CN105646598B - Asymmetric Branched polyethylene containing naphthyl substituted and the preparation method and application thereof - Google Patents
Asymmetric Branched polyethylene containing naphthyl substituted and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of asymmetric Branched polyethylene catalyst and the preparation method and application thereof containing naphthyl substituted.The structural formula of the nickel complex is as shown in formula I, wherein R1For two (phenyl) methyl or two (p-fluorophenyl) methyl, R2For hydrogen, two (phenyl) methyl or two (p-fluorophenyl) methyl；R3The alkyl for being 1-3 for carbon atom number, R4For hydrogen or methyl, X is selected from bromine or chlorine.Preparation method is as follows：Under anaerobic, ligand shown in formula V and (DME) NiBr2Or NiCl2·6H2O reacts, and obtains nickel complex shown in formula I.The nickel metal complex, in the presence ofs co-catalyst diethylaluminum chloride or/and methylaluminoxane etc., can preferable catalyzed ethylene polymerization, obtain the polymer of high molecular weight reduced branching degree, highest catalytic activity is up to 7.71 × 106g·mol‑1(Ni)·h‑1, there is extensive prospects for commercial application.
Description
Technical field
The invention belongs to coordinate catalytic field, and in particular to a kind of asymmetric acenaphthene diimine nickel containing naphthyl substituted is matched
Close object and the preparation method and application thereof.
Background technology
Polyolefin includes mainly polyethylene, and polypropylene and poly 1-butene etc., wherein polyvinyl resin (PE) are general synthesis
The maximum kind of yield in resin, and due to its excellent material property, it is widely used in industry, agricultural, military, doctor
Treat many fields such as health, daily life.Due to the tremendous economic interests, social benefit and numerous international monopolies of polyethylene industry
Covering layer by layer, cause China high-performance polyethylene new material production in be in very passive situation.China's polyethylene work
Industry remains some contradictions and disadvantage, and polyethylene product shows structural superfluous and structural shortage deficiency.?
In the production technology of all polyethylene, catalyst is all vital factor.Therefore, research and development are with innovative high property
Energy polyethylene catalysts have become the responsibility and realistic task of current China scientific research personnel.
The metal complex catalyzed ethylene oligomerization of nickel (SHOP techniques) is last century the eighties late transition metal catalysis ethylene
The contribution having an epoch-marking significance in reaction, the large-scale production based on alpha-olefin greatly advance the development of chemical industry.Its
Structure (Angew.Chem., Int.Ed.Engl.1978,17,466-467 as shown in following formula one；Angew.Chem.,
Int.Ed.Engl.1983,22,503；J.Chem.Soc.,Chem.Commun.1994,2203–2204):
Nineteen ninety-five, Brookhart seminar report a kind of novel alpha-diimine nickel, palladium complex for the first time, and by its
For catalyzed ethylene polymerization (J.Am.Chem.Soc.1995,117,6414-6415), the poly- second of high molecular weight, highly -branched is obtained
Alkene has started the research boom of transition metal nickel complex as catalyst alkene, and corresponding structural formula is as shown in following formula two.
Our seminars had been devoted to ethylene oligomerization, the exploitation of polymerization catalyst and Catalytic processes in the several years in past
Research, develops the ethylene oligomerization and polymerization catalyst of multiclass nickel metal complex.The single, double core pyridine imine nickel cooperation of design
Object carries out obtaining branched polymer weight northylen when vinyl polymerization catalysis, and as shown in following formula three, nuclear-magnetism is ground corresponding structural formula
Study carefully confirm branched chain be butyl (J.Organomet.Chem., 2005,690,1570-1580 and J.Organomet.Chem.,
2005,690,1739-1749), which can be used for synthesizing new polyvinyl resin.
The quinolinamine nickel compound that we report can show high catalytic activity under normal pressure, be catalyzed ethylene oligomerization
Activity up to 1.2 × 107g·mol–1·h–1atm-1(Chin.Chem.Lett.2001,12,691-692), corresponding structural formula
As shown in following formula four.
In addition, 2- benzimidazole -1,10- ferrosin nickel complexes that we design can be catalyzed ethylene oligomerization, activity reaches
To 1.27 × 107g·mol–1·h–1(Eur.J.Inorg.Chem.2007,3816-3826), corresponding structural formula such as following formula
Shown in five.
Our groups develop the cooperation of multiclass nickel in being dedicated to the research of ethylene oligomerization and polymerization catalyst and Catalytic processes
Object catalyst patent：Chinese patent ZL 00 1 21033.5, July 17 2000 applying date, authorized announcement date 2003.1.8；
Chinese Patent Application No. 01118455.8, May 31 2001 applying date；Chinese patent ZL 01 1 20214.9, the applying date：
On July 6th, 2001, authorized announcement date 2004.7.7；Chinese Patent Application No. 01120554.7, July 20 2001 applying date；
Chinese patent ZL 02 1 18523.9, April 26 2002 applying date, authorized announcement date 2004.12.22；Chinese patent ZL
02 1 23213.X, June 12 2002 applying date, authorized announcement date 2003.11.19；Chinese Patent Application No.
03137727.0, June 23 2003 applying date；Chinese Patent Application No. 03148378.X, July 2 2003 applying date；China
Number of patent application 03154463.0, October 8 2003 applying date；200410086284.7 applying date of Chinese Patent Application No.
On October 29th, 2004；December 30 2004 200410081711.2 applying date of Chinese Patent Application No.；Chinese patent application
Number July 19 2007 200710119281.2 applying date.
Late transition metal catalyst for olefin polymerization shows in result of study over the past decade and compares metallocene catalysis
The advantages of agent better performance (it is good to synthesize simple, at low cost and stability), this kind of catalyst, which also resides in, to be matched by adjusting
The structure of body reaches the control to catalytic activity and polymer performance.
Invention content
The object of the present invention is to provide a kind of asymmetric Branched polyethylene containing naphthyl substituted and its preparation side
Method and application.
Asymmetric Branched polyethylene provided by the present invention containing naphthyl substituted, general structure such as Formulas I institute
Show：
In the Formulas I, R1For two (phenyl) methyl or two (p-fluorophenyl) methyl；R2For hydrogen, two (phenyl) methyl or two
(p-fluorophenyl) methyl；R3The alkyl for being 1-3 for carbon atom number；R4For hydrogen or methyl；X is bromine or chlorine.
It is furthermore preferred that nickel metal complex of the present invention is selected from any one following complex：
C1:R1=CHPh2；R2=H；R3=Me；R4=H；X is Br.
C2:R1=CHPh2；R2=H；R3=Et；R4=H；X is Br.
C3:R1=CHPh2；R2=H；R3=i-Pr；R4=H；X is Br.
C4:R1=CHPh2；R2=H；R3=Me；R4=Me；X is Br.
C5:R1=CHPh2；R2=H；R3=Et；R4=Me；X is Br.
C6:R1=R2=CHPh2；R3=Me；R4=H；X is Br.
C7:R1=R2=CHPh2；R3=Et；R4=H；X is Br.
C8:R1=R2=CHPh2；R3=i-Pr；R4=H；X is Br.
C9:R1=R2=CHPh2；R3=Me；R4=Me；X is Br.
C10:R1=R2=CHPh2；R3=Et；R4=Me；X is Br.
C11:R1=CH (PhF)2；R2=H；R3=Me；R4=H；X is Br.
C12:R1=CH (PhF)2；R2=H；R3=Et；R4=H；X is Br.
C13:R1=CH (PhF)2；R2=H；R3=i-Pr；R4=H；X is Br.
C14:R1=CH (PhF)2；R2=H；R3=Me；R4=Me；X is Br.
C15:R1=CH (PhF)2；R2=H；R3=Et；R4=Me；X is Br.
C16:R1=R2=CH (PhF)2；R3=Me；R4=H；X is Br.
C17:R1=R2=CH (PhF)2；R3=Et；R4=H；X is Br.
C18:R1=R2=CH (PhF)2；R3=i-Pr；R4=H；X is Br.
C19:R1=R2=CH (PhF)2；R3=Me；R4=Me；X is Br.
C20:R1=R2=CH (PhF)2；R3=Et；R4=Me；X is Br.
C21:R1=R2=CH (PhF)2；R3=Me；R4=H；X is Cl.
Wherein, Ph represents phenyl；Me represents methyl；Et represents ethyl；I-Pr represents isopropyl.
The method provided by the present invention for preparing compound shown in above-mentioned Formulas I, includes the following steps：Under anaerobic,
Make ligand compound shown in Formula V and (DME) NiBr2Or NiCl2·6H2O is reacted in organic solvent, obtains Formulas I shownization
Close the solution of object；
Wherein, the R in Formula V1、R2、R3And R4The same Formulas I of definition.
In the above method, ligand compound shown in the Formula V and (DME) NiBr2Or NiCl2·6H2The molar ratio of O is
(1.2-1)：(1-1.2), specially 1.1：1.
(DME) NiBr2For (glycol dimethyl ether) nickelous bromide.
The organic solvent is dichloromethane.
The reaction temperature of the reaction is room temperature, and the reaction time is 8-24 hours, specially 12 hours.
Further include that ether is added into the solution of compound shown in the Formulas I to promote compound shown in Formulas I in the above method
The step of precipitation, then, filtering, ether are washed, drying.
The present invention also provides ligand compound shown in a kind of Formula V,
Wherein, the R in Formula V1、R2、R3And R4The same Formulas I of definition.
The method provided by the invention for preparing ligand compound shown in the Formula V, includes the following steps：
1) under Catalyzed by p-Toluenesulfonic Acid, so that acenaphthenequinone is reacted in organic solvent with compound shown in Formula II, obtain
Compound shown in formula III；
2) under Catalyzed by p-Toluenesulfonic Acid, make compound and formula IV compound represented shown in the formula III that step 1) obtains
Back flow reaction is carried out in organic solvent, obtains ligand compound shown in Formula V；
Wherein, the R in Formula II, formula III and formula IV1、R2、R3And R4The same Formulas I of definition.
In the above method, in step 1), the molar ratio of compound shown in the acenaphthenequinone and Formula II is (1.5-1)：(1-
1.5), specially 1：1.
The addition of the p-methyl benzenesulfonic acid is the 0.5%-5% of the acenaphthenequinone.
The organic solvent is selected from dichloromethane and/or ethyl alcohol；It is preferred that the mixed solvent of dichloromethane and ethyl alcohol, the two
Volume ratio is (10-30)：(1-3), specially 20：1.
The reaction temperature of the reaction is room temperature, and the reaction time is 12-36 hours, specially 24 hours.
In the above method, in step 2), the molar ratio of compound and formula IV compound represented shown in the formula III is
(1.5-1)：(1-1.5), specially 1：1.1.
The addition of the p-methyl benzenesulfonic acid is the 0.5%-5% of the formula III.
The organic solvent is toluene.
The reaction temperature of the back flow reaction is 105 DEG C -120 DEG C, and the reaction time is 6-10 hours, and preferably 8-10 is small
When.
Compound shown in the formula III purified in order to obtain, further include in step 1) compound shown in formula III is carried out it is as follows
The step of purifying：Compound shown in the formula III obtained in step 1) is dissolved in dichloromethane, silicagel column carries out column chromatography, with
The mixed solvent of petroleum ether and ethyl acetate is that eluent is eluted, and detects eluted fraction by thin-layer chromatography, wherein mixing
In solvent, the volume ratio of petroleum ether and ethyl acetate is (50-150)：1, preferably 80:1.
Ligand compound shown in the Formula V purified in order to obtain further includes to ligand shown in obtained Formula V in step 2)
The step of compound is purified as follows：Ligand compound shown in the Formula V obtained in step 2) is dissolved in dichloromethane, silica gel
Column carries out column chromatography, is eluted as eluent using the mixed solvent of petroleum ether and ethyl acetate, is washed by thin-layer chromatography detection
The separation of flow point, wherein the volume ratio of in the mixed solvent, petroleum ether and ethyl acetate is (50-250)：1, preferably 200:1.
The application of metal complex shown in Formulas I provided by the present invention is answering in the catalyst for preparing vinyl polymerization
With.
In addition, the present invention also provides a kind of carbon monoxide-olefin polymeric for vinyl polymerization, the carbon monoxide-olefin polymeric is by making
Compound and co-catalyst (namely activator) shown in Formulas I for major catalyst form；Wherein, the co-catalyst is selected from as follows
It is at least one：Aikyiaiurnirsoxan beta, alkyl aluminum and chlorination alkyl aluminum.
The molar ratio of nickel element and aluminium element in the aikyiaiurnirsoxan beta is 1 in nickel metal complex shown in the Formulas I：(1000-
3500), preferred molar ratio 1：(1000-3000).
The molar ratio of nickel element and aluminium element in the alkyl aluminum is 1 in nickel metal complex shown in the Formulas I：(200-
800), preferred molar ratio 1：(300-800).
The molar ratio of nickel element and aluminium element in the chlorination alkyl aluminum is 1 in nickel metal complex shown in the Formulas I：
(200-800), preferred molar ratio 1：(300-800).
In above-mentioned carbon monoxide-olefin polymeric, the aikyiaiurnirsoxan beta is selected from following at least one：Methylaluminoxane (MAO), three isobutyls
Methylaluminoxane (MMAO), ethylaluminoxane and the isobutyl aluminium alkoxide that base aluminium is modified, the aikyiaiurnirsoxan beta can be by various common
Trialkyl aluminium compound hydrolysis generate, such as：MMAO can be by trimethyl aluminium and compared with higher trialkylaluminum (such as three isobutyls
Base aluminium) hydrolysis generate.
The alkyl aluminum is selected from following at least one：Triethyl aluminum, trimethyl aluminium, triisobutyl aluminium, tri-n-hexyl aluminum and
Tri-n-octylaluminium.
The chlorination alkyl aluminum is selected from following at least one：Diethylaluminum chloride, chlorodimethylalumiu, ethylaluminium dichloride
With sesquialter aluminium (diethylaluminum chloride：Ethylaluminium dichloride=1:1 mixture).
The present invention also provides a kind of methods preparing polyethylene, include the following steps：With above-mentioned provided by the present invention
Carbon monoxide-olefin polymeric as catalyst under conditions of, catalysis ethylene carry out polymerisation, reaction finish to obtain the polyethylene.
In the above-mentioned method for preparing polyethylene, the temperature of the polymerisation is 0-70 DEG C, preferably 20-70 DEG C, more excellent
Select 30 DEG C or 40 DEG C.
The time of the polymerisation is 10-120 minutes, preferably 15-60 minutes, more preferable 30 minutes.
What the polymerisation carried out under elevated pressure, the pressure limit of the pressurization is 1-10atm, preferably 5-10atm.
The polymerisation carries out in a solvent, and the solvent is selected from toluene, dichloromethane, tetrahydrofuran, hexane and ring
At least one of hexane, preferably toluene and/or hexane, more preferable toluene.
The present invention has designed and synthesized asymmetric acenaphthene diimide ligand and its nickel complex containing N^N dentates, system
For simple for process, raw material is cheap, and there are very high activity, asymmetric acenaphthene diimide ligand structure logical catalyzed ethylene polymerization
Nuclear-magnetism, infrared and elemental analysis characterization are crossed, nickel complex also uses X-ray monocrystalline other than infrared and elemental analysis characterization
Diffractometer measures, it was confirmed that the crystal structure of complex C1, C4, C16.
Nickel complexes provided by the invention show extraordinary catalysis and live when being reacted for catalyzed ethylene polymerization
Property.At 30 DEG C, the activity of their catalyzed ethylene polymerizations is up to 7.71 × 106g·mol-1(Ni)·h-1, obtained polymer is height
The polyethylene of molecular weight reduced branching degree has extensive prospects for commercial application.
Description of the drawings
Fig. 1 is the preparation flow figure of Nickel complexes shown in Formulas I；
Fig. 2 is the crystal structure figure of complex C1；
Fig. 3 is the crystal structure figure of complex C4；
Fig. 4 is the crystal structure figure of complex C16.
Specific implementation mode
The method of the present invention is illustrated by specific embodiment below in conjunction with the accompanying drawings, but the invention is not limited in
This.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Concentration described in following embodiments is mass percentage concentration unless otherwise instructed.Following vinyl polymerization embodiments
The molecular weight and molecular weight distribution of middle resulting polymers are to measure and obtain according to conventional GPC method, and fusing point is according to normal
The DSC method of rule is measured and is obtained, and the polymerization activity of polymer is calculated according to following formula and obtained：Polymerization activity=polymerization produce
Amount/(catalyst amount polymerization time).
The preparation flow figure of Nickel complexes shown in Formulas I is as shown in Figure 1 in following embodiments.
Embodiment 1 prepares 2- bis- (phenyl) methyl naphthylamines
Naphthalidine (10g, 63.84mmol), two (phenyl) methanol (8.84g, 34.92mmol), anhydrous ZnCl2(5g,
It 36.68mmol) is added separately in round-bottomed flask, oil bath heating, temperature control is at 150 DEG C or so.React 8h.After stopping heating cooling
Addition DCM dissolvings, are filtered with diatomite, removing solvent, and the volume ratio of residue petroleum ether and ethyl acetate is 100:1 it is mixed
Bonding solvent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains aubergine powder 2.66g, produce
Rate 18.6%
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ7.80-7.89(m,2H),7.47-7.49
(m, 2H), 7.29-7.39 (m, 8H), 7.23 (d, J=7.2Hz, 5H), 6.96 (d, J=8.4Hz, 1H), 5.79 (s, 1H),
3.98(s,2H)。
13C NMR(100MHz,CDCl3,TMS):δ142.8,139.2,133.3,129.7,128.7,128.6,128.1,
126.8,125.5,125.1,123.8,122.9,120.5,118.2,52.5。
Embodiment 2 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone
Acenaphthenequinone (0.73g, 4mmol) and (phenyl) the methyl naphthylamines of 2- bis- (1.24g, 4mmol) are dissolved in ethanol in proper amount and dichloro
(the two volume ratio is 20 to the mixed solvent of methane：1) in, p-methyl benzenesulfonic acid (0.015g, 0.08mmol) is added, is stirred at room temperature
24h.The volume ratio of removing solvent, residue petroleum ether and ethyl acetate is 80:1 mixed solvent carries out silica gel column chromatography.
Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red powder 1.5g, yield 53%.
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 7.90 (d, J=8.0Hz, 1H), 7.82-
7.76 (m, 2H), 7.71 (d, J=8.4Hz, 1H), 7.63 (d, J=8.0Hz, 1H), 7.47 (t, J=8.0Hz, 2H), 7.35-
7.04 (m, 9H), 6.99 (d, J=8.0Hz, 1H), 6.85 (t, J=8.0Hz, 1H), 6.47 (t, J=7.6Hz, 2H), 5.54
(s,1H)。
13C NMR(100MHz,CDCl3,TMS):δ165.2,163.3,148.9,145.1142.7,141.4,140.5,
131.4,129.7,129.5,128.3,128.2,127.7,127.3,126.8,126.4,126.1,125.8,125.5,
125.1,125.0,124.8,124.1,123.5,123.3,122.9,52.7。
Embodiment 3 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- imino dimethyl benzenes) acenaphthylene [L1]
1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (3.06g, 6.46mmol) and 2,6- dimethylanilines (0.86g,
It 7.10mmol) is dissolved in 100mL toluene solutions, p-methyl benzenesulfonic acid (0.03g, 0.13mmol) is added, is heated to reflux, react 8h.
The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silica gel column chromatography.
Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.17g, yield：4.7%.Fusing point:160℃.
Structural identification data is as follows：FT-IR(KBr,cm-1):3054(w),2968(w),1663(w),1637(m),1592
(s),1493(s),1372(s),1274(m),1152(w),1032(m),918(w),829(m),778(vs),745(vs),696
(vs).1H NMR(400MHz,CDCl3,TMS):δ 7.89 (d, J=8.0Hz, 1H), 7.77-7.74 (m, 2H), 7.69 (d, J=
8.4Hz, 1H), 7.60 (d, J=8.0Hz, 1H), 7.44 (t, J=8.0Hz, 2H), 7.33-7.09 (m, 11H), 7.02 (d, J=
8.0Hz, 1H), 6.90 (t, J=8.0Hz, 1H), 6.64 (d, J=7.2Hz, 1H), 6.51 (t, J=7.6Hz, 2H), 6.29 (t,
J=7.6Hz, 1H), 6.01 (s, 1H), 5.73 (d, J=7.2Hz, 1H), 2.34 (s, 3H), 2.20 (s, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.8,161.5,149.4,146.2,143.7,141.9,140.7,
132.9,130.4,130.0,129.8,129.2,129.0,128.8,128.5,128.3,128.1,128.0,127.9,
127.7,127.5,126.3,126.1,126.0,125.3,125.1,125.0,124.1,123.9,123.6,123.1,
122.2,52.7,18.4,18.1。
Elemental analysis:C43H32N2(576.73) theoretical value:C,89.55；H,5.59；N,4.86.Experiment value:C,89.15；H,
5.66；N,4.65.
Embodiment 4 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethylbenzenes imido grpup) acenaphthylene [L2]
1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (3.06g, 6.46mmol) and 2,6- diethylanilines (1.01g,
It 7.10mmol) is dissolved in 100mL toluene solutions, p-methyl benzenesulfonic acid (0.03g, 0.13mmol) is added, is heated to reflux, react 8h.
The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silica gel column chromatography.
Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains crocus solid 0.59g, yield：15.3%.Fusing point:206℃.
Structural identification data is as follows：FT-IR(KBr,cm-1):3054(w),2966(w),1665(w),1639(m),1592
(w),1493(m),1375(s),1269(m),1149(w),1060(m),922(w),826(m),778(vs),743(vs),699
(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.88 (d, J=8.0Hz, 1H), 7.75-7.73 (m, 2H), 7.69 (d, J
=8.8Hz, 1H), 7.60 (d, J=8.4Hz, 1H), 7.43 (t, J=7.2Hz, 1H), 7.31-7.15 (m, 11H), 7.02 (d, J
=7.2Hz, 2H), 6.88 (t, J=7.6Hz, 1H), 6.62 (d, J=7.2Hz, 1H), 6.52 (t, J=7.6Hz, 2H), 6.30
(t, J=7.6Hz, 1H), 6.01 (s, 1H), 5.70 (d, J=7.2Hz, 1H), 2.84-2.74 (m, 1H), 2.70-2.59 (m,
2H), 2.52-2.42 (m, 1H), 1.28 (t, J=7.6Hz, 3H), 1.16 (t, J=7.2Hz, 3H)13C NMR(100MHz,
CDCl3,TMS):δ163.8,161.5,148.5,146.2,143.8,141.9,140.7,132.9,131.0,130.8,
130.4,130.0,129.8,129.2,128.9,128.7,128.5,128.3,128.1,127.7,127.5,126.5,
126.3,126.1,126.0,125.4,124.3,124.1,123.9,123.6,123.1,122.7,52.6,25.0,24.7,
14.6,14.0。
Elemental analysis:C45H36N2(604.78) theoretical value:C,89.37；H,6.00；N,4.63.Experiment value:C,89.13；H,
6.06；N,4.66.
Embodiment 5 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diisopropyls phenyl imido) acenaphthylene
[L3]
1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (3.06g, 6.46mmol) and 2,6- diisopropyl anilines
(1.26g, 7.10mmol) is dissolved in 100mL toluene solutions, and p-methyl benzenesulfonic acid (0.03g, 0.13mmol) is added, is heated to reflux,
React 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silicon
Plastic column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains crocus solid 1.00g, yield：25.0%.It is molten
Point:183℃.
Structural identification data is as follows：FT-IR(KBr,cm-1):2969(w),2903(w),1666(w),1639(m),1591
(w),1491(s),1378(s),1249(s),1151(w),1060(m),922(w),827(m),778(vs),722(vs),698
(vs).1H NMR(400MHz,CDCl3,TMS):δ 7.88 (d, J=8.4Hz, 1H), 7.75-7.72 (m, 2H), 7.69 (d, J=
8.8Hz, 1H), 7.59 (d, J=8.4Hz, 1H), 7.43 (t, J=7.2Hz, 1H), 7.34-7.16 (m, 11H), 7.01 (d, J=
7.6Hz, 2H), 6.87 (t, J=7.6Hz, 1H), 6.57 (d, J=7.2Hz, 1H), 6.51 (t, J=7.2Hz, 2H), 6.29 (t,
J=7.2Hz, 1H), 6.01 (s, 1H), 5.69 (d, J=7.2Hz, 1H), 3.32-3.23 (m, 1H), 3.10-3.02 (m, 1H),
1.36 (d, J=6.4Hz, 3H), 1.29 (d, J=6.8Hz, 3H), 0.96 (d, J=6.8Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.9,161.8,147.3,146.3,143.8,141.8,140.8,
135.8,135.6,132.9,130.4,130.0,129.8,129.1,128.9,128.7,128.5,128.3,128.1,
128.0,127.8,127.5,126.3,126.2,126.0,125.4,124.6,124.1,123.8,123.6,123.1,
123.0,52.6,28.8,28.7,24.0,23.8,23.7,23.4。
Elemental analysis:C47H40N2(632.83) theoretical value:C,89.20；H,6.37；N,4.43.Experiment value:C,89.14；H,
6.27；N,4.24.
Embodiment 6 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,4,6- trimethylbenzenes imido grpup) acenaphthylene
[L4]
1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (2.92g, 6.16mmol) and 2,4,6- trimethylanilines
(0.92g, 6.78mmol) is dissolved in 100mL toluene solutions, and p-methyl benzenesulfonic acid (0.02g, 0.12mmol) is added, is heated to reflux,
React 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silicon
Plastic column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.49g, yield：13.5%.Fusing point:
137℃。
Structural identification data is as follows：FT-IR(KBr,cm-1):3056(w),2958(w),1655(m),1635(m),1594
(s),1473(s),1446(s),1374(s),1274(s),1154(w),1055(m)921(w),832(m),783(vs),742
(vs),697(vs).1H NMR(400MHz,CDCl3,TMS):δ 7.88 (d, J=8.4Hz, 1H), 7.77-7.73 (m, 2H),
7.68 (d, J=8.4Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 7.43 (t, J=7.2Hz, 1H), 7.34-7.28 (m, 4H),
7.22 (d, J=7.2Hz, 1H), 7.16 (d, J=7.6Hz, 2H), 7.01 (d, J=8.8Hz, 4H), 6.89 (t, J=8.0Hz,
1H), 6.70 (d, J=7.2Hz, 1H), 6.50 (t, J=7.6Hz, 2H), 6.29 (t, J=7.2Hz, 1H), 6.00 (s, 1H),
5.72 (d, J=7.2Hz, 1H), 2.40 (s, 3H), 2.29 (s, 3H), 2.16 (s, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.9,161.6,146.9,146.2,143.7,141.9,140.6,
133.2,132.9,130.4,130.0,129.8,129.3,129.1,128.8,128.4,128.3,128.1,127.9,
127.7,127.5,126.3,126.1,126.0,125.3,124.9,124.7,124.0,123.9,123.5,123.2,
122.2,52.6,21.1,18.3,18.1。
Elemental analysis:C44H34N2(590.75) theoretical value:C,89.46；H,5.80；N,4.74.Experiment value:C,89.23；H,
6.17；N,4.53.
Embodiment 7 prepares 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethyl -4- methyl phenyl imido)
Acenaphthylene [L5]
1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (2.92g, 6.16mmol) and 2,6- diethyl -4- methylanilines
(1.11g, 6.78mmol) is dissolved in 100mL toluene solutions, and p-methyl benzenesulfonic acid (0.02g, 0.12mmol) is added, is heated to reflux,
React 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silicon
Plastic column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.75g, yield：19.7%.Fusing point:
154℃。
Structural identification data is as follows：FT-IR(KBr,cm-1):3057(w),2964(m),1661(m),1639(m),1595
(m),1491(m),1453(s),1373(s),1271(s),1155(m),1029(w),921(w),827(m),777(vs),743
(vs),698(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.87 (d, J=8.0Hz, 1H), 7.73 (d, J=8.0Hz, 2H), 7.68
(d, J=8.4Hz, 1H), 7.59 (d, J=8.4Hz, 1H), 7.43 (t, J=7.2Hz, 1H), 7.32-7.16 (m, 8H), 7.07-
7.01 (m, 4H), 6.87 (t, J=8.0Hz, 1H), 6.68 (d, J=7.2Hz, 1H), 6.51 (t, J=7.2Hz, 2H), 6.30
(t, J=7.2Hz, 1H), 6.01 (s, 1H), 5.70 (d, J=7.2Hz, 1H), 2.79-2.70 (m, 1H), 2.66-2.56 (m,
2H), 2.48-2.39 (m, 4H), 1.26 (t, J=7.6Hz, 3H), 1.15 (t, J=7.6Hz, 3H)13CNMR(100MHz,
CDCl3,TMS):δ163.8,161.7,146.3,146.0,143.8,141.8,140.6,133.4,130.8,130.6,
129.9,129.7,129.3,128.7,128.4,128.1,128.0,127.7,127.5,127.4,126.3,126.1,
126.0,125.3,124.0,123.9,123.5,123.1,122.7,52.6,25.0,24.7,21.4,14.7,14.1。
Elemental analysis:C46H38N2(618.81) theoretical value:C,89.28；H,6.19；N,4.53.Experiment value:C,88.86；H,
6.06；N,4.48.
Embodiment 8 prepares { 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- imino dimethyl benzenes) acenaphthene } conjunction bromine
Change nickel (II) [complex C1]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (phenyl) methyl naphthalenes
Imido grpup] -2- (2,6- imino dimethyl benzene) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, second be added
Ether has red solid precipitation, filtering, and ether washing, drying obtains dark red solid 0.14g.Yield：70.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3056(w),2973(w),1644(w),1622(m),1599
(s),1492(s),1376(m),1293(m),1151(w),1029(m),918(w),828(m),772(vs),744(vs),694
(vs)。
Elemental analysis:C43H32Br2N2Ni (795.23) theoretical value:C,64.94；H,4.06；N,3.52.Experiment value:C,
64.82；H,3.95；N,3.81.
Embodiment 9 prepares { 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethylbenzenes imido grpup) acenaphthene } conjunction bromine
Change nickel (II) [complex C2]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (phenyl) methyl naphthalenes
Imido grpup] -2- (2,6- diethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, second be added
Ether has red solid precipitation, filtering, and ether washing, drying obtains red solid 0.19g.Yield：78.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3057(w),2973(w),1648(w),1618(m),1581
(s),1491(s),1374(s),1291(s),1154(w),1051(m),914(w),832(m),782(vs),733(vs),700
(vs)。
Elemental analysis:C45H36Br2N2Ni (823.28) theoretical value:C,65.65；H,4.41；N,3.40.Experiment value:C,
65.55；H,4.53；N,3.43.
The crystal structure figure of complex C1 is as shown in Figure 2.
Embodiment 10 prepares { 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diisopropyls phenyl imido) acenaphthene }
Close nickelous bromide (II) [complex C3]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (phenyl) methyl naphthalenes
Imido grpup] -2- (2,6- diisopropyl phenyl imido) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, be added
Ether has red solid precipitation, filtering, and ether washing, drying obtains red solid 0.18g.Yield：72.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2967(w),2901(w),1646(w),1620(m),1582
(s),1493(s),1383(s),1293(s),1183(w),1052(m),957(w),830(m),775(vs),724(vs),698
(vs)。
Elemental analysis:C47H40Br2N2Ni (851.34) theoretical value:C,66.31；H,4.74；N,3.29.Experiment value:C,
65.98；H,4.97；N,3.26.
Embodiment 11 prepares { 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,4,6- trimethylbenzenes imido grpup) acenaphthene }
Close nickelous bromide (II) [complex C4]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (phenyl) methyl naphthalenes
Imido grpup] -2- (2,4,6- trimethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, be added
Ether has red solid precipitation, filtering, and ether washing, drying obtains dark red solid 0.19g.Yield：76.1%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3058(w),2974(w),1647(m),1622(m),1583
(s),1487(s),1373(s),1291(s),1154(m),1030(s),917(m),827(m),772(vs),749(vs),697
(vs)。
Elemental analysis:C44H34Br2N2Ni (809.26) theoretical value:C,65.30；H,4.23；N,3.46.Experiment value:C,
65.45；H,4.49；N,3.48.
The crystal structure figure of complex C4 is as shown in Figure 3.
Embodiment 12 prepares { 1- [(phenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethyl -4- methylbenzene imines
Base) acenaphthene } close nickelous bromide (II) [complex C5]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (phenyl) methyl naphthalenes
Imido grpup] -2- (2,6- diethyl -4- methyl phenyl imido) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.10g.Yield：
38.1%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3057(w),2967(w),1647(w),1622(m),1582
(s),1491(s),1452(s),1376(s),1294(s),1158(w),1031(m),961(w),828(m),774(vs),748
(vs),700(vs)。
Elemental analysis:C46H38Br2N2Ni (837.31) theoretical value:C,65.98；H,4.57；N,3.35.Experiment value:C,
65.59；H,4.62；N,3.38.
Embodiment 13 prepares 2,4- bis- [two (phenyl)] methyl naphthylamines
Naphthalidine (10g, 63.84mmol), two (phenyl) methanol (8.84g, 34.92mmol), anhydrous ZnCl2(5g,
It 36.68mmol) is added separately in round-bottomed flask, oil bath heating, temperature control is at 150 DEG C or so.React 8h.After stopping heating cooling
Addition DCM dissolvings, are filtered with diatomite, removing solvent, and the volume ratio of residue petroleum ether and ethyl acetate is 100:1 it is mixed
Bonding solvent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains aubergine powder 1.38g, produce
Rate 4.5%
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 7.82 (d, J=8.8Hz, 2H), 7.46-
7.38(m,3H),6.92-6.86(m,16H),6.84-6.80(m,4H),6.08(s,1H),6.01(s,2H),5.62(s,1H),
4.13(s,2H)。
13C NMR(100MHz,CDCl3,TMS):δ163.1,162.7,160.9,160.7,139.7,138.5,138.4,
132.2,130.7,130.4,129.5,127.0,126.4,123.9,121.7,115.8,115.6,115.3,51.4,51.1。
Embodiment 14 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone
Acenaphthenequinone (0.73g, 4mmol) and 2,4- bis- [two (phenyl)] methyl naphthylamines (1.90g, 4mmol) are dissolved in ethanol in proper amount
With the in the mixed solvent of dichloromethane, p-methyl benzenesulfonic acid (0.015g, 0.08mmol) is added, is stirred at room temperature for 24 hours.Solvent is removed,
The volume ratio of residue petroleum ether and ethyl acetate is 80:1 mixed solvent carries out silica gel column chromatography.Pass through thin layer silica gel plate
Eluted fraction is detected, solvent is removed and obtains red powder 1.3g, yield 50.8%.
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 7.92 (d, J=8.4Hz, 1H), 7.81 (d,
J=8.4Hz, 2H), 7.74 (d, J=8.0Hz, 1H), 7.44-7.31 (m, 4H), 7.22 (t, J=8.2Hz, 2H), 7.05 (t, J
=8.6Hz, 3H), 7.02-6.93 (m, 7H), 6.86-6.80 (m, 5H), 6.64 (d, J=7.2Hz, 1H), 6.49 (s, 1H),
6.22 (d, J=8.6Hz, 2H), 5.41 (s, 1H), 5.39 (s, 1H).
13C NMR(100MHz,CDCl3,TMS):δ164.8,162.9,161.3,140.7,138.8,129.7,128.2,
127.8,127.4,126.3,123.9,51.8,50.8。
Embodiment 15 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- imino dimethyl benzenes)
Acenaphthylene [L6]
1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.280g, 2.00mmol) and 2,6- dimethylanilines
(0.267g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to reflux,
React 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 150:1 mixed solvent carries out silicon
Plastic column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.32g, yield：21.5%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2867(w),2740(w),1881(w),1667(m),1635
(m),1598(m),1511(vs),1245(vs),1156(s),1023(m),825(vs),771(vs),726(m).1HNMR
(400MHz,CDCl3,TMS):δ 7.97.94 (d, J=8.4Hz, 1H), 7.83 (d, J=8.4Hz, 2H), 7.73 (d, J=
8.0Hz, 1H), 7.43-7.29 (m, 4H), 7.20 (t, J=8.2Hz, 2H), 7.03 (t, J=8.6Hz, 3H), 6.99-6.91
(m, 7H), 6.88-6.82 (m, 5H), 6.79 (t, J=7.0Hz, 2H), 6.67 (d, J=7.2Hz, 1H), 6.49 (s, 1H),
6.24 (s, 1H), 6.20 (d, J=8.6Hz, 2H), 5.85 (s, 1H), 5.79 (d, J=7.2Hz, 1H), 2.28 (s, 3H), 2.20
(s,3H)。
13C NMR(100MHz,CDCl3,TMS):δ164.0,162.4,161.4,140.8,139.6,130.7,129.4,
128.7,127.3,126.1,124.7,123.9,122.5,115.3,114.3,51.8,50.8,18.3,18.1。
Elemental analysis:C56H42N2(742.95) theoretical value:C,90.53；H,5.70；N,3.77.Experiment value:C,90.42；H,
6.12；N,3.81.
Embodiment 16 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diethylbenzenes imido grpup)
Acenaphthylene [L7]
1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.280g, 2.00mmol) and 2,6- diethylanilines
(0.328g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to reflux,
React 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 150:1 mixed solvent carries out silicon
Plastic column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.43g, yield：27.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2963(w),2935(w),2873(w),1894(w),1663
(m),1638(m),1604(m),1514(vs),1222(vs),1157(s),1019(m),828(vs),772(vs),734(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.95 (d, J=8.4Hz, 1H), 7.81 (d, J=8.0Hz, 2H), 7.73
(d, J=8.4Hz, 1H), 7.42 (t, J=7.4Hz, 1H), 7.36-7.30 (m, 2H), 7.27-7.20 (m, 2H), 7.07 (t, J
=6.0Hz, 2H), 7.01 (t, J=8.4Hz, 2H), 6.97-6.87 (m, 8H), 6.85 (t, J=6.2Hz, 4H), 6.73 (t, J
=6.6Hz, 2H), 6.65 (d, J=7.2Hz, 1H), 6.48 (s, 1H), 6.25 (s, 1H), 6.19 (t, J=8.2Hz, 2H),
5.84 (s, 1H), 5.79 (d, J=7.2Hz, 1H), 2.77-2.69 (m, 1H), 2.67-2.56 (m, 2H), 2.53-2.45 (m,
1H), 1.27 (t, J=7.2Hz, 6H)13C NMR(100MHz,CDCl3,TMS):δ164.1,162.7,161.4,160.4,
148.5,145.3,140.8,139.6,138.8,135.2,130.6,129.7,128.9,127.4,126.2,124.5,
123.8,115.2,114.4,51.4,50.9,24.8,24.7,14.4,14.2。
Elemental analysis:C58H46N2(771.00) theoretical value:C,90.35；H,6.01；N,3.63.Experiment value:C,90.12；H,
5.98；N,4.03.
Embodiment 17 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diisopropyl benzene imines
Base) acenaphthylene [L8]
1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.280g, 2.00mmol) and 2,6- diisopropyl benzenes
Amine (0.390g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, heats back
Stream reacts 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 150:1 mixed solvent carries out
Silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.40g, yield：25.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2944(w),2923(w),2866(w),1883(w),1665
(m),1641(w),1600(m),1515(vs),1233(vs),1163(s),1028(w),833(s),772(vs),729(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.96 (d, J=8.4Hz, 1H), 7.81 (d, J=6.0Hz, 2H), 7.73
(d, J=8.4Hz, 1H), 7.42 (t, J=7.4Hz, 1H), 7.35 (t, J=7.4Hz, 5H), 7.11 (t, J=6.4Hz, 2H),
7.03 (t, J=8.4Hz, 2H), 6.98-6.81 (m, 11H), 6.77 (t, J=6.4Hz, 2H), 6.59 (d, J=7.2Hz, 1H),
6.46 (s, 1H), 6.25 (s, 1H), 6.18 (t, J=8.4Hz, 2H), 5.82 (s, 1H), 5.75 (d, J=7.2Hz, 1H),
3.22-3.14 (m, 1H), 3.09-3.01 (m, 1H), 1.36 (d, J=6.8Hz, 3H), 1.29 (d, J=6.8Hz, 3H), 1.15
(d, J=6.8Hz, 3H), 0.99 (d, J=6.8Hz, 3H)
13C NMR(100MHz,CDCl3,TMS):δ164.1,162.7,162.4,161.8,161.4,160.5,160.3,
147.2,145.1,140.5,139.7,135.2,130.4,130.1,128.6,128.3,126.5,125.8,124.6,
124.3,123.7,123.2,115.2,114.7,51.2,50.7,28.6,28.4,23.7,23.5,23.3,23.1。
Embodiment 18 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,4,6- trimethylbenzene imines
Base) acenaphthylene [L9]
1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.280g, 2.00mmol) and 2,4,6- trimethylbenzenes
Amine (0.297g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, heats back
Stream reacts 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 150:1 mixed solvent carries out
Silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.39g, yield：25.8%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2966(w),2931(w),2857(w),1896(w),1668
(m),1636(m),1597(m),1509(vs),1229(vs),1164(s),1011(m),822(s),775(s),722(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.87 (d, J=8.4Hz, 1H), 7.74 (d, J=8.4Hz, 2H), 7.65
(d, J=8.0Hz, 1H), 7.32 (t, J=6.2Hz, 1H), 7.25-7.19 (m, 2H), 7.01 (t, J=6.8Hz, 2H), 6.95-
6.91 (m, 4H), 6.89-6.83 (m, 7H), 6.81-6.74 (m, 4H), 6.69 (t, J=6.8Hz, 2H), 6.65 (d, J=
7.2Hz, 1H), 6.37 (s, 1H), 6.12 (s, 1H), 6.09 (t, J=8.4Hz, 2H), 5.76 (s, 1H), 5.67 (d, J=
7.2Hz,1H),2.33(s,3H),2.17(s,3H),2.06(s,3H)。
13C NMR(100MHz,CDCl3,TMS):δ164.2,162.7,162.4,161.3,160.4,159.4,146.9,
145.5,140.7,139.4,137.7,133.5,132.3,130.8,129.5,127.3,126.1,124.4,123.7,
115.2,114.8,51.5,51.1,21.2,19.1,18.0。
Elemental analysis:C57H44N2(756.97) theoretical value:C,90.44；H,5.86；N,3.70.Experiment value:C,90.17；H,
5.87；N,3.32.
Embodiment 19 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diethyl -4- methylbenzenes
Imido grpup) acenaphthylene [L10]
1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.280g, 2.00mmol) and 2,6- diethyl -4-
Methylaniline (0.359g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added,
It is heated to reflux, reacts 10h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 150:1 mixing is molten
Agent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.47g, yield：
29.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2959(w),2924(w),2861(w),1895(w),1661
(m),1637(m),1607(m),1505(vs),1223(vs),1166(s),1017(w),831(vs),777(vs),732(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.96 (d, J=8.4Hz, 1H), 7.81 (d, J=8.4Hz, 2H), 7.74
(d, J=8.4Hz, 1H), 7.41-7.33 (m, 2H), 7.34-7.25 (m, 1H), 7.06-6.95 (m, 6H), 6.91-6.85 (m,
7H), 6.83-6.79 (m, 4H), 6.77-6.73 (m, 2H), 6.70 (d, J=6.8Hz, 1H), 6.49 (s, 1H), 6.23 (s,
1H), 6.16 (t, J=8.4Hz, 2H), 5.85 (s, 1H), 5.72 (d, J=6.8Hz, 1H), 2.76-2.65 (m, 2H), 2.63-
2.51 (m, 2H), 2.46 (s, 3H), 1.25 (t, J=7.6Hz, 3H), 1.16 (t, J=7.4Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ164.3,163.0,161.4,160.6,146.1,140.5,138.6,
135.6,133.8,131.1,130.5,129.6,127.8,124.2,115.8,114.7,51.6,51.0,25.3,24.7,
21.7,14.5,14.0。
Elemental analysis:C59H48N2(785.03) theoretical value:C,90.27；H,6.16；N,3.57.Experiment value:C,89.94；H,
6.08；N,3.89.
Embodiment 20 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- imino dimethyl benzenes)
Acenaphthene closes nickelous bromide (II) [complex C6]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- { 2,4- bis- [two (phenyl)]
Methyl naphthalene imido grpup } -2- (2,6- imino dimethyl benzene) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection,
Ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.14g, yield：72.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2932(w),2867(w),1886(w),1649(w),1624
(m),1595(m),1498(vs),1227(vs),1136(s),1023(m),826(s),776(vs),745(m)。
Elemental analysis:C56H42Br2N2Ni (961.45) theoretical value:C,69.96；H,4.40；N,2.91.Experiment value:C,
69.57；H,3.97；N,2.83.
Embodiment 21 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diethylbenzenes imido grpup)
Acenaphthene closes nickelous bromide (II) [complex C7]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- { 2,4- bis- [two (phenyl)]
Methyl naphthalene imido grpup } -2- (2,6- diethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection,
Ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.17g, yield：85.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2956(w),2879(w),1904(w),1647(w),1622
(m),1594(m),1502(vs),1233(vs),1145(s),1026(m),832(s),779(m),733(m)。
Elemental analysis:C58H46Br2N2Ni (989.50) theoretical value:C,70.40；H,4.69；N,2.83.Experiment value:C,
69.87；H,4.23；N,2.38.
Embodiment 22 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diisopropyl benzene imines
Base) acenaphthene conjunction nickelous bromide (II) [complex C8]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- { 2,4- bis- [two (phenyl)]
Methyl naphthalene imido grpup } -2- (2,6- diisopropyl phenyl imido) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.18g, yield：
88.7%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2965(w),2907(w),2873(w),1888(w),1644
(w),1621(m),1591(m),1504(vs),1221(s),1157(s),1016(w),825(s),772(s),729(w)。
Elemental analysis:C60H50Br2N2Ni (1017.55) theoretical value:C,70.82；H,4.95；N,2.75.Experiment value:C,
70.93；H,4.86；N,2.31.
Embodiment 23 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,4,6- trimethylbenzene imines
Base) acenaphthene conjunction nickelous bromide (II) [complex C9]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- { 2,4- bis- [two (phenyl)]
Methyl naphthalene imido grpup } -2- (2,4,6- trimethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.12g, yield：
61.5%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2958(w),2911(w),2869(w),1900(w),1647
(w),1624(m),1597(m),1511(vs),1230(vs),1148(s),1018(m),827(vs),777(s),723(w)。
Elemental analysis:C57H44Br2N2Ni (975.47) theoretical value:C,70.18；H,4.55；N,2.87.Experiment value:C,
70.02；H,4.37；N,3.12.
Embodiment 24 prepares 1- { 2,4- bis- [two (phenyl)] methyl naphthalene imido grpup } -2- (2,6- diethyl -4- methylbenzenes
Imido grpup) acenaphthene conjunction nickelous bromide (II) [complex C10]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- { 2,4- bis- [two (phenyl)]
Methyl naphthalene imido grpup } -2- (2,6- diethyl -4- methyl phenyl imido) acenaphthylene dichloromethane solution in, under nitrogen protection
12h is stirred, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.15g, yield：
75.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2974(w),2928(w),2881(w),1905(w),1645
(w),1622(w),1599(m),1508(vs),1226(vs),1152(s),1016(w),829(s),774(m),727(w)。
Elemental analysis:C59H48Br2N2Ni (1003.53) theoretical value:C,70.61；H,4.82；N,2.79.Experiment value:C,
70.38；H,4.78；N,2.47.
Embodiment 25 prepares 2- bis- (p-fluorophenyl) methyl naphthylamines
Naphthalidine (5g, 34.92mmol), two (p-fluorophenyl) methanol (7.69g, 34.92mmol), anhydrous ZnCl2
(2.5g, 17.46mmol) is added separately in round-bottomed flask, oil bath heating, and temperature control is at 150 DEG C or so.React 8h.Stop heating
Addition DCM dissolvings, are filtered with diatomite after cooling, removing solvent, and the volume ratio of residue petroleum ether and ethyl acetate is
150:1 mixed solvent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red oil
1.23g, yield 24.8%.
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ7.77-7.75(m,2H),7.44-7.42
(m, 2H), 7.22 (d, J=8.4Hz, 1H), 7.09-6.96 (m, 2H), 6.80 (d, J=8.4Hz, 1H), 5.64 (s, 1H),
4.07(s,2H)。
13C NMR(100MHz,CDCl3,TMS):δ162.9,162.7,160.6,160.3,139.7,138.2,137.1,
131.3,130.5,130.1,126.1,125.1,124.2,121.4,115.7,115.3,115.1,50.3。
Embodiment 26 prepares 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone
Acenaphthenequinone (0.73g, 4mmol) and (p-fluorophenyl) the methyl naphthylamines of 2- bis- (1.38g, 4mmol) be dissolved in ethanol in proper amount and
The in the mixed solvent of dichloromethane is added p-methyl benzenesulfonic acid (0.015g, 0.08mmol), is stirred at room temperature for 24 hours.Solvent is removed, is remained
The volume ratio of excess petroleum ether and ethyl acetate is 80:1 mixed solvent carries out silica gel column chromatography.It is examined by thin layer silica gel plate
Eluted fraction is surveyed, solvent is removed and obtains red powder 0.7g, yield 34%.
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 7.90 (d, J=8.0Hz, 1H), 7.81-
7.77 (m, 2H), 7.73 (d, J=8.4Hz, 1H), 7.65 (d, J=8.0Hz, 1H), 7.39 (t, J=8.0Hz, 2H), 7.34-
7.09 (m, 7H), 7.03 (d, J=8.0Hz, 1H), 6.88 (t, J=8.0Hz, 1H), 6.50 (t, J=7.6Hz, 2H), 5.56
(s,1H)。
13C NMR(100MHz,CDCl3,TMS):δ165.2,163.3,148.7,144.8,142.9,140.9,140.4,
131.2,128.8,128.5,128.1,128.0,127.7,127.3,127.1,126.6,126.1,125.8,125.5,
125.1,124.7,124.5,123.8,123.5,122.4,121.7,52.7。
Embodiment 27 prepares 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- imino dimethyl benzenes) acenaphthene
Alkene [L11]
1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (1.019g, 2.00mmol) and 2,6- dimethylanilines
(0.267g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to reflux,
React 8h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silica gel
Column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.16g, yield：13.1%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3057(w),3041(w),2958(w),1663(m),1639
(m),1592(s),1495(s),1376(m),1267(m),1158(w),1025(m),923(w),829(m),775(vs),746
(s),697(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.86 (d, J=8.0Hz, 1H), 7.75-7.73 (m, 2H), 7.66 (d, J
=8.4Hz, 1H), 7.58 (d, J=8.0Hz, 1H), 7.41 (t, J=8.0Hz, 2H), 7.31-7.06 (m, 9H), 7.00 (d, J
=8.0Hz, 1H), 6.88 (t, J=8.0Hz, 1H), 6.61 (d, J=7.2Hz, 1H), 6.49 (t, J=7.6Hz, 2H), 6.26
(t, J=7.6Hz, 1H), 6.00 (s, 1H), 5.71 (d, J=7.2Hz, 1H), 2.32 (s, 3H), 2.20 (s, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.9,161.4,149.7,145.8142.7,141.1,140.0,
131.7,130.1,129.3,128.5,128.2,127.9,127.6,127.2,126.5,126.1,125.8,125.5,
125.3,125.2,125.0,124.8,124.7,124.4,124.1,123.8,123.5,123.3,122.9,122.2,
121.8,52.7,18.4,18.2。
Elemental analysis:C43H30F2N2(612.71) theoretical value:C,84.29；H,4.94；N,4.57.Experiment value:C,84.31；
H,4.78；N,4.65.
Embodiment 28 prepares 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethylbenzenes imido grpup) acenaphthene
Alkene [L12]
1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (1.019g, 2.00mmol) and 2,6- diethylanilines
(0.328g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to back
Stream reacts 8h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out
Silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.17g, yield：13.3%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3055(w),3043(w),2962(w),1665(m),1637
(m),1594(m),1497(m),1375(s),1265(m),1151(w),1048(m),922(w),828(m),779(vs),745
(s),696(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.85 (d, J=8.0Hz, 1H), 7.74-7.71 (m, 2H), 7.67 (d, J
=8.8Hz, 1H), 7.60 (d, J=8.4Hz, 1H), 7.42 (t, J=7.2Hz, 1H), 7.30-7.13 (m, 9H), 7.01 (d, J
=7.2Hz, 2H), 6.88 (t, J=7.6Hz, 1H), 6.61 (d, J=7.2Hz, 1H), 6.50 (t, J=7.6Hz, 2H), 6.24
(t, J=7.6Hz, 1H), 5.94 (s, 1H), 5.70 (d, J=7.2Hz, 1H), 2.84-2.76 (m, 1H), 2.70-2.61 (m,
2H), 2.50-2.42 (m, 1H), 1.26 (t, J=7.6Hz, 3H), 1.15 (t, J=7.2Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.8,161.5,148.3,146.0,143.5,141.1,140.0,
132.3,131.0,130.5,130.3,130.0,129.1,128.9,128.6,128.3,127.9,127.3,127.1,
126.8,126.5,126.1,125.9,125.4,125.1,124.8,124.2,123.9,123.7,123.5,123.0,
122.4,52.4,25.0,24.5,14.4,14.0。
Elemental analysis:C45H34F2N2(640.76) theoretical value:C,84.35；H,5.35；N,4.37.Experiment value:C,84.29；
H,5.41；N,4.64.
Embodiment 29 prepares 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diisopropyls phenyl imido)
Acenaphthylene [L13]
1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (1.019g, 2.00mmol) and 2,6- diisopropyl anilines
(0.390g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to back
Stream reacts 8h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out
Silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.19g, yield：14.2%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3051(w),2969(w),2907(w),1666(w),1635
(m),1591(m),1492(s),1377(s),1253(s),1155(w),1054(m),925(w),829(m),778(vs),732
(s),698(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.86 (d, J=8.4Hz, 1H), 7.75-7.71 (m, 2H), 7.68 (d, J
=8.8Hz, 1H), 7.59 (d, J=8.4Hz, 1H), 7.41 (t, J=7.2Hz, 1H), 7.33-7.14 (m, 9H), 7.00 (d, J
=7.6Hz, 2H), 6.85 (t, J=7.6Hz, 1H), 6.54 (d, J=7.2Hz, 1H), 6.51 (t, J=7.2Hz, 2H), 6.27
(t, J=7.2Hz, 1H), 5.97 (s, 1H), 5.64 (d, J=7.2Hz, 1H), 3.32-3.22 (m, 1H), 3.11-3.03 (m,
1H), 1.34 (d, J=6.4Hz, 3H), 1.27 (d, J=6.8Hz, 3H), 0.98 (d, J=6.8Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.9,161.8,147.1,146.4,143.6,141.4,140.1,
135.2,135.0,132.5,130.1,129.6,129.2,129.0,128.5,128.3,128.0,127.8,127.4,
127.1,126.8,126.5,126.2,126.1,125.9,125.2,124.3,124.1,123.5,123.2,123.0,
122.9,52.5,28.7,28.6,24.2,23.8,23.6,23.4。
Elemental analysis:C47H38F2N2(668.81) theoretical value:C,84.40；H,5.73；N,4.19.Experiment value:C,84.21；
H,5.32；N,4.34.
Embodiment 30 prepares 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,4,6- trimethylbenzenes imido grpup)
Acenaphthylene [L14]
1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (1.019g, 2.00mmol) and 2,4,6- trimethylanilines
(0.297g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, is heated to reflux,
React 8h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent carries out silica gel
Column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.23g, yield：18.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3056(w),2959(w),1661(m),1637(m),1596
(m),1483(s),1446(s),1371(s),1272(s),1147(w),1045(m)921(w),833(m),785(vs),742
(s),697(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.88 (d, J=8.4Hz, 1H), 7.76-7.73 (m, 2H), 7.67 (d, J
=8.4Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 7.42 (t, J=7.2Hz, 1H), 7.33-7.26 (m, 4H), 7.01 (d, J
=8.8Hz, 4H), 6.90 (t, J=8.0Hz, 1H), 6.71 (d, J=7.2Hz, 1H), 6.52 (t, J=7.6Hz, 2H), 6.28
(t, J=7.2Hz, 1H), 6.03 (s, 1H), 5.74 (d, J=7.2Hz, 1H), 2.41 (s, 3H), 2.30 (s, 3H), 2.18 (s,
3H)。
13C NMR(100MHz,CDCl3,TMS):δ163.9,161.6,146.7,146.1,143.5,141.9,140.8,
133.1,132.6,130.5,130.0,129.9,129.2,129.0,128.9,128.3,128.2,128.1,127.7,
127.6,127.4,126.4,126.0,125.9,125.3,125.1,124.9,124.0,123.8,123.5,123.3,
122.4,52.6,21.3,18.5,18.3。
Elemental analysis:C44H32F2N2(626.74) theoretical value:C,84.32；H,5.15；N,4.47.Experiment value:C,84.28；
H,5.45；N,4.08.
Embodiment 31, preparing 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2-, (2,6- diethyl -4- methylbenzenes are sub-
Amido) acenaphthylene [L15]
1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] acenaphthene ketone (1.019g, 2.00mmol) and 2,6- diethyl -4- first
Base aniline (0.359g, 2.20mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, adds
Heat reflux, reacts 8h.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent
Carry out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.18g, yield：
13.8%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3055(w),2964(m),1665(m),1638(m),1592
(m),1483(m),1457(s),1376(s),1266(s),1154(m),1036(w),924(w),827(m),777(vs),743
(s),698(vs)。
1H NMR(400MHz,CDCl3,TMS):δ 7.87 (d, J=8.0Hz, 1H), 7.72 (d, J=8.0Hz, 2H), 7.69
(d, J=8.4Hz, 1H), 7.58 (d, J=8.4Hz, 1H), 7.41 (t, J=7.2Hz, 1H), 7.32-7.17 (m, 6H), 7.05-
7.00 (m, 4H), 6.86 (t, J=8.0Hz, 1H), 6.69 (d, J=7.2Hz, 1H), 6.53 (t, J=7.2Hz, 2H), 6.32
(t, J=7.2Hz, 1H), 6.01 (s, 1H), 5.73 (d, J=7.2Hz, 1H), 2.77-2.70 (m, 1H), 2.64-2.56 (m,
2H), 2.49-2.38 (m, 4H), 1.25 (t, J=7.6Hz, 3H), 1.15 (t, J=7.6Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ163.8,161.7,146.1,145.9,143.6,141.5,140.8,
133.7,131.2,130.5,129.8,129.7,129.4,128.8,128.3,128.1,128.0,127.9,127.4,
127.3,126.5,126.2,126.0,125.4,124.1,124.0,123.6,123.3,122.8,52.6,25.2,24.9,
21.3,14.7,14.3。
Elemental analysis:C46H36F2N2(654.79) theoretical value:C,84.38；H,5.54；N,4.28.Experiment value:C,84.15；
H,5.66；N,4.65.
Embodiment 32 prepares { 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- imino dimethyl benzenes)
Acenaphthene } close nickelous bromide (II) [complex C11]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (p-fluorophenyl) first
Base naphthalene imido grpup] -2- (2,6- imino dimethyl benzene) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, add
Entering ether has red solid precipitation, filtering, and ether washing, drying obtains dark red solid 0.10g.Yield：60.2%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3058(w),3047(w),2976(w),1654(w),1623
(m),1601(m),1487(s),1374(m),1298(m),1156(w),1033(m),917(w),824(m),772(vs),741
(s),695(vs)。
Elemental analysis:C43H30Br2F2N2Ni (831.21) theoretical value:C,62.13；H,3.64；N,3.37.Experiment value:C,
62.02；H,3.95；N,3.51.
Embodiment 33 prepares { 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diethylbenzenes imido grpup)
Acenaphthene } close nickelous bromide (II) [complex C12]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (p-fluorophenyl) first
Base naphthalene imido grpup] -2- (2,6- diethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection, add
Entering ether has red solid precipitation, filtering, and ether washing, drying obtains dark red solid 0.14g.Yield：81.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3055(w),2965(w),1649(w),1626(m),1592
(m),1491(s),1378(s),1293(s),1154(w),1044(m),916(w),822(m),781(vs),740(s),693
(vs)。
Elemental analysis:C45H34Br2F2N2Ni (859.26) theoretical value:C,62.90；H,3.99；N,3.26.Experiment value:C,
62.82；H,3.95；N,3.48.
Embodiment 34 prepares { 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,6- diisopropyls phenyl imido)
Acenaphthene } close nickelous bromide (II) [complex C13]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (p-fluorophenyl) first
Base naphthalene imido grpup] -2- (2,6- diisopropyl phenyl imido) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection,
Ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.16g.Yield：90.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3047(w),2961(w),2896(w),1646(w),1625
(m),1589(m),1493(s),1385(s),1297(s),1176(w),1056(m),951(w),827(m),775(vs),736
(m),698(vs)。
Elemental analysis:C47H38Br2F2N2Ni (887.32) theoretical value:C,63.62；H,4.32；N,3.16.Experiment value:C,
63.86；H,3.91；N,3.34.
Embodiment 35 prepares { 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2- (2,4,6- trimethylbenzenes imido grpup)
Acenaphthene } close nickelous bromide (II) [complex C14]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (p-fluorophenyl) first
Base naphthalene imido grpup] -2- (2,4,6- trimethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir 12h under nitrogen protection,
Ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.14g.Yield：82.8%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3058(w),2985(w),1647(m),1619(m),1594
(m),1485(s),1373(s),1294(s),1162(m),1048(s),937(m),834(m),782(vs),739(s),696
(vs)。
Elemental analysis:C44H32Br2F2N2Ni (845.24) theoretical value:C,62.52；H,3.82；N,3.31.Experiment value:C,
62.28；H,3.45；N,3.67.
Embodiment 36 prepares the { (2,6- diethyl -4- methylbenzenes Asias 1- [(p-fluorophenyl) methyl naphthalenes of 2- bis- imido grpup] -2-
Amido) acenaphthene } close nickelous bromide (II) [complex C15]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1- [2- bis- (p-fluorophenyl) first
Base naphthalene imido grpup] -2- (2,6- diethyl -4- methyl phenyl imido) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h is mixed, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.12g.Yield：
68.6%.
Structural identification data is as follows：FT-IR(KBr,cm-1):3055(w),2978(w),1644(w),1623(m),1592
(m),1491(s),1438(s),1375(s),1298(s),1169(w),1046(m),945(w),828(m),775(vs),741
(s),697(vs)。
Elemental analysis:C46H36Br2F2N2Ni (873.29) theoretical value:C,63.27；H,4.16；N,3.21.Experiment value:C,
63.52；H,3.95；N,3.04.
Embodiment 37 prepares 2,4- bis- [two (p-fluorophenyl)] methyl naphthylamines
Naphthalidine (4.7g, 32.88mmol), two (p-fluorophenyl) methanol (7.24g, 32.88mmol), anhydrous ZnCl2
(2.3g, 16.44mmol) is added separately in round-bottomed flask, oil bath heating, and temperature control is at 150 DEG C or so.React 8h.Stop heating
Addition DCM dissolvings, are filtered with diatomite after cooling, removing solvent, and the volume ratio of residue petroleum ether and ethyl acetate is
150:1 mixed solvent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains crocus solid
3.61g, yield 20%,
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 7.82 (d, J=8.8Hz, 2H), 7.46-
7.38(m,3H),6.91-6.86(m,16H),6.08(s,1H),6.02(s,2H),5.56(s,1H),4.15(s,2H)。
13C NMR(100MHz,CDCl3,TMS):δ163.0,162.7,160.6,160.3,139.7,138.2,138.1,
131.3,130.8,130.1,129.5,126.1,125.1,124.2,121.4,115.7,115.3,115.1,51.4,50.9。
Embodiment 38 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone
Acenaphthenequinone (0.73g, 4mmol) and 2,4- bis- [two (p-fluorophenyl)] methyl naphthylamines (2.19g, 4mmol) are dissolved in right amount
The in the mixed solvent of ethyl alcohol and dichloromethane is added p-methyl benzenesulfonic acid (0.015g, 0.08mmol), is stirred at room temperature for 24 hours.It removes molten
The volume ratio of agent, residue petroleum ether and ethyl acetate is 80:1 mixed solvent carries out silica gel column chromatography.Pass through thin-layer silicon
Offset plate detects eluted fraction, removes solvent and obtains red powder 1.5g, yield 53%.
Structural identification data is as follows：1H NMR(400MHz,CDCl3,TMS):δ 8.12 (t, J=8.8Hz, 2H), 7.93 (d,
J=8.4Hz, 1H), 7.85-7.77 (m, 2H), 7.67 (d, J=8.0Hz, 1H), 7.39 (t, J=7.6Hz, 1H), 7.29-
7.26 (m, 1H), 7.06-7.00 (m, 5H), 6.94-6.87 (m, 4H), 6.80 (d, J=7.2Hz, 4H), 6.67-6.64 (m,
2H), 6.47 (s, 1H), 6.20 (s, 1H), 6.13 (t, J=8.4Hz, 2H), 5.78 (d, J=7.6Hz, 1H), 5.66 (s, 1H).
13C NMR(100MHz,CDCl3,TMS):δ164.0,162.4,161.3,140.1,139.4,130.5,129.4,
128.3,127.5,126.3,124.4,123.7,122.6,115.1,114.3,51.3,50.6。
Embodiment 39 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- dimethyl benzene imines
Base) acenaphthylene [L16]
1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.247g, 1.78mmol) and 2,6- dimethyl
Aniline (0.215g, 1.78mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.007g, 0.04mmol), heating is added
To reflux, 10h is reacted.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent
Carry out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.21g, yield：
13.8%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2864(w),2730(w),1888(w),1669(m),1635
(m),1600(s),1504(vs),1225(vs),1156(s),1017(m),821(vs),771(vs),723(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.93 (d, J=8.4Hz, 1H), 7.81 (d, J=8.4Hz, 2H), 7.72
(d, J=8.0Hz, 1H), 7.41-7.28 (m, 4H), 7.20 (t, J=8.2Hz, 2H), 7.00 (t, J=8.6Hz, 3H), 6.96-
6.89 (m, 5H), 6.86-6.81 (m, 5H), 6.76 (t, J=7.0Hz, 2H), 6.65 (d, J=7.2Hz, 1H), 6.47 (s,
1H), 6.21 (s, 1H), 6.17 (d, J=8.6Hz, 2H), 5.83 (s, 1H), 5.78 (d, J=7.2Hz, 1H), 2.27 (s, 3H),
2.18(s,3H)。
13C NMR(100MHz,CDCl3,TMS):δ164.0,162.4,161.3,140.5,139.4,130.5,129.1,
128.3,127.1,126.0,124.5,123.7,122.4,115.1,114.3,51.4,50.8,18.2,18.0。
Elemental analysis:C56H38F4N2(814.91) theoretical value:C,82.54；H,4.70；N,3.44.Experiment value:C,82.15；
H,4.56；N,3.65.
Embodiment 40 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- diethylbenzene imines
Base) acenaphthylene [L17]
1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone (0.711g, 1.00mmol) and 2,6- diethyl
Aniline (0.156g, 1.10mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.004g, 0.02mmol), heating is added
To reflux, 10h is reacted.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixed solvent
Carry out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.30g, yield：
35.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2963(w),2927(w),2870(w),1890(w),1668
(m),1636(m),1599(s),1504(vs),1224(vs),1157(s),1016(m),820(vs),772(vs),723(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.93 (d, J=8.4Hz, 1H), 7.80 (d, J=8.0Hz, 2H), 7.71
(d, J=8.4Hz, 1H), 7.39 (t, J=7.4Hz, 1H), 7.34-7.29 (m, 2H), 7.27-7.20 (m, 2H), 7.07 (t, J
=6.0Hz, 2H), 7.01 (t, J=8.4Hz, 2H), 6.97-6.87 (m, 6H), 6.83 (t, J=6.2Hz, 4H), 6.74 (t, J
=6.6Hz, 2H), 6.63 (d, J=7.2Hz, 1H), 6.48 (s, 1H), 6.22 (s, 1H), 6.18 (t, J=8.2Hz, 2H),
5.84 (s, 1H), 5.76 (d, J=7.2Hz, 1H), 2.77-2.68 (m, 1H), 2.66-2.55 (m, 2H), 2.50-2.40 (m,
1H), 1.25 (t, J=7.2Hz, 6H).
13C NMR(100MHz,CDCl3,TMS):δ164.1,162.7,161.2,160.3,148.2,145.2,140.5,
139.5,138.6,135.1,130.6,129.4,128.8,127.1,126.2,124.3,123.6,115.2,114.3,51.4,
50.8,24.8,24.6,14.4,14.1。
Elemental analysis:C58H42F4N2(842.96) theoretical value:C,82.64；H,5.02；N,3.32.Experiment value:C,82.25；
H,4.76；N,5.35.
Embodiment 41 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- diisopropyl base benzene
Imido grpup) acenaphthylene [L18]
1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone (1.420g, 2.00mmol) and 2,6- diisopropyls
Base aniline (0.370g, 2.10mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.008g, 0.04mmol) is added, adds
Heat reacts 10h to flowing back.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixing is molten
Agent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.30g, yield：
17.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2925(w),2927(w),2866(w),1893(w),1675
(m),1646(w),1600(m),1505(vs),1225(vs),1157(s),1016(w),822(s),772(vs),721(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.94 (d, J=8.4Hz, 1H), 7.80 (d, J=6.0Hz, 2H), 7.71
(d, J=8.4Hz, 1H), 7.40 (t, J=7.4Hz, 1H), 7.32 (t, J=7.4Hz, 5H), 7.09 (t, J=6.4Hz, 2H),
7.02 (t, J=8.4Hz, 2H), 6.96-6.80 (m, 9H), 6.76 (t, J=6.4Hz, 2H), 6.60 (d, J=7.2Hz, 1H),
6.49 (s, 1H), 6.23 (s, 1H), 6.17 (t, J=8.4Hz, 2H), 5.84 (s, 1H), 5.74 (d, J=7.2Hz, 1H),
3.23-3.16 (m, 1H), 3.07-3.00 (m, 1H), 1.34 (d, J=6.8Hz, 3H), 1.28 (d, J=6.8Hz, 3H), 1.13
(d, J=6.8Hz, 3H), 0.97 (d, J=6.8Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ164.1,162.7,162.6,161.6,161.4,160.3,160.2,
147.0,145.2,140.6,139.5,135.4,130.7,130.4,128.8,128.4,126.5,126.0,124.5,
124.3,123.6,123.3,115.3,114.6,51.4,50.8,28.7,28.6,23.8,23.6,23.5,23.2。
Elemental analysis:C60H46F4N2(871.01) theoretical value:C,82.74；H,5.32；N,3.22.Experiment value:C,82.45；
H, 4.96；N, 3.35.
Embodiment 42, preparing 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2-, (2,4,6- trimethylbenzenes are sub-
Amido) acenaphthylene [L19]
1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone (0.711g, 1.00mmol) and 2,4,6- front threes
Base aniline (0.148g, 1.10mmol) is dissolved in 50mL toluene solutions, and p-methyl benzenesulfonic acid (0.004g, 0.02mmol) is added, adds
Heat reacts 10h to flowing back.The volume ratio of removing solvent toluene, residue petroleum ether and ethyl acetate is 200:1 mixing is molten
Agent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid 0.17g, yield：
21.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2956(w),2920(w),2857(w),1889(w),1668
(m),1636(m),1600(m),1504(vs),1224(vs),1157(s),1016(m),820(s),775(s),722(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.85 (d, J=8.4Hz, 1H), 7.73 (d, J=8.4Hz, 2H), 7.64
(d, J=8.0Hz, 1H), 7.29 (t, J=6.2Hz, 1H), 7.23-7.18 (m, 2H), 7.00 (t, J=6.8Hz, 2H), 6.95-
6.90 (m, 4H), 6.88-6.81 (m, 5H), 6.79-6.73 (m, 4H), 6.69 (t, J=6.8Hz, 2H), 6.64 (d, J=
7.2Hz, 1H), 6.39 (s, 1H), 6.14 (s, 1H), 6.08 (t, J=8.4Hz, 2H), 5.76 (s, 1H), 5.69 (d, J=
7.2Hz,1H),2.32(s,3H),2.16(s,3H),2.07(s,3H)。
13C NMR(100MHz,CDCl3,TMS):δ164.2,162.8,162.6,161.7,160.4,159.2,146.6,
145.3,140.5,139.1,137.4,133.3,132.4,130.8,129.2,127.1,126.0,124.6,123.8,
115.3,114.5,51.5,50.9,21.0,19.3,18.2。
Elemental analysis:C57H40F4N2(828.93) theoretical value:C,82.59；H,4.86；N,3.38.Experiment value:C,82.45；
H,4.96；N,3.35.
Embodiment 43 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- diethyl -4- first
Base phenyl imido) acenaphthylene [L20]
1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } acenaphthene ketone (0.711g, 1.00mmol) and 2,6- diethyls
Base -4- methylanilines (0.179g, 1.10mmol) are dissolved in 50mL toluene solutions, addition p-methyl benzenesulfonic acid (0.004g,
0.02mmol), it is heated to flowing back, reacts 10h.Solvent toluene is removed, the volume ratio of residue petroleum ether and ethyl acetate is
200:1 mixed solvent carries out silica gel column chromatography.Eluted fraction is detected by thin layer silica gel plate, solvent is removed and obtains red solid
0.27g, yield：32.0%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2963(w),2926(w),2867(w),1892(w),1660
(m),1635(m),1598(m),1504(vs),1223(vs),1158(s),1016(w),821(vs),770(vs),722(m)。
1H NMR(400MHz,CDCl3,TMS):δ 7.93 (d, J=8.4Hz, 1H), 7.80 (d, J=8.4Hz, 2H), 7.70
(d, J=8.4Hz, 1H), 7.40-7.34 (m, 2H), 7.32-7.25 (m, 1H), 7.09-6.98 (m, 6H), 6.95-6.89 (m,
5H), 6.86-6.81 (m, 4H), 6.78-6.74 (m, 2H), 6.70 (d, J=6.8Hz, 1H), 6.48 (s, 1H), 6.21 (s,
1H), 6.17 (t, J=8.4Hz, 2H), 5.83 (s, 1H), 5.74 (d, J=6.8Hz, 1H), 2.73-2.64 (m, 2H), 2.62-
2.53 (m, 2H), 2.44 (s, 3H), 1.23 (t, J=7.6Hz, 3H), 1.14 (t, J=7.4Hz, 3H).
13C NMR(100MHz,CDCl3,TMS):δ164.3,163.0,161.6,160.4,146.0,140.7,138.9,
135.3,133.7,131.0,130.7,129.2,127.4,124.5,115.3,114.7,51.7,51.0,25.0,24.8,
21.4,14.7,14.1。
Elemental analysis:C59H44F4N2(856.99) theoretical value:C,82.69；H,5.18；N,3.27.Experiment value:C,82.53；
H,4.73；N,3.21.
Embodiment 44 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- dimethyl benzene imines
Base) acenaphthene] close nickelous bromide (II) [complex C16]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,6- imino dimethyl benzene) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.12g.Yield：
81.9%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2800(w),2771(w),1889(w),1649(w),1622
(m),1602(s),1507(vs),1227(vs),1155(s),1017(m),830(s),776(vs),737(m)。
Elemental analysis:C56H38Br2F4N2Ni (1033.41) theoretical value:C,65.09；H,3.71；N,2.71.Experiment value:C,
64.79；H,4.16；N,3.01.
The crystal structure figure of complex C16 is as shown in Figure 4.
Embodiment 45 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- diethylbenzene imines
Base) acenaphthene] close nickelous bromide (II) [complex C17]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,6- diethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.08g.Yield：
72.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2974(w),2937(w),2876(w),1908(w),1647
(w),1621(m),1600(s),1505(vs),1225(vs),1157(s),1016(m),835(s),776(m),723(m)。
Elemental analysis:C58H42Br2F4N2Ni (1061.46) theoretical value:C,65.63；H,3.99；N,2.64.Experiment value:C,
64.81；H,4.32；N,2.78.
Embodiment 46, preparing 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2-, (2,6- diisopropyl benzenes are sub-
Amido) acenaphthene] close nickelous bromide (II) [complex C18]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,6- diisopropyl phenyl imido) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h is mixed, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.15g.Yield：
92.6%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2968(w),2930(w),2867(w),1889(w),1650
(w),1621(m),1602(m),1505(vs),1227(s),1154(s),1018(w),827(s),772(s),723(w)。
Elemental analysis:C60H46Br2F4N2Ni (1089.52) theoretical value:C,66.14；H,4.26；N,2.57.Experiment value:C,
65.72；H,4.23；N,2.89.
Embodiment 47, preparing 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2-, (2,4,6- trimethylbenzenes are sub-
Amido) acenaphthene] close nickelous bromide (II) [complex C19]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,4,6- trimethylbenzene imido grpup) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h is mixed, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.03g.Yield：
31.7%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2950(w),2913(w),2853(w),1900(w),1652
(w),1624(m),1600(s),1503(vs),1220(vs),1157(s),1015(m),827(vs),777(s),713(w)。
Elemental analysis:C57H40Br2F4N2Ni (1047.44) theoretical value:C,65.36；H,3.85；N,2.67.Experiment value:C,
65.01；H,3.97；N,2.74.
Embodiment 48 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- diethyl -4- first
Base phenyl imido) acenaphthene] close nickelous bromide (II) [complex C20]
At room temperature, in molar ratio 1:1.1 by (DME) NiBr2Dichloromethane solution is added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,6- diethyl -4- methyl phenyl imido) acenaphthylene dichloromethane solution in, nitrogen protect
Shield is lower to stir 12h, and ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.10g.Production
Rate：93.4%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2971(w),2934(w),2874(w),1910(w),1647
(w),1620(w),1599(m),1505(vs),1225(vs),1158(s),1015(w),828(s),777(m),717(w)。
Elemental analysis:C59H44Br2F4N2Ni (1075.49) theoretical value:C,65.89；H,4.12；N,2.60.Experiment value:C,
64.93；H,3.85；N,2.97.
Embodiment 49 prepares 1- { 2,4- bis- [two (p-fluorophenyl)] methyl naphthalene imido grpup } -2- (2,6- dimethyl benzene imines
Base) acenaphthene] close nickel chloride (II) [complex C21]
At room temperature, in molar ratio 1:1.1 by NiCl2·6H2O dichloromethane solutions are added drop-wise to 1-, and { [two (to fluorobenzene by 2,4- bis-
Base)] methyl naphthalene imido grpup -2- (2,6- imino dimethyl benzene) acenaphthylene dichloromethane solution in, stir under nitrogen protection
12h, ether, which is added, red solid precipitation, filters, and ether washing, drying obtains dark red solid 0.15g.Yield：80%.
Structural identification data is as follows：FT-IR(KBr,cm-1):2800(w),2773(w),1890(w),1647(w),1621
(m),1602(s),1507(vs),1227(vs),1155(s),1017(m),830(s),776(vs),737(m)。
Elemental analysis:C56H38Cl2F4N2Ni (944.51) theoretical value:C,71.21；H,4.06；N,2.97.Experiment value:C,
71.32；H,4.18；N,3.06.
Embodiment 50 utilizes complex C3 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
A) vinyl polymerization under pressurizeing is stainless using one 300 milliliters equipped with mechanical agitation paddle and temperature control equipment
Steel polymeric kettle.Polymeric kettle is vacuumized and is heated to 100 DEG C, heating time continues two hours.It is being replaced in kettle in advance with ethylene
Under conditions of nitrogen, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Three times with toluene rinse kettle, then successively
50mL toluene is added, 20mL is dissolved with the toluene solution of 2 μm of ol catalyst (C3), 0.5mL co-catalysts (Et2AlCl,1.17mol/
The toluene solution of L) and residual toluene (so that toluene total amount is 100 milliliters).Polymeric kettle is closed, logical ethylene simultaneously maintains second
The pressure of alkene is constant (10atm).After polymerisation reaches the preset time (30min), the ethylene pressure in kettle is released
It puts, 100mL ethyl alcohol is added into mixed liquor, has checked whether polyethylene generation.If there is polyethylene generates, after filtration washing
It is dried to constant weight, according to the Production rate polymerization activity of polymer in 60 DEG C of baking oven.Polymerization activity：2.96×106g·mol-1
(Ni)·h-1, polymer Mw=419kgmol-1,Mw/Mn=2.4.
B) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 0.7mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.87×106g·mol-1(Ni)·h-1, gather
Close object Mw=402kgmol-1,Mw/Mn=2.8.
C) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L) and residual toluene (so that first
Benzene total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.45×106g·mol-1(Ni)·h-1, polymer Mw=335kgmol-1,Mw/Mn=2.9.
D) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L) and residual toluene (so that first
Benzene total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：7.71×106g·mol-1(Ni)·h-1, polymer Mw=329kgmol-1,Mw/Mn=2.7.
E) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.2mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L) and residual toluene (so that first
Benzene total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.10×106g·mol-1(Ni)·h-1, polymer Mw=278kgmol-1,Mw/Mn=3.2.
F) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.83×106g·mol-1(Ni)·h-1, polymer
Mw=572kgmol-1,Mw/Mn=2.5.
G) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：6.25×106g·mol-1(Ni)·h-1, polymer
Mw=257kgmol-1,Mw/Mn=3.6.
H) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.39×106g·mol-1(Ni)·h-1, polymer
Mw=187kgmol-1,Mw/Mn=2.6.
I) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.23×106g·mol-1(Ni)·h-1, polymer
Mw=135kgmol-1,Mw/Mn=2.5.
J) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：10.38×106g·mol-1
(Ni)·h-1, polymer Mw=274kgmol-1,Mw/Mn=3.1.
K) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：5.69×106g·mol-1
(Ni)·h-1, polymer Mw=330kgmol-1,Mw/Mn=2.4.
L) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：4.83×106g·mol-1
(Ni)·h-1, polymer Mw=333kgmol-1,Mw/Mn=3.7.
M) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL)；2, ethylene pressure 5atm.Polymerization activity：4.36×106g·mol-1(Ni)·h-1, polymer Mw=
238kg·mol-1,Mw/Mn=3.3.
Embodiment 51 utilizes complex C1 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C1)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.13×106g·mol-1(Ni)·h-1, polymer
Mw=209kgmol-1,Mw/Mn=3.4.
Embodiment 52 utilizes complex C2 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C2)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.33×106g·mol-1(Ni)·h-1, polymer
Mw=263kgmol-1,Mw/Mn=3.1.
Embodiment 53 utilizes complex C4 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C4)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.92×106g·mol-1(Ni)·h-1, polymer
Mw=334kgmol-1,Mw/Mn=2.7.
Embodiment 54 utilizes complex C5 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C5)
Toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.72×106g·mol-1(Ni)·h-1, polymer
Mw=429kgmol-1,Mw/Mn=3.2.
Embodiment 55 utilizes the vinyl polymerization under complex C3 and MAO joint catalysis pressurization：
1) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 1.4mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.84×106g·mol-1(Ni)·h-1, polymer
Mw=559kgmol-1,Mw/Mn=1.9.
2) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.1mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.49×106g·mol-1(Ni)·h-1, polymer
Mw=404kgmol-1,Mw/Mn=3.3.
3) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：6.27×106g·mol-1(Ni)·h-1, polymer
Mw=497kgmol-1,Mw/Mn=2.8.
4) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 3.4mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.47×106g·mol-1(Ni)·h-1, polymer
Mw=567kgmol-1,Mw/Mn=2.4.
5) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 4.1mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.61×106g·mol-1(Ni)·h-1, polymer
Mw=579kgmol-1,Mw/Mn=2.2.
6) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.62×106g·mol-1(Ni)·h-1, polymer
Mw=636kgmol-1,Mw/Mn=2.8.
7) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.65×106g·mol-1(Ni)·h-1, polymer
Mw=426kgmol-1,Mw/Mn=2.3.
8) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.72×106g·mol-1(Ni)·h-1, polymer
Mw=329kgmol-1,Mw/Mn=2.1.
9) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C3)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.45×106g·mol-1(Ni)·h-1, polymer
Mw=281kgmol-1,Mw/Mn=2.0.
10) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：10.24×106g·mol-1(Ni)·h-1, polymer Mw=465kgmol-1,Mw/Mn=3.0.
11) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：4.67×106g·mol-1(Ni)·h-1,
Polymer Mw=548kgmol-1,Mw/Mn=2.7.
12) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：3.93×106g·mol-1(Ni)·h-1,
Polymer Mw=571kgmol-1,Mw/Mn=2.4.
13) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C3) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL)；2, ethylene pressure 5atm.Polymerization activity：3.78×106g·mol-1(Ni)·h-1, polymer Mw=489kg
mol-1,Mw/Mn=2.9.
Embodiment 56 utilizes the vinyl polymerization under complex C1 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C1)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.73×106g·mol-1(Ni)·h-1, polymer
Mw=315kgmol-1,Mw/Mn=2.8.
Embodiment 57 utilizes the vinyl polymerization under complex C2 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C2)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.40×106g·mol-1(Ni)·h-1, polymer
Mw=436kgmol-1,Mw/Mn=2.6.
Embodiment 58 utilizes the vinyl polymerization under complex C4 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C4)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.79×106g·mol-1(Ni)·h-1, polymer
Mw=351kgmol-1,Mw/Mn=2.7.
Embodiment 59 utilizes the vinyl polymerization under complex C5 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C5)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：7.26×106g·mol-1(Ni)·h-1, polymer
Mw=454kgmol-1,Mw/Mn=2.6.
Embodiment 60 utilizes complex C8 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
1) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.4mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：0.15×106g·mol-1(Ni)·h-1, gather
Close object Mw=302kgmol-1,Mw/Mn=1.99.
2) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.5mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.31×106g·mol-1(Ni)·h-1, gather
Close object Mw=353kgmol-1,Mw/Mn=1.84.
3) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.6mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.58×106g·mol-1(Ni)·h-1, gather
Close object Mw=378kgmol-1,Mw/Mn=1.73.
4) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.19×106g·mol-1(Ni)·h-1, gather
Close object Mw=418kgmol-1,Mw/Mn=1.70.
5) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.73×106g·mol-1(Ni)·h-1, gather
Close object Mw=345kgmol-1,Mw/Mn=1.63.
6) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.45×106g·mol-1(Ni)·h-1, gather
Close object Mw=439kgmol-1,Mw/Mn=1.53.
7) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.32×106g·mol-1(Ni)·h-1, gather
Close object Mw=334kgmol-1,Mw/Mn=1.76.
8) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.12×106g·mol-1(Ni)·h-1, gather
Close object Mw=321kgmol-1,Mw/Mn=1.56.
9) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：1.37×106g·mol-1(Ni)·h-1, gather
Close object Mw=298kgmol-1,Mw/Mn=1.41.
10) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slow
It is cooled to the polymerization temperature (70 DEG C) of imagination；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C8) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：0.42×106g·mol-1(Ni)·h-1, gather
Close object Mw=211kgmol-1,Mw/Mn=1.20.
11) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C8), 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：6.87×106g·mol-1
(Ni)·h-1, polymer Mw=221kgmol-1,Mw/Mn=1.66.
12) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C8), 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：3.65×106g·mol-1
(Ni)·h-1, polymer Mw=252kgmol-1,Mw/Mn=1.78.
13) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C8), 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：3.34×106g·mol-1
(Ni)·h-1, polymer Mw=328kgmol-1,Mw/Mn=1.82.
14) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C8), 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, ethylene pressure 5atm.Polymerization activity：3.12×106g·mol-1(Ni)·h-1, polymer Mw=
198kg·mol-1,Mw/Mn=1.63.
Embodiment 61 utilizes complex C6 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C6) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.43×106g·mol-1(Ni)·h-1, gather
Close object Mw=231kgmol-1,Mw/Mn=1.58.
Embodiment 62 utilizes complex C7 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C7) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.72×106g·mol-1(Ni)·h-1, gather
Close object Mw=254kgmol-1,Mw/Mn=1.67.
Embodiment 63 utilizes complex C9 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C9) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene is total
Amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.13×106g·mol-1(Ni)·h-1, gather
Close object Mw=214kgmol-1,Mw/Mn=1.85.
Embodiment 64 utilizes complex C10 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C10) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.29×106g·mol-1(Ni)·h-1,
Polymer Mw=290kgmol-1,Mw/Mn=1.49.
Embodiment 65 utilizes complex C13 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations：
1) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.4mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.15×106g·mol-1(Ni)·h-1,
Polymer Mw=243kgmol-1,Mw/Mn=2.3.
2) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.5mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.31×106g·mol-1(Ni)·h-1,
Polymer Mw=269kgmol-1,Mw/Mn=2.2.
3) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.6mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.54×106g·mol-1(Ni)·h-1,
Polymer Mw=318kgmol-1,Mw/Mn=2.0.
4) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.47×106g·mol-1(Ni)·h-1,
Polymer Mw=323kgmol-1,Mw/Mn=1.8.
5) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.57×106g·mol-1(Ni)·h-1,
Polymer Mw=334kgmol-1,Mw/Mn=1.6.
6) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.32×106g·mol-1(Ni)·h-1,
Polymer Mw=363kgmol-1,Mw/Mn=2.2.
7) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.79×106g·mol-1(Ni)·h-1,
Polymer Mw=334kgmol-1,Mw/Mn=2.0.
8) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.01×106g·mol-1(Ni)·h-1,
Polymer Mw=311kgmol-1,Mw/Mn=1.9.
9) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：1.28×106g·mol-1(Ni)·h-1,
Polymer Mw=258kgmol-1,Mw/Mn=1.9.
10) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slow
It is cooled to the polymerization temperature (70 DEG C) of imagination；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：0.46×106g·mol-1(Ni)·h-1,
Polymer Mw=198kgmol-1,Mw/Mn=1.8.
11) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：7.01×106g·mol-1
(Ni)·h-1, polymer Mw=246kgmol-1,Mw/Mn=2.3.
12) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：4.75×106g·mol-1
(Ni)·h-1, polymer Mw=283kgmol-1,Mw/Mn=1.9.
13) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：3.45×106g·mol-1
(Ni)·h-1, polymer Mw=330kgmol-1,Mw/Mn=1.8.
14) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL)；2, ethylene pressure 5atm.Polymerization activity：3.32×106g·mol-1(Ni)·h-1, polymer Mw=
220kg·mol-1,Mw/Mn=1.9.
Embodiment 66 utilizes complex C11 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C11)
Toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.41×106g·mol-1(Ni)·h-1, polymer
Mw=231kgmol-1,Mw/Mn=2.3.
Embodiment 67 utilizes complex C12 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C12)
Toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.78×106g·mol-1(Ni)·h-1, polymer
Mw=269kgmol-1,Mw/Mn=2.1.
Embodiment 68 utilizes complex C14 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C14)
Toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.96×106g·mol-1(Ni)·h-1, polymer
Mw=224kgmol-1,Mw/Mn=2.0.
Embodiment 69 utilizes complex C15 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C15)
Toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.45×106g·mol-1(Ni)·h-1, polymer
Mw=276kgmol-1,Mw/Mn=1.9
Embodiment 70 utilizes the vinyl polymerization under complex C13 and MAO joint catalysis pressurization：
1) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 1.4mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.34×106g·mol-1(Ni)·h-1, polymerization
Object Mw=439kgmol-1,Mw/Mn=3.0.
2) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.1mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.31×106g·mol-1(Ni)·h-1, polymerization
Object Mw=404kgmol-1,Mw/Mn=2.9.
3) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.27×106g·mol-1(Ni)·h-1, polymerization
Object Mw=397kgmol-1,Mw/Mn=2.8.
4) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 3.4mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.27×106g·mol-1(Ni)·h-1, polymerization
Object Mw=367kgmol-1,Mw/Mn=2.5.
5) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 4.1mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.81×106g·mol-1(Ni)·h-1, polymerization
Object Mw=398kgmol-1,Mw/Mn=2.3.
6) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.31×106g·mol-1(Ni)·h-1, polymerization
Object Mw=533kgmol-1,Mw/Mn=2.4.
7) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.34×106g·mol-1(Ni)·h-1, polymerization
Object Mw=446kgmol-1,Mw/Mn=2.3.
8) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.12×106g·mol-1(Ni)·h-1, polymerization
Object Mw=425kgmol-1,Mw/Mn=2.1.
9) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：1.87×106g·mol-1(Ni)·h-1, polymerization
Object Mw=382kgmol-1,Mw/Mn=2.0.
10) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slow
It is cooled to the polymerization temperature (70 DEG C) of imagination；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：1.21×106g·mol-1(Ni)·h-1, polymerization
Object Mw=312kgmol-1,Mw/Mn=1.9.
11) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：6.94×106g·mol-1(Ni)·
h-1, polymer Mw=356kgmol-1,Mw/Mn=2.4.
12) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：4.37×106g·mol-1(Ni)·
h-1, polymer Mw=518kgmol-1,Mw/Mn=2.5.
13) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：3.13×106g·mol-1(Ni)·
h-1, polymer Mw=543kgmol-1,Mw/Mn=2.3.
14) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst
(C13) toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount
For 100mL)；2, ethylene pressure 5atm.Polymerization activity：3.25×106g·mol-1(Ni)·h-1, polymer Mw=359kg
mol-1,Mw/Mn=2.5.
Embodiment 71 utilizes the vinyl polymerization under complex C11 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C11)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.81×106g·mol-1(Ni)·h-1, polymer
Mw=376kgmol-1,Mw/Mn=2.0.
Embodiment 72 utilizes the vinyl polymerization under complex C12 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C12)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.51×106g·mol-1(Ni)·h-1, polymer
Mw=334kgmol-1,Mw/Mn=2.5.
Embodiment 73 utilizes the vinyl polymerization under complex C14 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C14)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.38×106g·mol-1(Ni)·h-1, polymer
Mw=359kgmol-1,Mw/Mn=2.3.
Embodiment 74 utilizes the vinyl polymerization under complex C15 and MAO joint catalysis pressurization：
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 2 μm of ol catalyst (C15)
Toluene solution, 2.7mL co-catalysts (toluene solution of MAO, 1.46mol/L), residual toluene is (so that toluene total amount is
100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.24×106g·mol-1(Ni)·h-1, polymer
Mw=371kgmol-1,Mw/Mn=2.0.
Embodiment 75 utilizes complex C18 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
1) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.5mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：0.18×106g·mol-1(Ni)·h-1,
Polymer Mw=320kgmol-1,Mw/Mn=1.99.
2) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.64mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.74×106g·mol-1(Ni)·h-1,
Polymer Mw=363kgmol-1,Mw/Mn=1.74.
3) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.8mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.85×106g·mol-1(Ni)·h-1,
Polymer Mw=368kgmol-1,Mw/Mn=1.73.
4) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.79×106g·mol-1(Ni)·h-1,
Polymer Mw=373kgmol-1,Mw/Mn=1.72.
5) substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 1.0mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.76×106g·mol-1(Ni)·h-1,
Polymer Mw=480kgmol-1,Mw/Mn=1.70.
6) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (20 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：0.73×106g·mol-1(Ni)·h-1,
Polymer Mw=558kgmol-1,Mw/Mn=1.48.
7) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (40 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.45×106g·mol-1(Ni)·h-1,
Polymer Mw=211kgmol-1,Mw/Mn=1.29.
8) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (50 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.58×106g·mol-1(Ni)·h-1,
Polymer Mw=144kgmol-1,Mw/Mn=1.67.
9) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slowly cold
But to the polymerization temperature (60 DEG C) imagined；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：2.09×106g·mol-1(Ni)·h-1,
Polymer Mw=86kgmol-1,Mw/Mn=1.40.
10) substantially it is same a), difference lies in：1, under conditions of replacing nitrogen in kettle in advance with ethylene, make polymeric kettle slow
It is cooled to the polymerization temperature (70 DEG C) of imagination；2,50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5μMol catalyst
(C18) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：1.01×106g·mol-1(Ni)·h-1,
Polymer Mw=80kgmol-1,Mw/Mn=1.31.
11) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C18), 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that first
Benzene total amount is 100mL)；2, polymerisation reaches the preset time for 15min.Polymerization activity：6.69×106g·mol-1
(Ni)·h-1, polymer Mw=210kgmol-1,Mw/Mn=1.66.
12) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C18), 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that first
Benzene total amount is 100mL)；2, polymerisation reaches the preset time for 45min.Polymerization activity：4.30×106g·mol-1
(Ni)·h-1, polymer Mw=213kgmol-1,Mw/Mn=1.89.
13) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C18), 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that first
Benzene total amount is 100mL)；2, polymerisation reaches the preset time for 60min.Polymerization activity：3.42×106g·mol-1
(Ni)·h-1, polymer Mw=230kgmol-1,Mw/Mn=1.82.
14) substantially it is same a), difference lies in：1,50mL toluene is sequentially added into reaction kettle, 20mL is catalyzed dissolved with 1.5 μm of ol
The toluene solution of agent (C18), 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that first
Benzene total amount is 100mL)；2, ethylene pressure 5atm.Polymerization activity：3.42×106g·mol-1(Ni)·h-1, polymer Mw=
158kg·mol-1,Mw/Mn=1.33.
Embodiment 76 utilizes complex C16 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C16) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.61×106g·mol-1(Ni)·h-1,
Polymer Mw=96kgmol-1,Mw/Mn=1.22.
Embodiment 77 utilizes complex C17 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C17) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：3.58×106g·mol-1(Ni)·h-1,
Polymer Mw=217kgmol-1,Mw/Mn=1.81.
Embodiment 78 utilizes complex C19 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C19) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.46×106g·mol-1(Ni)·h-1,
Polymer Mw=92kgmol-1,Mw/Mn=1.99.
Embodiment 79 utilizes complex C20 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C20) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：5.00×106g·mol-1(Ni)·h-1,
Polymer Mw=217kgmol-1,Mw/Mn=1.97.
Embodiment 80 utilizes complex C21 and Et2Vinyl polymerization under AlCl joint catalysis pressurizations
Substantially it is same a), difference lies in：50mL toluene is sequentially added into reaction kettle, 20mL is dissolved with 1.5 μm of ol catalyst
(C21) toluene solution, 0.9mL co-catalysts (Et2The toluene solution of AlCl, 1.17mol/L), residual toluene is (so that toluene
Total amount is 100mL).According to the Production rate polymerization activity of polymer.Polymerization activity：4.98×106g·mol-1(Ni)·h-1,
Polymer Mw=239kgmol-1,Mw/Mn=1.99.
Claims (1)
1. a kind of method preparing polyethylene, includes the following steps：Using carbon monoxide-olefin polymeric as catalyst, catalysis ethylene carries out
Polymerisation, reaction finish to obtain the polyethylene；
The temperature of the polymerisation is 30 DEG C；
The time of the polymerisation is 15 minutes；
What the polymerisation carried out under elevated pressure, the pressure of the pressurization is 10atm；
The polymerisation carries out in a solvent, and the solvent is toluene；
The carbon monoxide-olefin polymeric nickel metal complex and co-catalyst shown in Formulas I form；
In the Formulas I, R1=CHPh2；R2=H；R3=i-Pr；R4=H；X is Br；
Wherein, Ph represents phenyl；I-Pr represents isopropyl；
The co-catalyst is diethylaluminum chloride；
The molar ratio of nickel element and aluminium element in the diethylaluminum chloride is 1 in nickel metal complex shown in the Formulas I：585.
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| CN108864340B (en) * | 2017-05-12 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst composition and olefin polymerization process |
| CN107955088B (en) * | 2017-09-28 | 2020-05-05 | 东华大学 | Catalyst, preparation method thereof, composition prepared from catalyst and application of composition |
| CN109957050B (en) * | 2017-12-25 | 2022-03-08 | 杭州星庐科技有限公司 | Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof |
| CN110041456B (en) * | 2018-01-17 | 2021-08-31 | 中国石油天然气股份有限公司 | Supported catalyst for preparing polypropylene elastomer montmorillonite composite material and preparation method thereof |
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| CN109400777B (en) * | 2018-11-09 | 2021-01-22 | 河北师范大学 | Vanadium complex based on acenaphthoquinone diimine ligand and preparation method and application thereof |
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