CN101948489B - Nickel complex and preparation and application thereof - Google Patents

Nickel complex and preparation and application thereof Download PDF

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CN101948489B
CN101948489B CN2010102350393A CN201010235039A CN101948489B CN 101948489 B CN101948489 B CN 101948489B CN 2010102350393 A CN2010102350393 A CN 2010102350393A CN 201010235039 A CN201010235039 A CN 201010235039A CN 101948489 B CN101948489 B CN 101948489B
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toluene
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ethene
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polymeric kettle
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CN101948489A (en
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金永利
曾艳宁
余建刚
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Abstract

The invention discloses a nickel complex. The structure of the nickel complex is shown in the formula I, wherein R1 is C1-C3 alkyl; R2 is hydrogen, methyl or ethyl; R3 is hydrogen, halogen or aromatic base; and X is halogen. The invention also provides a preparation method and application of the nickel complex. The nickel complex has better catalytic property in the ethylene oligomerization and polymerization reactions in the presence of a cocatalyst aluminoxane or alkylaluminum. The polymerization activity of the complex reaches 1.24*10<7>g.mol<-1> (Ni).h<-1>, at the same time, the molecularweight distribution can be lowered to 1.8 and the oligomerization activity of the complex can reach 9.5*10<6>g.mol<-1> (Ni).h<-1>. The formula I is shown in the specification.

Description

Nickel metal complexes and preparation thereof and application
Technical field
The present invention relates to a kind of nickel metal complexes and preparation and application.
Background technology
The develop rapidly of ethylene oligomerization polymerization industry has benefited from development and the terminal olefin and the huge applications of Vilaterm in current life, industry of its catalyzer to a great extent.The method of the linear alhpa olefin of the previous main industrial production of order is an application of SH OP type catalyzer, its structure be shown below (Angew.Chem., Int.Ed.Engl.1978,17,466-467; Angew.Chem., Int.Ed.Engl.1983,22,503; J.Chem.Soc., Chem.Commun.1994,2203-2204):
And Ziegler-Natta type catalyzer (DE patent, 889229.1953-09-07; IT patent, 545332.1954; IT patent, 536899.1955; Belg patent, 533326.1955-05-05; Angew chem.1955,67,541-547; J Polym Sci PartA:Chem, 1955,16:143-154), Phillips type catalyzer (Belg patent 530617.1955; USpatent, 2825721.1958-03-04; Adv Catalysis, 1985,33:47-56) and metallocene type catalyst (Metalorganic Catalysis for Synthesis and Polymerization.Berlin:Springer, 1999.1-674; Advances in Organomet Chem, 1980,18:99-105; Angew.Chem.Int.Ed.1980,19:390-392).
People are when making great efforts to improve existing catalyzer (comprising synthetic and preparation), and the continuous more excellent new catalyst of exploratory development catalytic performance is for fresh blood has been injected in the development of ethylene oligomerization and polymerization industry.Wherein late transition metal catalyst development is particularly rapid, receives people's extensive attention, like recent patent: PCT Int.Appl.WO 9951550 A1 14 Oct 1999, this patent report one type of three tooth cobalt salt title complex be used for ethylene reaction; Jan.Kokai Tokyo Koho JP 11060627, A22 Mar 1999 Heisei have reported that then one type of bidentate nickel salt title complex is used for the ethylene oligomerization reaction.
Nineteen ninety-five, Brookhart group has reported that alpha-diimine type Ni (II) title complex is used for vinyl polymerization.Because part is synthetic simple, the steric hindrance of part and Electronic Performance are easy to modify and regulate, and this report has caused the upsurge to the research of late transition metal complex alkene catalyst.This complex structure as follows (J.Am.Chem.Soc., 1995,117,6414-6415):
The contriver is devoted to the research of ethylene oligomerization and polymerizing catalyst and Catalytic processes in the past in the several years always; Researched and developed the ethylene oligomerization catalyst of multiclass nickel complex: patent ZL 00 1 21033.5; July 17 2000 applying date, Granted publication day 2003.1.8; Patented claim 01118455.8, the May 31 calendar year 2001 applying date; Patent ZL 01120214.9, the applying date: July 6 calendar year 2001, Granted publication day 2004.7.7; Patented claim 01120554.7, the July 20 calendar year 2001 applying date; Patent ZL02118523.9, April 26 2002 applying date, Granted publication day 2004.12.22; Patent ZL 02123213.X, June 12 2002 applying date, Granted publication day 2003.11.19; Patented claim 03137727.0, June 23 2003 applying date; Patented claim 03148378.X, July 2 2003 applying date; Patented claim 03154463.0, October 8 2003 applying date; October 29 2004 200410086284.7 applying date of patented claim; December 30 2004 200410081711.2 applying date of patented claim; Patented claim 2007100642731.2, on 03 08th, 2007 applying date; July 19 2007 200710119281.2 applying date of patented claim.In above catalyst research and performance history, exist the problem of some: be not only the problem that the ethylene reaction activity is difficult to improve, and exist ethylene oligomerization and polymerization to be difficult to obtain single catalysis.In addition, the nickel complex as catalyst agent is synthetic all to be that the multistep building-up process is accomplished, and has increased operation, presses for the method for preparing catalyzer simply and easily.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention provides a kind of nickel metal complexes, and the structure of said nickel metal complexes is suc as formula shown in the I:
Figure BSA00000202689100021
Formula I
Wherein, R 1Alkyl for C1～C3; R 2Be hydrogen, methyl or ethyl; R 3Be hydrogen, halogen or aromatic base; X is a halogen.
Preferably, R 1Be methyl, ethyl or sec.-propyl, R 3Be hydrogen, chlorine or phenyl, X is a chlorine or bromine.
The present invention provides a kind of method for preparing above-mentioned nickel metal complexes, comprises the steps:
1) with 2-R 3-5,6,7-three hydrogen quinoline-8-ketone and 2,6-two R 1-4-R 2After-aniline mixes, add p-methyl benzenesulfonic acid, in toluene solvant, nitrogen protection refluxed reaction 4-5 hour, purifying promptly obtains 2-R 3-5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-two R 1-4-R 2-aniline part, wherein, R 1Be the alkyl of C1～C3, R 2Be hydrogen, methyl or ethyl, R 3Be hydrogen, X is a halogen;
2) step 1) gained part is mixed with the nickel salt of halogen, stirring at room is 8 hours under the nitrogen protection, and deposition is separated out, and filters, and ether washing three times obtains described nickel metal complexes,
The present invention provides the method for the above-mentioned nickel metal complexes of another kind of preparation, comprises the steps:
With 2-R 3-5,6,7-three hydrogen quinoline-8-ketone and 2,6-two R 1-4-R 2The nickel salt of-aniline and halogen adds the 3h that refluxes in the acetate, and the solvent of distillation removal under reduced pressure adds dissolve with ethanol, adds ether, and solid settles out, and the back gets said nickel metal complexes with the ether washing.Wherein, R 1Be the alkyl of C1～C3, R 2Be hydrogen, methyl or ethyl, R 3Be chlorine or aromatic base, X is a halogen.
As preferably, the nickel salt of above-mentioned halogen is NiCl 26H2O or (DME) NiBr 2
The present invention provides a kind of ethylene oligomerization and polymeric catalyst system, and in the said catalyst system, catalyzer is above-mentioned nickel metal complexes.
Preferably, also contain promotor in the above-mentioned catalyst system, said promotor is one or more in aikyiaiurnirsoxan beta, modified alumoxane and the aluminum alkyls.Further as preferred, above-mentioned aikyiaiurnirsoxan beta is MAO (MAO), and above-mentioned modified alumoxane is modified methylaluminoxane (MMAO); Abovementioned alkyl aluminium is triethyl aluminum (AlEt 3), diethylaluminum chloride (AlEt 2Cl) or ethyl aluminium sesqui chloride (EASC).
The mol ratio of metallic aluminium is in above-mentioned catalyst center metallic nickel and the above-mentioned promotor: Ni: Al=1: 200～1: 2500.
The present invention provides a kind of method of carrying out ethylene polymerization, comprises the steps:
1) polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times;
2) replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to 20～100 ℃ of polymerization temperatures; Wash said polymeric kettle three times with toluene, add toluene then successively, be dissolved with the toluene solution of said catalyzer and be dissolved with the toluene solution of promotor;
3) seal said polymeric kettle, pressure is 10atm in feeding ethene to the polymeric kettle, and keeps constant pressure;
4) behind polyreaction 10～120min, the ethylene pressure in the still is discharged, the filtration washing after drying is to constant weight.
The present invention also provides a kind of method of carrying out the ethylene oligomerization reaction, comprises the steps:
1) polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.
2) replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to 20～100 ℃ of polymerization temperatures; With toluene or the said polymeric kettle of heptane three times, add toluene or heptane then successively, be dissolved with the toluene or the n-heptane solution of said catalyzer and be dissolved with the toluene or the n-heptane solution of promotor;
3) seal said polymeric kettle, pressure is 10atm in feeding ethene to the polymeric kettle, and keeps constant pressure;
4) behind polyreaction 10～120min, the ethylene pressure in the still is discharged, collect polymeric solution, said polymeric solution is stopped polymerization with ethanol solution hydrochloride.As preferably, the mass percent concentration of said ethanol solution hydrochloride is 5%.
The present invention designs that to have synthesized structural formula be the nickel metal complexes of formula I.As the ethylene oligomerization catalyst for reaction, above-mentioned nickel metal complexes is at promotor MAO, MMAO, AlEt 3, AlEt 2Cl or EASC effect show excellent performance: 1) R in nickel metal complexes shown in the formula I down in ethylene oligomerization or polyreaction 3During for the less hydrogen of steric hindrance, the ethylene polymerization activity of above-mentioned title complex is higher, and works as R 3During for bigger chlorine of steric hindrance or phenyl, the ethylene oligomerization activity of above-mentioned title complex is higher.2) under the activation of promotor, R 3Nickel metal complexes for hydrogen shows higher ethylene polymerization activity, and under the activation of diethylaluminum chloride, high reactivity can reach 1.21 * 10 7Gmol -1(Ni) h -13) with R 3For the nickel metal complexes of hydrogen carries out ethylene polymerization as catalyzer, the molecular weight distribution of gained is narrow, and lowest molecular weight distributes can reach 1.8; 4) R 3For the nickel metal complexes of chlorine or phenyl, under the activation of ethyl aluminium sesqui chloride, carry out ethylene oligomerization reaction, high reactivity can reach 9.5 * 10 6Gmol -1(Ni) h -1, C4 and alpha selective are all more than 80%.
Description of drawings
Figure one is title complex Ni1 (R 1=Me; R 2=H; R 3=H, X=Cl) crystalline structure synoptic diagram;
Figure two is title complex Ni3 (R 1=i-Pr; R 2=H; R 3=H, X=Cl) crystalline structure synoptic diagram;
Figure three is title complex Ni7 (R 1=Et; R 2=H; R 3=Cl, X=Cl) crystalline structure synoptic diagram;
Figure four is title complex Ni8 (R 1=iPr; R 2=H; R 3=Cl, X=Cl) crystalline structure synoptic diagram;
Figure five is title complex Ni13 (R 1=i-Pr; R 2=H; R 3=Ph, X=Cl) crystalline structure synoptic diagram;
Figure six is title complex Ni15 (R 1=Et; R 2=Me; R 3=Ph, X=Cl) crystalline structure synoptic diagram.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is described further so that those skilled in the art can better understand the present invention and implementing, but the embodiment that lifts not conduct to qualification of the present invention.
Embodiment one
1, the preparation of part: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-diisopropyl aniline [L3]: with 5; 6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; After 6-diisopropyl aniline (0.6 gram, 5.1 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 0.5 mmole), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, gets the yellow oily part, productive rate 66%.FT-IR(KBr，cm -1)：3047，2960，2866，2829，1929.3，1864，1640(v?C＝N)，1571，1476，1426，1329，1254，1194，1104，1050，1016，796，771，674. 1H?NMR(400MHz，CDCl 3)：δ?8.73(d，J＝4.1?Hz，1H，Py?H)；7.57(d，J＝7.7Hz，1H，Py?H)；7.30(t，J＝4.5Hz，1H，Py?H)；7.14(d，J＝7.5?Hz，2H，Ar?H)；7.07(t，J＝6.7?Hz，1H，Ar?H)；2.95(t，J＝6.0?Hz，2H，CH 2)；2.85(m，2H，2×CH)；2.43(t，J＝6.1Hz，2H，CH 2)；1.93(m，2H，CH 2)；1.15(m，12H，4×CH 3). 13C?NMR(100?MHz，CDCl 3)：δ164.7，148.9?146.7，137.5，137.1，136.2?125.0，123.5，123.0，122.9，31.0，21.6，28.1，23.6，22.3.Anal.Calcd?for?C 21H 26N 2(306)：C，82.31；H，8.55；N，9.14.Found：C，82.57；H，8.23；N，9.06。
2, the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-diisopropyl aniline closes nickelous chloride (II) [Ni3] in preparation
Under the room temperature, with one times of normal NiCl 26H 2The O ethanolic soln is for being added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts 2, and in the ethanolic soln of 6-xylidine, stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under the nitrogen guarantor expands.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, get bluish yellow look title complex, productive rate 82% through 8 hours.FT-IR(KBr，disk，cm -1)：3201，3064，2946，2865，2363，1626，1586，1459，1330，1217，1136，1050，807，779，735，661.Anal.Calcd?for?C 21H 26Cl 2N 2Ni(436)：C，57.84，H，6.01；N，6.42.Found：C，57.57；H，5.64；N，6.09。The crystalline structure synoptic diagram is seen accompanying drawing 2.
3, add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of setting.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5mol catalyzer (Ni3), 0.38mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, remains to be toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30 min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.7.
Embodiment two
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20 mL are dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.35mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.8 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.3kgmol -1, M w/ M n=1.8.
Embodiment three
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.41mL promotor (AlEt 3, the toluene solution of 0.74mol/L), the mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.8 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.3kgmol -1, M w/ M n=1.8.
Embodiment four
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 1.0mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 1000 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.5kgmol -1, M w/ M n=1.9.
Embodiment five
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.78mL promotor (MMAO, the toluene solution of 1.93mol/L); The mol ratio of metallic aluminium is about 1: 1000 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.2kgmol -1, M w/ M n=1.8.
Embodiment six
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.5mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.2kgmol -1, M w/ M n=1.6.
Embodiment seven
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 1.5mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 1500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.9 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.5kgmol -1, M w/ M n=1.9.
Embodiment eight
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.0mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2000 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.3kgmol -1, M w/ M n=1.9.
Embodiment nine
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.5 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.3kgmol -1, M w/ M n=1.9.
Embodiment ten
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.5mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.5kgmol -1, M w/ M n=1.9.
Embodiment 11
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.9 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.4kgmol -1, M w/ M n=2.0.
Embodiment 12
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=2.3kgmol -1, M w/ M n=1.6.
Embodiment 13
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 2.6 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.3kgmol -1, M w/ M n=2.4.
Embodiment 14
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (80 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=6.9kgmol -1, M w/ M n=3.5.
Embodiment 15
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (100 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=24.3kgmol -1, M w/ M n=12.2.
Embodiment 16
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (10min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.6 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.1kgmol -1, M w/ M n=2.1.
Embodiment 17
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (20min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.5 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.2kgmol -1, M w/ M n=2.0.
Embodiment 18
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (40min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.3 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.5kgmol -1, M w/ M n=2.1.
Embodiment 19
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (60min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.0 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.8kgmol -1, M w/ M n=2.1.
Embodiment 20
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (90min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.9 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=5.1kgmol -1, M w/ M n=1.9.
Embodiment 21
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (120min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.8 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=5.0kgmol -1, M w/ M n=2.1.
Embodiment 22
1, the preparation of part: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-xylidine [L1]: with 5; 6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; After 6-xylidine (0.5 gram, 5 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 0.5 mmole), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, can obtain the yellow oily part, productive rate 66%.FT-IR(KBr，cm -1)：3038，2928，2828，1925，1641(vC＝N)，1476，1435，1279，1195，1099，1041，794，796，673. 1HNMR(400MHz，CDCl 3，TMS)：δ8.72(d，J＝4.0Hz，1H，Py?H)；7.56(d，J＝7.6Hz，1H，Py?H)；7.29(m，1H，Py?H)；7.02(d，J＝7.5Hz，2H，Ar?H)；6.90(t，J＝7.5Hz，1H，Ar?H)；2.94(t，J＝6.0Hz，2H，CH2)；2.35(t，J＝6.2Hz，2H，CH2)；2.04(s，6H，2×CH3)；1.93(m，2H，CH2). 13CNMR(100MHz，CDCl 3，TMS)：δ164..6，150.1，149.0，137.3，137.1，128.3，125.3，122.7，122.1，30.6，29.6，22.4，18.4，18.3.Anal.Calcd?forC 17H 18N 2(250)：C，81.56；H，7.25；N，11.19.Found：C，81.87；H，7.30；N，10.71。
2, the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-xylidine closes nickelous chloride (II) [Ni1]: under the room temperature, with one times of normal NiCl in preparation 26H 2The O ethanolic soln is for being added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts 2, and in the ethanolic soln of 6-xylidine, stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under nitrogen protection.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, obtain the title complex N1 that wants, productive rate 76% through 8 hours.FT-IR(KBr，disk，cm -1)：3347，3067，2949，1624，1683，1461，1336，1217，1197，1131，1107，789，656.Anal.Calcd?for?C 17H 18C1 2N 2Ni(380)：C，53.74；H，4.78；N，7.37.Found：C，53.12；H，4.42；N，7.03。The crystalline structure synoptic diagram is seen accompanying drawing 1
3, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni1), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=9.2kgmol -1, M w/ M n=2.2.
Embodiment 23
1, the preparation of part: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-Diethyl Aniline [L2]: with 5; 6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; After 6-Diethyl Aniline (0.5 gram, 5 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 0.5 mmole), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, gets the yellow oily part, productive rate 62%.FT-IR(KBr，cm -1)：3034，2963，2932，2870，2831，1940，1639(vC＝N)，1462，1422，1277，1191，1101，819，675. 1H?NMR(400MHz，CDCl 3)：δ8.72(d，J＝4.4Hz，1H，Py?H)；7.56(d，J＝7.4Hz，1H，Py?H)；7.28(m，1H，Py?H)；7.08(d，J＝7.6Hz，2H，Ar?H)；7.00(m，1H，Ar?H)；2.93(t，J＝6.1Hz，2H，CH 2)；2.45(t，J＝7.4Hz，2H，CH 2)；2.35(m，4H，2×CH 2)；1.91(m，2H，CH 2)；1.14(t，J＝7.5Hz，6H，2×CH 3). 13C?NMR(100MHz，CDCl 3)：δ164.4，150.5，149.9，148.9，137.0，134.7，131.0，125.5?124.9，122.9，6，30.8，29.5，24.4，22.3，13.9.Anal.Calcd?for?C 17H 18N 2(278)：C，81.97；H，7.97；N，10.06.Found：C，82.11；H，7.60；N，9.76。
2, the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-Diethyl Aniline closes nickelous chloride (II) [Ni2]: with one times of normal NiCl in preparation 26H 2The O ethanolic soln is for being added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts 2, and in the ethanolic soln of 6-Diethyl Aniline, stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under nitrogen protection.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, get bluish yellow look title complex, productive rate 78% through 8 hours.FT-IR(KBr，disk，cm -1)：3348，3068，2963，2932，2873，1623，1585，1487，1334，1287，1217，1192，1131，1046，927，859，779，661.Anal.Calcd?for?C 19H 22Cl 2N 2Ni(408)：C，55.93；H，5.44；N，6.87.Found：C，55.61；H，5.15；N，6.53。
3, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni2), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=6.0kgmol -1, M w/ M n=2.2.
Embodiment 24
1, the preparation of part: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,4; 6-trimethylaniline [L4]: with 5,6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; 4, after 6-trimethylaniline (0.5 gram, 5 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 0.5 mmole), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, gets the yellow oily part, productive rate 81%.FT-IR(KBr，cm -1)：3001，2916，2841，2728，1942，1902，1861，1636(vC＝N)，1566，1480，1410，1268，1098，1021，846，793，668. 1H?NMR(400MHz，CDCl 3)：δ8.72(d，J＝4.1Hz，1H，Py?H)；7.56(d，J＝7.7Hz，1H，Py?H)；7.29(m，1H，Py?H)；6.85(s，2H，Ar?H)；2.93(t，J＝6.0Hz，2H，CH 2)；2.36(t，J＝6.1Hz，2H，CH 2)；2.27(s，3H，CH 3)；2.01(s，6H)；1.93(m，2H). 13C?NMR(100MHz，CDCl 3)：δ164.7，150.1，149.0，146.8，137.2，137.0，131.7，128.9，128.4，125.1，124.8，30.5，29.5，22.4，20.8，18.3，18.1.Anal.Calcd?for?C 18H 20N 2(264)：C，81.78；H，7.63；N，10.60.Found：C，82.03；H，7.42；N，10.32。
2, the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone 2 that contracts closes nickelous chloride (II) [Ni4]: with one times of normal NiCl in preparation 26H 2In O ethanolic soln generation, be added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts in the ethanolic soln of 2, and stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under nitrogen protection.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, get bluish yellow look title complex, productive rate 72% through 8 hours.FT-IR(KBr，disk，cm -1)：3339，2920，1626，1585，1456，1332，1285，1213，1131，924，854，789，661.Anal.Calcd?for?C 18H 20Cl 2N 2Ni(394)：C，54.88，H，5.12；N，7.11.Found：C，55.09；H，5.51；N，7.27。
3, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni4), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.5 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=5.5kgmol -1, M w/ M n=2.2.
Embodiment 25
1, the preparation of part: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-dimethyl-4-MEA [L5]: with 5; 6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; After 6-diethylammonium-4-monomethylaniline (0.6 gram, 5 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 5 mmoles), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, gets the yellow oily part, productive rate 74%.FT-IR(KBr，cm -1)：2964，2930，2873，2828，1743，1640(vC＝N)，1571，1531，1426，1326，1293，1270，1195，1098，859，193，677. 1H?NMR(400MHz，CDCl 3)：δ8.72(d，J＝4.4Hz，1H，Py?H)；7.56(d，J＝7.4Hz，1H，Py?H)；7.30(m，1H，Py?H)；6.89(s，2H，Ar?H)；2.93(t，J＝6.0Hz，1H，CH 2)；2.40(t，J＝6.0Hz，2H，CH 2)；2.33(m，7H)；1.91(m，2H，CH 2)；1.13(t，J＝7.5Hz，6H，2×CH 3). 13C?NMR(100MHz，CDCl 3)：δ164.7，150.2，149.0，145.7，137.3，137.2，137.0，132.0，131.0，127.1，126.3，124.8，30.7，29.6，24.7，24.4，22.3，21.2，14.0.Anal.Calcd?for?C 20H 24N 2(292)：C，82.15；H，8.27；N，9.58.Found：C，82.32；H，8.14；N，9.46。
2., the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone contracts 2, and 6-dimethyl-4-MEA closes nickelous chloride (II) [Ni5]: with one times of normal NiCl in preparation 26H 2The O ethanolic soln is for being added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts 2, and in the ethanolic soln of 6-dimethyl--4-MEA, stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under nitrogen protection.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, get bluish yellow look title complex, productive rate 75% through 8 hours.FT-IR(KBr，disk，cm -1)：3331，2051，2930，2872，1623，1583，1460，1336，1287，1212，1130，1045，923，859，796，663.Anal.Calcd?for?C 20H 24Cl 2N 2Ni(422)：C，56.92，H，5.73；N，6.64.Found：C，56.53；H，5.45；N，6.25。
3, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni5), 2.25mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 2250 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.6 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=5.4kgmol -1, M w/ M n=2.1.
Embodiment 26
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.76mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), residual toluene (making that the toluene total amount is 100 milliliters).The mol ratio of metallic aluminium is 1: 400 in said catalyst center metallic nickel and the promotor, and with still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.9.Melting temperature: 74.1 ℃.
Embodiment 27
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.5 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.1kgmol -1, M w/ M n=1.8.
Embodiment 28
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 1.14mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 600 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.3 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=2.9kgmol -1, M w/ M n=2.0.
Embodiment 29
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 1.52mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 800 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=2.8kgmol -1, M w/ M n=1.8.Melting temperature: 71.6 ℃.
Embodiment 30
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.1 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=1.8kgmol -1, M w/ M n=1.9.Melting temperature: 71.4 ℃.
The embodiment hentriaconta-
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.8 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.4kgmol -1, M w/ M n=2.4.Melting temperature: 82.1 ℃.
Embodiment 32
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (80 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=8.4kgmol -1, M w/ M n=4.3.Melting temperature: 96.2 ℃.
Embodiment 33
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (100 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 2.5 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=51.7kgmol -1, M w/ M n=25.3.Melting temperature: 118.7 ℃.
Embodiment 34
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (10min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=2.9kgmol -1, M w/ M n=1.7.Melting temperature: 71.4 ℃.
Embodiment 35
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (20min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.1kgmol -1, M w/ M n=1.7.Melting temperature: 73.4 ℃.
Embodiment 36
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (40min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.9 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.9.
Embodiment 37
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (40min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.9 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.9.
Embodiment 38
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (60min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.4 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.9.
Embodiment 39
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (90min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.3 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=4.7kgmol -1, M w/ M n=2.0.
Embodiment 40
1, the preparation of catalyst n i3 is as embodiment one.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni3), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (120min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.7 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=5.4kgmol -1, M w/ M n=1.9.
Embodiment 41
1, the preparation of catalyst n i1 is as embodiment 22.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni1), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.7 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=2.3kgmol -1, M w/ M n=1.8.
Embodiment 42
1, the preparation of catalyst n i2 is as embodiment 23.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni2), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.9kgmol -1, M w/ M n=2.1 melting temperatures: 87.5 ℃.
Embodiment 43
1, the preparation of catalyst n i4 is as embodiment 24.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni4), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.16 * 10 7Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.9, melting temperature: 82.1 ℃.
Embodiment 44
1, the preparation of catalyst n i5 is as embodiment 25.
2, pressurization vinyl polymerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni5), 0.95mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.24 * 10 7Gmol -1(Ni) h -1, polymkeric substance M w=3.4kgmol -1, M w/ M n=2.0.
Embodiment 45
1, the preparation of title complex: preparation [2-chloro-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-diisopropyl aniline closes nickelous chloride (II) [Ni8]: with 2-chloro-5,6,7-three hydrogen quinoline-8-ketone and 2,6-diisopropyl aniline and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, oven dry can obtain title product.Get dark green title complex, productive rate 23%.FT-IR(KBr，disk，cm -1)：3345，2931，1567，1488，1409，1341，1239，1123，1028，866，783，675，616，502，403.Anal.Calcd?for?C 17H 17Cl 3N 2Ni(414)：C，49.27；H，4.14；N，6.76.Found：C，49.21；H，4.51；N，6.29.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni8), 1.4mL promotor (AlEt 3, the toluene solution of 0.74mol/L), the mol ratio of metallic aluminium is about 1: 690 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After reaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 1.2 * 10 5Gmol -1(Ni) h -1, C4/ ∑ C=81.1%, α-C4/C4=78.0%.
Embodiment 46
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 3.4mL promotor (MAO, the toluene solution of 1.46mol/L); The mol ratio of metallic aluminium is about 1: 1000 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 3.1 * 10 5Gmol -1(Ni) h -1, C4/ ∑ C=87.1%, α-C4/C4=98.0%.
Embodiment 47
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.With heptane still three times; Add the 50mL heptane then successively; 20mL is dissolved with the n-heptane solution of 5 μ mol catalyzer (Ni8), 2.6mL promotor (MMAO, the n-heptane solution of 1.93mol/L); The mol ratio of metallic aluminium is about 1: 1000 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 9.3 * 10 5Gmol -1(Ni) h -1, C4/ ∑ C=86.9%, α-C4/C4=89%.
Embodiment 48
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 1.3mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 9.4 * 10 5Gmol -1(Ni) h -1, C4/ ∑ C=84.3%, α-C4/C4=84.3%.
Embodiment 49
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 1.1mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 4.5 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=92.5%, α-C4/C4＞99.0%.
Embodiment 50
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5mol catalyzer (Ni8), 1.7mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 300 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 5.1 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=89.4%, α-C4/C4=97.1%.
Embodiment 51
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 8.7 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=89.6%, α-C4/C4＞99.0%.
Embodiment 52
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.9mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 500 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 5.9 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=88.0%, α-C4/C4＞99.0%.
Embodiment 53
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 3.5mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 600 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 5.4 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=85.1%, α-C4/C4＞99.0%.
Embodiment 54
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 7.6 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=77.9%, α-C4/C4=94.2%.
Embodiment 55
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 6.5 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=81.2%, α-C4/C4=87.4%.
Embodiment 56
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (80 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 5.8 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=73.9%, α-C4/C4=76.7%.
Embodiment 57
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (10min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 9.5 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=91.5%, α-C4/C4＞99.0%.
Embodiment 58
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (20min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 9.0 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=86.7%, α-C4/C4＞99.0%.
Embodiment 59
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (40min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 5.8 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=87.5%, α-C4/C4＞99.0%.
Embodiment 60
1, the preparation of catalyst n i8 is as embodiment 45.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni8), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (50min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 4.7 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=86.8%, α-C4/C4＞99.0%.
Embodiment 61
1, the preparation of title complex: preparation [2-chloro-5; 6; 7-three hydrogen quinoline-8-ketone contracts 2; The 6-xylidine closes nickelous chloride (II) [Ni6]: with 2-chloro-5,6, the halogenide of 7-three hydrogen quinoline-8-ketone and band alkyl or substituent aniline of halogen and corresponding nickel is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, oven dry can obtain title product.Get dark green title complex, productive rate 23%.FT-IR(KBr，disk，cm -1)：3345，2931，1567，1488，1409，1341，1239，1123，1028，866，783，675，616，502，403.Anal.Calcd?for?C 17H 17Cl 3N 2Ni(414)：C，49.27；H，4.14；N，6.76.Found：C，49.21；H，4.51；N，6.29.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni6), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 3.7 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=88.5%, α-C4/C4=98.0%.
Embodiment 62
1, the preparation of title complex: preparation [2-chloro-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-Diethyl Aniline closes nickelous chloride (II) [Ni7]: with 2-chloro-5,6,7-three hydrogen quinoline-8-ketone and 2,6-Diethyl Aniline and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add and add ether behind the suitable dissolve with methanol title complex is settled out, dry get final product green title complex, productive rate 26%.FT-IR(KBr，disk，cm-1)：3049，2963，2930，2875，1581，1449，1262，1237，1190，1156，1124，864，817，781，676，641，521.Anal.Calcd?for?C19H21C13N2Ni(442)：C，51.58；H，4.78；N，6.33.Found：C，51.53；H，5.12；N，5.95。The crystalline structure synoptic diagram is seen accompanying drawing 3.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni7), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 7.1 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=87.0%, α-C4/C4=90.1%.
Embodiment 63
1, the preparation of title complex: preparation [2-chloro-5,6,7-three hydrogen quinoline-8-ketone contracts 2,4; The 6-trimethylaniline closes nickelous chloride (II) [Ni9]: and preparation [2-chloro-5,6,7-three hydrogen quinoline-8-ketone contracts 2; 4, the 6-trimethylaniline closes nickelous chloride (II) [Ni9]: with 2-chloro-5,6; 7-three hydrogen quinoline-8-ketone and 2 and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add and add ether behind the suitable dissolve with methanol title complex is settled out, dry get final product dark green title complex, productive rate 23%.FT-IR(KBr，disk，cm -1)：2923，1575，1412，1235，1210，1122，1035，1011，817，680，562，505.Anal.Calcd?for?C 18H 19Cl 3N 2Ni(428)：C，50.46；H，4.47；N，6.54.Found：C，50.34；H，4.86；N，5.91.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni9), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 2.4 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=79.3%, α-C4/C4＞99.0%.
Embodiment 64
1, the preparation of title complex: preparation [2-chloro-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and 4-diethylammonium-6-monomethylaniline closes nickelous chloride (II) [Ni10]: with 2-chloro-5,6,7-three hydrogen quinoline-8-ketone and 2 and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add and add ether behind the suitable dissolve with methanol title complex is settled out, dry get final product dark green title complex, productive rate 21%.FT-IR(KBr，disk，cm -1)：2956，2933，2872，2854，1626，1578，1444，1341，1243，1142，1121，922，858，646，501.Anal.Calcd?for?C 20H 23Cl 3N 2Ni(456)：C，60.58；H，4.86；N，6.14.Found：C，60.28；H，5.29；N，6.02.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni10), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 2.5 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=89.1%, α-C4/C4=94.4%.
Embodiment 65
1, the preparation of title complex: preparation [2-phenyl-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-xylidine closes nickelous chloride (II) [Ni11]: with 2-phenyl-5,6,7-three hydrogen quinoline-8-ketone and 2,6-xylidine and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, oven dry can obtain title product.Get green title complex, productive rate 18%.FT-IR(KBr，disk，cm -1)：3272，2928，1558，1401，1341，1162，1122，1034，1009，815，763，679，614，482.Anal.Calcd?for?C 23H 22Cl 2N 2Ni(456)：C，60.58；H，4.86；N，6.14.Found：60.24；H，4.63；N，6.55.
2, pressurization ethylene oligomerization: polymeric kettle is vacuumized and be heated to 100 ℃, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5mol catalyzer (Ni11), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 3.1 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=84.5%, α-C4/C4=90.2%.
Embodiment 66
1, the preparation of title complex: preparation [2-phenyl-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-Diethyl Aniline closes nickelous chloride (II) [Ni12]: with 2-phenyl-5,6,7-three hydrogen quinoline-8-ketone and 2,6-Diethyl Aniline and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add and add ether behind the suitable dissolve with methanol title complex is settled out, dry get final product green title complex, productive rate 19%.FT-IR(KBr，disk，cm-1)：3272，2933，1555，1400，1341，1166，1122，1034，1009，679，614，494.Anal.Calcd?for?C25H26Cl2N2Ni(484)：C，62.03；H，5.41；N，5.79.Found：C，61.82；H，5.77；N，5.42.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni12), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 3.4 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=84.5%, α-C4/C4=87.1%.
Embodiment 67
1, the preparation of title complex: preparation [2-phenyl-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-diisopropyl aniline closes nickelous chloride (II) [Ni13]: with 2-phenyl-5,6,7-three hydrogen quinoline-8-ketone and 2,6-diisopropyl aniline and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, dry green title complex, productive rate 21%.FTIR(KBr；cm -1)：3358，2969，1557，1406，1341，1027，762，677，616，508，403.Anal.Calcd?for?C 27H 30Cl 2N 2Ni(442)：C，63.32；H，5.90；N，5.47.Found：C，49.00；H，4.27；N，6.51。The crystalline structure synoptic diagram is seen accompanying drawing 5
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni13), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 4.1 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=85.8%, α-C4/C4=85.6%.
Embodiment 68
1, the preparation of title complex: preparation [2-phenyl-5,6, the 7-three hydrogen quinoline-8-ketone 2 that contracts closes nickelous chloride (II) [Ni14]: with 2-phenyl-5,6, and 7-three hydrogen quinoline-8-ketone and 2 and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, dry dark green title complex, productive rate 18%.FT-IR(KBr，disk，cm -1)：2247，2927，1566，1406，1342，1214，1124，1034，1010，681，615，480.Anal.Calcd?for?C 24H 24Cl 2N 2Ni(470)：C，61.32；H，5.15；N，5.96.Found：C，60.97；H，5.52；N，5.58.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni14), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 2.5 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=79.5%, α-C4/C4＞89.7%.
Implement row 69
1, the preparation of title complex: preparation [2-phenyl-5,6,7-three hydrogen quinoline-8-ketone contracts 2, and 4-diethylammonium-6-monomethylaniline closes nickelous chloride (II) [Ni15]: with 2-phenyl-5,6,7-three hydrogen quinoline-8-ketone and 2 and NiCl 26H 2O is by 1.0: 1.0: 1.1 molar ratio reflux three hours in acetic acid soln.Accomplish back decompression rotary distillation and remove solvent, add suitable dissolve with methanol after the adding ether title complex is settled out, dry dark green title complex, productive rate 20%.FT-IR(KBr，disk，cm -1)：3305，2601，1567，1417，1344，1234，1120，1033，764，682，504.Anal.Calcd?for?C 26H 28Cl 2N 2Ni(498)：C，62.69，H，5.67；N，5.62.Found：C，62.31，H，5.37；N，5.81。The crystalline structure synoptic diagram is seen accompanying drawing 6.
2, pressurization ethylene oligomerization: polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of imagination.Wash still three times with toluene; Add 50mL toluene then successively; 20mL is dissolved with the toluene solution of 5 μ mol catalyzer (Ni15), 2.3mL promotor (EASC, the toluene solution of 0.43mol/L); The mol ratio of metallic aluminium is about 1: 400 in said catalyst center metallic nickel and the promotor, residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.With of the ethanol solution hydrochloride termination polymerization of this polymer fluid sample, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph with mass percent concentration 5%.The output of oligopolymer is to calculate according to the amount of solvent for use, and prerequisite is that the integral area of certain component in the gc spectrogram is directly proportional with the quality of this component.Therefore, the integral area per-cent of the total amount of oligopolymer=(the integral area per-cent sum of the amount * oligopolymer of solvent)/solvent.Oligomerisation is active: 4.0 * 10 6Gmol -1(Ni) h -1, C4/ ∑ C=87.7%, α-C4/C4=83.1%.
Implement row 70
1, the preparation of title complex: preparation 5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-diisopropyl aniline [L3]: with 5; 6,7-three hydrogen quinoline-8-ketone (0.59 gram, 5 mmoles) is with 2; After 6-diisopropyl aniline (0.6 gram, 5.1 mmoles) is pressed and is waited molar ratio to mix, (86 milligrams of the tosic acid of adding catalytic amount; 0.5 mmole), at 100 milliliters reflux in toluene reaction 3h, this reaction must be carried out under nitrogen protection.Can install simultaneously water trap additional to improve productive rate, reaction finishes rear oxidation aluminium column chromatography for separation, gets the yellow oily part, productive rate 66%.FT-IR(KBr，cm -1)：3047，2960，2866，2829，1929.3，1864，1640(v?C＝N)，1571，1476，1426，1329，1254，1194，1104，1050，1016，796，771，674. 1H?NMR(400MHz，CDCl 3)：δ8.73(d，J＝4.1Hz，1H，Py?H)；7.57(d，J＝7.7Hz，1H，Py?H)；7.30(t，J＝4.5Hz，1H，Py?H)；7.14(d，J＝7.5Hz，2H，Ar?H)；7.07(t，J＝6.7Hz，1H，Ar?H)；2.95(t，J＝6.0Hz，2H，CH 2)；2.85(m，2H，2×CH)；2.43(t，J＝6.1Hz，2H，CH 2)；1.93(m，2H，CH 2)；1.15(m，12H，4×CH 3). 13C?NMR(100MHz，CDCl 3)：δ164.7，148.9?146.7，137.5，137.1，136.2?125.0，123.5，123.0，122.9，31.0，21.6，28.1，23.6，22.3.Anal.Calcd?for?C 21H 26N 2(306)：C，82.31；H，8.55；N，9.14.Found：C，82.57；H，8.23；N，9.06。
2, the preparation of title complex: [5,6,7-three hydrogen quinoline-8-ketone contracts 2, and the 6-diisopropyl aniline closes nickelous bromide (II) [Ni16] in preparation
Under the room temperature, with one times of normal (DME) NiBr 2Ethanolic soln is for being added to 5,6, and 7-three hydrogen quinoline-8-ketone contracts 2, and in the ethanolic soln of 6-xylidine, stirring reaction promptly had bluish yellow look throw out to separate out after 8 hours under nitrogen protection.Filter with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, wash three times with ether the back.To leach thing and put into oven drying, take out, get bluish yellow look title complex, productive rate 78% through 8 hours.FT-IR(KBr，disk?cm -1)：3176，3055，2947，2870，2353，1630，1591，1455，1333，1220，1141，1048，811，789，733，670.Anal.Calcd?for?C 21H 26Br 2N 2Ni(525)：C，48.05，H，4.99；N，5.34.Found：C，48.22；H，5.12；N，4.98。
3, add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (20 ℃) of setting.Wash still three times with toluene, add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 1.5 μ mol catalyzer (Ni16), 0.38mL promotor (AlEt 2Cl, the toluene solution of 0.79mol/L), the mol ratio of metallic aluminium is about 1: 200 in said catalyst center metallic nickel and the promotor, remains to be toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, in mixed solution, add 100mL ethanol, whether check has Vilaterm to generate.There is Vilaterm to generate through check, in 60 ℃ baking oven, is dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.2 * 10 6Gmol -1(Ni) h -1, polymkeric substance M w=3.2kgmol -1, M w/ M n=1.7.
The above embodiment is the preferred embodiment that proves absolutely that the present invention lifts, and protection scope of the present invention is not limited thereto.Being equal to that the technician in present technique field is done on basis of the present invention substitutes or conversion, all within protection scope of the present invention.

Claims (10)

1. a nickel metal complexes is characterized in that, the structure of said nickel metal complexes is suc as formula shown in the I:
Figure 831672DEST_PATH_IMAGE001
Formula I
Wherein, R 1Alkyl for C 1 ~ C 3; R 2Be hydrogen, methyl or ethyl; R 3Be hydrogen, halogen or aromatic base; X is a halogen.
2. nickel metal complexes according to claim 1 is characterized in that R 1Be methyl, ethyl or sec.-propyl, R 3Be hydrogen, chlorine or phenyl, X is a chlorine or bromine.
3. prepare the method for the described nickel metal complexes of claim 1, it is characterized in that, comprise the steps:
1) with 2-R 3-5,6,7-three hydrogen quinoline-8-ketone and 2,6-two R 1-4-R 2After-aniline mixes, add p-methyl benzenesulfonic acid, in toluene solvant, nitrogen protection refluxed reaction 4-5 hour, purifying promptly obtains 2-R 3-5,6,7-three hydrogen quinoline-8-ketone contracts 2,6-two R 1-4-R 2-aniline part, wherein, R 1Be the alkyl of C 1 ~ C 3, R 2Be hydrogen, methyl or ethyl, R 3Be hydrogen, X is a halogen;
2) step 1) gained part is mixed with the nickel salt of halogen, stirring at room is 8 hours under the nitrogen protection, and deposition is separated out, and filters, and ether washing three times obtains described nickel metal complexes.
4. prepare the method for the described nickel metal complexes of claim 1, it is characterized in that, comprise the steps:
With 2-R 3-5,6,7-three hydrogen quinoline-8-ketone and 2,6-two R 1-4-R 2The nickel salt of-aniline and halogen adds the 3h that refluxes in the acetate, and the solvent of distillation removal under reduced pressure adds dissolve with ethanol, adds ether, and solid settles out, and the back gets said nickel metal complexes with the ether washing, wherein, and R 1Be the alkyl of C 1 ~ C 3, R 2Be hydrogen, methyl or ethyl, R 3Be chlorine or aromatic base, X is a halogen.
5. according to claim 3 or 4 described preparing methods, it is characterized in that the nickel salt of said halogen is NiCl 26H 2O or (DME) NiBr 2
6. ethylene oligomerization and polymeric catalyst system is characterized in that in the said catalyst system, catalyzer is the described nickel metal complexes of claim 1.
7. ethylene oligomerization according to claim 6 and polymeric catalyst system is characterized in that, also contain promotor in the said catalyst system, and said promotor is one or more in aikyiaiurnirsoxan beta, modified alumoxane and the aluminum alkyls.
8. ethylene oligomerization according to claim 7 and polymeric catalyst system is characterized in that, the mol ratio of metallic aluminium is in said catalyst center metallic nickel and the promotor: Ni:Al=1:200 ~ 1:2500.
9. the method for ethylene polymerization is carried out in claim 7 or 8 described ethylene oligomerizations and the catalysis of polymeric catalyst system, it is characterized in that, comprises the steps:
1) polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times;
2) replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to 20 ~ 100 ℃ of polymerization temperatures; With toluene or the said polymeric kettle of heptane three times, add toluene or heptane then successively, be dissolved with the toluene or the n-heptane solution of said catalyzer and be dissolved with the toluene or the n-heptane solution of said promotor;
3) seal said polymeric kettle, pressure is 10atm in feeding ethene to the polymeric kettle, and keeps constant pressure;
4) behind polyreaction 10 ~ 120 min, the ethylene pressure in the still is discharged, the filtration washing after drying is to constant weight.
10. the method for ethylene oligomerization reaction is carried out in claim 7 or 8 described ethylene oligomerizations and the catalysis of polymeric catalystsystem, it is characterized in that, comprises the steps:
1) polymeric kettle is heated to 100 ℃, vacuumizes while hot and with nitrogen replacement 3 times;
2) replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to 20 ~ 100 ℃ of polymerization temperatures; With toluene or the said polymeric kettle of heptane three times, add toluene or heptane then successively, be dissolved with the toluene or the n-heptane solution of said catalyzer and be dissolved with the toluene or the n-heptane solution of said promotor;
3) seal said polymeric kettle, pressure is 10atm in feeding ethene to the polymeric kettle, and keeps constant pressure;
4) behind polyreaction 10 ~ 120 min, the ethylene pressure in the still is discharged, collect polymeric solution, said polymeric solution is stopped polymerization with ethanol solution hydrochloride.
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