount was 3.64mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni became 3500: 1. Polymerization Activity: 6.1X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝70.3℃，M_w＝7.5×10⁵g·mol^-1，PDI＝3.2。

g) Essentially the same as a), except that: the cocatalyst amount was 4.16mL of cocatalyst MMAO (1.93mol/L toluene solution) so that Al/Ni became 4000: 1. Polymerization Activity: 5.15X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝78.9℃，M_w＝11.5×10⁵g·mol^-1，PDI＝2.7。

h) Substantially the same as e), except that: the polymerization temperature was 20 ℃. Polymerization Activity: 4.18X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝94.0℃，M_w＝5.4×10⁵g·mol^-1，PDI＝3.2。

i) Substantially the same as e), except that: the polymerization temperature was 40 ℃. Polymerization Activity: 3.12X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝53.9℃，M_w＝5.0×10⁵g·mol^-1，PDI＝2.0。

j) Substantially the same as e), except that: the polymerization temperature was 50 ℃. Polymerization Activity: 3.11X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝47.0℃，M_w＝3.1×10⁵g·mol^-1，PDI＝2.6。

k) Substantially the same as e), except that: the polymerization time was 5 min. Polymerization Activity: 9.82X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝77.0℃，M_w＝11.8×10⁵g·mol^-1，PDI＝1.9。

l) is substantially the same as e), except that: the polymerization time was 10 min. Polymerization Activity: 8.31X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝79.8℃，M_w＝9.4×10⁵g·mol^-1，PDI＝1.8。

m) is substantially the same as e), except that: the polymerization time was 15 min. Polymerization Activity: 9.08X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝63.4℃，M_w＝4.9×10⁵g·mol^-1，PDI＝2.1。

n) is substantially the same as e), except that: the polymerization time was 45 min. Polymerization Activity: 6.73X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝68.5℃，M_w＝6.9×10⁵g·mol^-1，PDI＝2.6。

o) is substantially the same as e), except that: the polymerization time was 60 min. Polymerization Activity: 5.53X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝68.7℃，M_w＝8.2×10⁵g·mol^-1，PDI＝3.1。

Example 30

Ethylene polymerization under pressure with Complex C2 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C2. Polymerization Activity: 6.13X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝60.0℃，M_w＝5.1×10⁵g·mol^-1，PDI＝2.8。

Example 31

Ethylene polymerization under pressure with Complex C3 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C3. Polymerization Activity: 5.88X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝53.4℃，M_w＝30.8×10⁵g·mol^-1，PDI＝2.4。

Example 32

Ethylene polymerization under pressure with Complex C4 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C4. Polymerization Activity: 8.2X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝59.0℃，M_w＝15.7×10⁵g·mol^-1，PDI＝1.9。

Example 33

Ethylene polymerization under pressure with Complex C5 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C5. Polymerization Activity: 6.00X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝63.1℃，M_w＝19.8×10⁵g·mol^-1，PDI＝2.5。

Example 34

Ethylene polymerization under pressure with Complex C6 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C6. Polymerization Activity: 5.12X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝92.9℃，M_w＝15.5×10⁵g·mol^-1，PDI＝2.1。

Example 35

Ethylene polymerization under pressure with Complex C7 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C7. Polymerization Activity: 3.75X 10⁶g·mol^-1(Ni)·h^-1The polymer Tm is 85.2 ℃ and Mw is 12.4X 10⁵g·mol^-1，PDI＝2.3。

Example 36

Ethylene polymerization under pressure with Complex C8 and MMAO cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C8. Polymerization Activity: 3.71X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝72.7℃，M_w＝14.3×10⁵g·mol^-1，PDI＝2.4。

Example 37

Ethylene polymerization under pressure with Complex C9 and MMAO cocatalyst:

essentially the same as example 29e), except that: primary catalysisThe agent is C9. Polymerization Activity: 5.31X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝82.3℃，M_w＝10.4×10⁵g·mol^-1，PDI＝3.1。

Example 38

Ethylene polymerization under pressure with Complex C10 and EASC cocatalyst:

essentially the same as example 29e), except that: the main catalyst is C10. Polymerization Activity: 4.48X 10⁶g·mol^-1(Ni)·h^-1Of a polymer T_m＝73.6℃，M_w＝13.5×10⁵g·mol^-1，PDI＝2.9。

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. A tert-butyl group containing asymmetric α -diimine nickel complex of the following formula (I):

formula (I)

Wherein R is¹Is selected from C_1-6An alkyl group;

R²selected from H or methyl;

x is Cl or Br.

2. The nickel complex according to claim 1, wherein R¹Selected from methyl, ethyl or isopropyl.

3. The nickel complex according to claim 2, wherein the complex of formula (I) is selected from complexes having the following group definitions:

C1: R¹= Me；R²= H; x is Br;

C2: R¹= Et；R²= H; x is Br;

C3: R¹= i-Pr；R²= H; x is Br;

C4: R¹= Me；R²= Me; x is Br;

C5: R¹= Et；R²= Me; x is Br;

C6: R¹= Me；R²= H; x is Cl;

C7: R¹= Et；R²= H; x is Cl;

C8: R¹= i-Pr；R²= H; x is Cl;

C9: R¹= Me；R²= Me; x is Cl;

C10: R¹= Et；R²= Me; and X is Cl.

4. An intermediate of a tert-butyl group-containing asymmetric α -diimine nickel complex represented by the following formula (II):

formula (II)

Wherein R is¹And R²Has the definition as set forth in any one of claims 1 to 3.

5. A catalyst composition comprising a procatalyst and a cocatalyst, wherein the procatalyst is selected from the group consisting of a nickel complex according to any of claims 1-3;

the cocatalyst is selected from one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride.

6. The catalyst composition of claim 5, wherein the aluminoxane is selected from one or both of Methylaluminoxane (MAO) or triisobutylaluminum-Modified Methylaluminoxane (MMAO);

the alkylaluminum chloride is selected from diethylaluminum chloride (Et)₂AlCl), dimethylaluminum chloride (Me)₂AlCl) and/or aluminum sesquiethylate chloride (EASC).

7. The catalyst composition of claim 6, wherein the catalyst composition comprises a cocatalyst, and the molar ratio of the metal Al in the cocatalyst to the central metal Ni of the nickel complex represented by the formula (I) is (200-4000): 1.

8. The catalyst composition of claim 7, wherein when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of the metal Al in the Methylaluminoxane (MAO) to the central metal Ni of the nickel complex represented by the formula (I) is (1000-3000): 1;

the cocatalyst is dimethyl aluminum chloride (Me)₂AlCl), dimethylaluminum chloride (Me)₂The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (100-1000) to 1;

when the cocatalyst is triisobutylaluminum-Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutylaluminum-Modified Methylaluminoxane (MMAO) to the central metal Ni of the nickel complex shown in the formula (I) is (500-4000): 1;

the cocatalyst is diethylaluminum chloride (Et)₂AlCl), diethylaluminum chloride (Et)₂The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (200-1000): 1.

9. A process for preparing a nickel complex according to any one of claims 1 to 3, comprising the steps of:

carrying out a complexation reaction on the intermediate of claim 4 and a nickel-containing compound to obtain a nickel complex shown as a formula (I);

the nickel-containing compound is selected from nickel-containing halides.

10. The production method according to claim 9, wherein the halide containing nickel is (DME) NiBr₂、NiCl₂·6H₂O or NiBr₂One or more of;

the reaction is carried out under the condition of no oxygen;

the molar ratio of the nickel-containing compound to the compound shown in the formula (II) is 1: 1-2.

11. A process for the preparation of the intermediate of claim 4 comprising the steps of:

1) performing substitution reaction on acenaphthenone shown in a formula (III) and aniline shown in a formula (IV) to obtain 2-aniline acenaphthenone shown in a formula (V);

2) carrying out condensation reaction on the 2-phenylamine acenaphthenone shown in the formula (V) obtained in the step 1) and a compound shown in the formula (VI) to obtain a compound shown in the formula (II);

formula (III)

Formula (IV)

Formula (V)

Formula (VI).

12. The production method according to claim 11, wherein:

in the step 1), the substitution reaction is carried out under the catalysis of p-toluenesulfonic acid; the substitution reaction is carried out in an aromatic hydrocarbon solvent;

the molar charge ratio of acenaphthylene diketone shown in the formula (III) and aniline shown in the formula (IV) in the reaction system of the substitution reaction is 1: 1-2;

in step 2), the condensation reaction is carried out under the catalysis of p-toluenesulfonic acid;

the condensation reaction is carried out in an aromatic hydrocarbon solvent;

the molar charge ratio of the 2-phenylaniline acenaphthenone shown in the formula (V) and the compound shown in the formula (VI) obtained in the step 1) in the condensation reaction system is 1: 1-2.

13. A process for the preparation of polyethylene, comprising polymerizing ethylene with the aid of a catalyst composition as claimed in any of claims 6 to 8.

14. The production method according to claim 13, wherein:

the temperature of the polymerization reaction is 20-100 ℃;

the pressure of the polymerization reaction is 0.5-10 atm;

the solvent for the polymerization reaction is one or more selected from toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane.

15. Use of a nickel complex according to any of claims 1 to 3 or a catalyst composition according to any of claims 5 to 8 for catalysing the polymerisation of olefins.

16. Use according to claim 15, for catalysing the polymerisation of ethylene.

17. Use of an intermediate as claimed in claim 4 for the preparation of a nickel complex as claimed in any one of claims 1 to 3.

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