CN100406479C

CN100406479C - Beta-diketone monoimine vanadium catalyst containing trifluoromethyl radical for olefinic polymerization and its preparation method and uses

Info

Publication number: CN100406479C
Application number: CNB2006100168737A
Authority: CN
Inventors: 李悦生; 段轶群; 李彦国; 张贵宝; 唐丽明; 张所波
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changzhou Institute Of Energy Storage Materials & Devices
Priority date: 2006-05-25
Filing date: 2006-05-25
Publication date: 2008-07-30
Anticipated expiration: 2026-05-25
Also published as: CN1884310A

Abstract

The present invention discloses a beta-diketone monoimine vanadium catalyst containing a trifluoromethyl radical, which is used for olefinic polymerization, and a preparation method thereof, and the use of the catalyst for catalyzing ethylene polymerization, ethylene and norbornene copolymerization and ethylene and alpha-olefin or norbornene copolymerization. A beta-diketone compound containing the trifluoromethyl radical, and aniline or a derivative of the aniline carry out condensation reaction in a methanol solution under the catalytic action of methanoic acid to obtain schiff base. The schiff base and n-butyl lithium react under the anhydrous and anaerobic condition to obtain a negative ion ligand. The negative ion ligand and vanadium trichloride carry out coordination reaction under the anhydrous and anaerobic condition to obtain the beta-diketone monoimine vanadium catalyst containing the trifluoromethyl radical, which is supplied by the present invention. The catalyst can catalyze the ethylene polymerization and the ethylene and alpha-olefin or norbornene copolymerization under the action of diethyl aluminium chloride or modified methylaluminoxane.

Description

Contain beta-diketo mono imine vanadium olefinic polymerization catalyst and the preparation method and the application of trifluoromethyl

Technical field

The present invention relates to contain the beta-diketo mono imine vanadium olefinic polymerization catalyst and the preparation method of trifluoromethyl.

The invention still further relates to the above-mentioned application of beta-diketo mono imine vanadium olefinic polymerization catalyst in catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close that contains trifluoromethyl.

Background technology

Twentieth century fifties, Ziegler and Natta have independently found catalyst system that early transition metal and alkylaluminium cpd form the effectively homopolymerization and the copolymerization of catalyzed alkene separately, from then on, polyolefin catalyst has brought revolutionary variation for people's life.Polyolefine has been widely used in industry, agricultural, national defence, communications and transportation and the daily life as the most important macromolecular material of a class.Catalyzer is made up of organic ligand and transition metal, but the carrying out of catalytic polymerization, and therefore the structure of controlling polymers and performance, are carried out effective Molecular Structure Design to organic ligand and occupy core status in catalyzer research and development fields.Traditional vanadium is that Ziegler-Natta catalyst has characteristics such as active centre point is single, the olefin-copolymerization ability is strong, but low, the easy inactivation of its catalytic activity, high temperature tolerance power is poor.One of reason of active low easy inactivation is in polymerization process, and the vanadium catalytic active center is reduced into ion at a low price easily, thus inactivation, and one of way that addresses this problem is stablized the vanadium catalytic active center with assistant ligand exactly.

1999, the study group of Canada scientist Gambarotta once found to contain V (acac) 3 title complexs of several different substituents, under the activation of promotors such as Et2AlCl or Et3Al2Cl3, can effectively carry out ethylene-propylene copolymer and close reaction (organometallic compound Organometallics, 1999,18:2773-2781).Recently, people such as Japanese scientist Nomura reported aryl acyl enamine vanadium catalyzer with high catalytic activity (macromole Macromolecules 2005,38:5905-5913), but its catalyzed alkene copolymerization is indifferent, resistance to elevated temperatures is poor.

Summary of the invention

For overcoming these shortcomings, the invention discloses a kind of beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl, it has easy to prepare, advantage such as catalytic activity is high, Heat stability is good and copolymerization ability are strong.

The purpose of this invention is to provide a kind of beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl.

Another purpose of the present invention provides the above-mentioned preparation method who contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl

The 3rd purpose of the present invention provides the above-mentioned beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl under the effect of diethyl aluminum chloride (DEAC) or modified methylaluminoxane (MMAO), the application during catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close.

The invention provides a kind of its structure of beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl as:

R1 is the tertiary butyl, furyl, thienyl, pyridyl, phenyl, tolyl, ethylbenzene base, xylyl, p-methoxy-phenyl or fluorophenyl in the formula; R2 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R3 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R4 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R5 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R6 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group.

R1 is the tertiary butyl, furyl, thienyl, pyridyl, phenyl, tolyl, ethylbenzene base, 3,5-dimethylphenyl, p-methoxy-phenyl or fluorophenyl in the formula; R2 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R6 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R3 is hydrogen, methyl or methoxy; R5 is hydrogen, methyl or methoxy; R4 is hydrogen, methyl, ethyl or methoxyl group.

R1 is the tertiary butyl, phenyl, tolyl, ethylbenzene base, 3,5-dimethylphenyl, p-methoxy-phenyl or fluorophenyl in the formula; R2 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R6 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R3 is hydrogen, methyl or methoxy; R5 is hydrogen, methyl or methoxy; R4 is hydrogen, methyl or methoxy.

R1 is the tertiary butyl, phenyl, tolyl or p-methoxy-phenyl in the formula; R2 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R6 is hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R3 is hydrogen, methyl or methoxy; R5 is hydrogen, methyl or methoxy; R4 is hydrogen, methyl or methoxy.

R1 is the tertiary butyl, phenyl, tolyl or p-methoxy-phenyl in the formula; R2 hydrogen, methyl, ethyl or sec.-propyl; R6 hydrogen, methyl, ethyl or sec.-propyl; R3 is hydrogen or methyl; R5 is hydrogen or methyl; R4 is hydrogen, methyl.

Another purpose of the present invention provides the above-mentioned preparation method who contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl, is divided into two steps:

The western Buddhist alkali of step 1 preparation: the derivative, methyl alcohol, the formic acid that in the exsiccant reactor, add the beta-diketone compounds, aniline or the aniline that contain trifluoromethyl, its ratio range is 20-40mmol: 20-40mmol: 15-30mL: 1-2mL, heating reflux reaction 24-48h.Steam solvent methanol with Rotary Evaporators, make eluent, resistates is carried out column chromatography, obtain the western Buddhist alkali shown in the following formula with the sherwood oil that contains 1% ethyl acetate:

Step 2-preparation contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl: under nitrogen atmosphere, adding mol number and volume proportion are 1mol in the exsiccant reactor: the western Buddhist alkali and the anhydrous tetrahydro furan that obtain above the 10L, stirring at room reaction 10min is cooled to-78 ℃; Within 5min, be that the hexane solution of 1.60mol/L n-Butyl Lithium joins in the reaction flask with concentration, the mol proportioning of n-Butyl Lithium and western Buddhist alkali is 1: 1.1, obtains negative ion part as follows:

Solution slowly rises to room temperature again by the colourless scarlet that becomes at this moment, restir reaction 4h; In exsiccant Schlenk reactor, add title complex VCl33THF, the mol proportioning of title complex VCl33THF and western Buddhist alkali is 1: 1, be chilled to-78 ℃ under stirring, then in 30min, the lithium salt solution that obtains is above joined in the Schlenk reactor, stirring reaction 1h, slowly rise to room temperature, continue stirring reaction 12h, solvent removed in vacuo gets black solid, adds the dry toluene dissolving and also stirs 20min, the volume ratio of west Buddhist alkali mol number and dry toluene and western Buddhist alkali is 1mol: 10L, after the vacuum filtration, filtrate is concentrated, add anhydrous hexane, separate out brown crystalline compound, obtain containing the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl at last.

A further object of the present invention provides the above-mentioned beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl that contains under the effect of diethyl aluminum chloride (DEAC) or modified methylaluminoxane (MMAO), application during catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close, its step and condition are as follows:

Under the ethene atmosphere, in the exsiccant polymerization reactor, add dry toluene 30mL successively, concentration is the n-heptane solution 2.5mL of 2.0mol/L MMAO, after stirring 5 minutes under 25 ℃, the beta-diketo mono imine vanadium olefinic polymerization catalyst toluene solution 1ml that contains trifluoromethyl that adds above-mentioned preparation, this catalyst concn is 5 μ mol/mL, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL1% hydrochloric acid, filter, 1% ethanol solution hydrochloride washing 2 times, washing with alcohol 2 times, vacuum-drying can make polyethylene specimen.

Under the ethene atmosphere, in the exsiccant polymerization reactor, add dry toluene 30mL successively, concentration is the toluene solution 2.86mL of the diethyl aluminum chloride of 0.7mol/L, concentration is the toluene solution 0.3mL of the chloracetic acid ethyl ester of 0.5mol/L, after stirring 5 minutes under 25-70 ℃, the beta-diketo mono imine vanadium olefinic polymerization catalyst toluene solution 1ml that contains trifluoromethyl that adds above-mentioned preparation, this catalyst concn is 0.5 μ mol/mL, stir polyreaction 5min down, reactant is poured in the ethanolic soln of 300mL0.5% hydrochloric acid, filter, 0.5% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying obtains polyethylene specimen.

Under the ethene atmosphere, in the exsiccant polymerization reactor, add dry toluene 25mL successively, norbornylene 2.5g, concentration is the toluene solution 2.14mL of the diethyl aluminum chloride of 0.7mol/L, concentration is the toluene solution 0.3mL of the chloracetic acid ethyl ester of 0.5mol/L, after stirring 5 minutes under 25-70 ℃, the beta-diketo mono imine vanadium olefinic polymerization catalyst toluene solution 1ml that contains trifluoromethyl that adds above-mentioned preparation, this catalyst concn is 0.5 μ mol/mL, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter, 0.5% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying gets the cyclic olefine copolymer sample.

Under the ethene atmosphere, in the exsiccant polymerization reactor, add dry toluene 25mL successively, 1-hexene 1mL, concentration is the toluene solution 2.86mL of the diethylaluminum chloride of 0.7mol/L, concentration is the toluene solution 0.3mL of the chloracetic acid ethyl ester of 0.5mol/L, after stirring 5 minutes under 25 ℃, the beta-diketo mono imine vanadium olefinic polymerization catalyst toluene solution 1ml that contains trifluoromethyl that adds above-mentioned preparation, this catalyst concn is 0.5 μ mol/mL, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter 1% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying gets the new LDPE (film grade) sample.

Beneficial effect of the present invention:

Under the effect of modified methylaluminoxane (MMAO), under 25 ℃, contain the beta-diketo mono imine vanadium olefinic polymerization catalyst catalyzed ethylene polymerization activity of trifluoromethyl: 1.20-2.76 * 105gPE/molVh;

Under the effect of diethyl aluminum chloride (DEAC), the beta-diketo mono imine vanadium olefinic polymerization catalyst catalyzed ethylene polymerization activity that under 25 ℃, contains trifluoromethyl: 1.54-2.69 * 107gPE/molVh, 1 beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl is wherein examined or check at 50 ℃ and 70 ℃ of following catalyzed ethylene polymerizations, and polymerization activity can reach 1.44 * 107gPE/molVh in the time of 70 ℃;

Under the effect of diethyl aluminum chloride (DEAC), the beta-diketo mono imine vanadium olefinic polymerization catalyst catalyzed ethylene and norbornylene copolymerization activity: the 6.60-11.2 * 106gPE/molVh that under 25 ℃, contain trifluoromethyl, norbornylene insertion rate 34.1-43.5%; 1 beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl is wherein examined or check at 50 ℃ and 70 ℃ of following catalyzed ethylenes and norbornylene copolymerization, and polymerization activity can reach 4.29 * 106gPE/molVh in the time of 70 ℃, norbornylene insertion rate 42.8%;

Under the effect of diethyl aluminum chloride (DEAC), the beta-diketo mono imine vanadium olefinic polymerization catalyst catalyzed ethylene and the 1-hervene copolymer that contain trifluoromethyl under 25 ℃ close activity: 6.12-8.16 * 106gPE/molVh, 1-hexene insertion rate 7.5-17.6%.

Embodiment

Now the invention will be further described by following embodiment.

Embodiment 1

In exsiccant 100mL reaction flask, add 1,1,1-three fluoro-5,5-dimethyl-2,4-hexanedione 7.85g is equivalent to 40mmol, aniline 3.73g, is equivalent to 40mmol, methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 24h.Steam solvent methanol with Rotary Evaporators, make eluent, resistates is carried out column chromatography, get white solid shape west Buddhist alkali 5.64g, yield 52% with the sherwood oil that contains 1% ethyl acetate.Mass spectroscopy, molecular ion peak m/e is 271.Ultimate analysis measured value: C, 61.78%; H, 5.90%; N, 5.19%; Theoretical value (C14H16F3NO): C, 61.98%; H, 5.94%; N, 5.16%.

Under nitrogen protection, in exsiccant 100mL reaction flask, add the western Buddhist alkali 0.54g that embodiment 1 obtains, be equivalent to 2mmol and anhydrous tetrahydro furan 20mL, stirring at room reaction 10min is cooled to-78 ℃.Within 5min, the hexane solution 1.375mL with the 1.60mol/L n-Butyl Lithium is equivalent to 2.2mmol and joins in the reaction flask.Solution slowly rises to room temperature by the colourless scarlet that becomes, restir reaction 4h.The tetrahydrofuran (THF) title complex VCl33THF 0.75g that in exsiccant 100mL Schlenk bottle, adds vanadium trichloride, be equivalent to 2.0mmol, be chilled to-78 ℃ under stirring, then in 30min, the lithium salt solution that obtains is above joined in the Schlenk bottle, stirring reaction 1h slowly rises to room temperature, continues stirring reaction 12h.Solvent removed in vacuo gets black solid, adds dry toluene 20mL dissolving and also stirs 20min, after the vacuum filtration, filtrate is concentrated, add anhydrous hexane, separate out brown crystal, must contain the beta-diketo mono imine vanadium olefinic polymerization catalyst 0.55g of trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 536.Ultimate analysis measured value: C, 49.09%; H, 5.79%; N, 2.57%; Theoretical value (C22H31Cl2F3NO3V): C, 49.27%; H, 5.83%; N, 2.61%.

Embodiment 2

Use o-toluidine 4.29g, be equivalent to the aniline in the 40mmol alternate embodiment 1, experimental implementation gets white solid shape west Buddhist alkali 5.48g, yield 48% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 285.Ultimate analysis measured value: C, 63.32%; H, 6.31%; N, 4.94%; Theoretical value (C15H18F3NO): C, 63.15%; H, 6.36%; N, 4.91%.

With the western Buddhist alkali 0.57g of embodiment 2 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.54g that contains trifluoromethyl, yield 49%.Mass spectroscopy, molecular ion peak m/e is 550.Ultimate analysis measured value: C, 50.10%; H, 5.99%; N, 2.53%; Theoretical value (C22H33Cl2F3N03V): C, 50.19%; H, 6.04%; N, 2.55%.

Embodiment 3

Use 2 5.41g, be equivalent to the aniline in the 40mmol alternate embodiment 1, experimental implementation gets white solid shape west Buddhist alkali 5.26g, yield 42% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 313.The ultimate analysis measured value; C, 65.29%; H, 7.12%; N, 7.42%; Theoretical value (C17H22F3NO): C, 65.16%; H, 7.08%; N, 4.47%.

With the western Buddhist alkali 0.63g of embodiment 3 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.52g that contains trifluoromethyl, yield 45%.Mass spectroscopy, molecular ion peak m/e is 578.Ultimate analysis measured value: C, 51.72%; H, 6.48%; N, 2.39%; Theoretical value (C25H37Cl2F3NO3V): C, 51.91%; H, 6.45%; N, 2.42%.

Embodiment 4

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(2-furyl)-1,3-dimethyl diketone 8.24g, be equivalent to 40mmol, aniline 3.73g, be equivalent to 40mmol, methyl alcohol 30mL, formic acid 2mL, heating reflux reaction 48h other with embodiment 1, get white solid shape west Buddhist alkali 5.06g, yield 45%.Mass spectroscopy, molecular ion peak m/e is 281.Ultimate analysis measured value: C, 59.55%; H, 3.54%; N, 6.83%; Theoretical value (C14H10F3NO2): C, 59.79%; H, 3.58%; N, 6.81%.

With the western Buddhist alkali 0.56g of embodiment 4 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.56g that contains trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 546.Ultimate analysis measured value: C, 48.22%; H, 4.63%; N, 2.51%; Theoretical value (C22H25Cl2F3NO4V): C, 48.37%; H, 4.61%; N, 2.56%.

Embodiment 5

With to ethylaniline 4.85g, be equivalent to the aniline in the 40mmol alternate embodiment 4, experimental implementation gets white solid shape west Buddhist alkali 5.07g, yield 41% with embodiment 4.Mass spectroscopy, molecular ion peak m/e is 309.Ultimate analysis measured value: C, 62.11%; H, 4.52%; N, 4.50%; Theoretical value (C16H14F3NO2): C, 62.13%; H, 4.56%; N, 4.53%.

With the western Buddhist alkali 0.52g of embodiment 5 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.55g that contains trifluoromethyl, yield 48%.Mass spectroscopy, molecular ion peak m/e is 574.Ultimate analysis measured value: C, 50.38%; H, 5.13%; N, 2.41%; Theoretical value (C24H29Cl2F3NO4V): C, 50.19%; H, 5.09%; N, 2.44%.

Embodiment 6

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(2-thienyl)-1,3-dimethyl diketone 4.44g, be equivalent to 20mmol, aniline 1.86g, be equivalent to 20mmol, methyl alcohol 20mL, formic acid 1.5mL, heating reflux reaction 36h other with embodiment 1, get white solid shape west Buddhist alkali 3.09g, yield 52%.Mass spectroscopy, molecular ion peak m/e is 297.Ultimate analysis measured value: C, 56.38%; H, 3.36%; N, 4.76%; Theoretical value (C14H10F3NOS): C, 56.56%; H, 3.39%; N, 4.71%.

With the western Buddhist alkali 0.59g of embodiment 6 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.63g that contains trifluoromethyl, yield 56%.Mass spectroscopy, molecular ion peak m/e is 562.Ultimate analysis measured value: C, 46.86%; H, 4.45%; N, 2.52%; Theoretical value (C22H25Cl2F3NO3SV): C, 46.99%; H, 4.48%; N, 2.49%.

Embodiment 7

With o-isopropyl aniline 2.70g, be equivalent to the aniline in the 20mmol alternate embodiment 6, experimental implementation gets white solid shape west Buddhist alkali 3.12g, yield 46% with embodiment 6.Mass spectroscopy, molecular ion peak m/e is 339.Ultimate analysis measured value: C, 60.27%; H, 4.71%; N, 4.16%; Theoretical value (C17H16F3NOS): C, 60.16%; H, 4.75%; N, 4.13%.

With the western Buddhist alkali 0.68g of embodiment 7 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.48g that contains trifluoromethyl, yield 40%.Mass spectroscopy, molecular ion peak m/e is 604.Ultimate analysis measured value: C, 49.45%; H, 5.12%; N, 2.28%; Theoretical value (C25H31Cl2F3NO3SV): C, 49.68%; H, 5.17%; N, 2.32%.

Embodiment 8

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(2-pyridyl)-1,3-dimethyl diketone 4.34g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.92g, yield 50% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 292.Ultimate analysis measured value: C, 61.41%; H, 3.75%; N, 9.56%; Theoretical value (C15H11F3N2O): C, 61.64%; H, 3.79%; N, 9.59%.

With the western Buddhist alkali 0.58g of embodiment 8 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.52g that contains trifluoromethyl, yield 47%.Mass spectroscopy, molecular ion peak m/e is 557.Ultimate analysis measured value: C, 49.43%; H, 4.66%; N, 4.97%; Theoretical value (C23H26Cl2F3N2O3V): C, 49.57%; H, 4.70%; N, 5.03%.

Embodiment 9

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-phenyl-1,3-dimethyl diketone 4.32g is equivalent to 20mmol, o-toluidine 2.14g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.87g, yield 47% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 305.Ultimate analysis measured value: C, 66.69%; H, 4.67%; N, 4.56%; Theoretical value (C17H14F3NO): C, 66.88%; H, 4.62%; N, 4.59%.

With the western Buddhist alkali 0.61g of embodiment 9 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.62g that contains trifluoromethyl, yield 54%.Mass spectroscopy, molecular ion peak m/e is 570.Ultimate analysis measured value: C, 52.43%; H, 5.08%; N, 2.42%; Theoretical value (C25H29Cl2F3NO3V): C, 52.65%; H, 5.13%; N, 2.46%.

Embodiment 10

Use 2 2.70g, be equivalent to the aniline in the 20mmol alternate embodiment 9, experimental implementation gets white solid shape west Buddhist alkali 2.80g, yield 42% with embodiment 9.Mass spectroscopy, molecular ion peak m/e is 333.Ultimate analysis measured value: C, 68.32%; H, 5.39%; N, 4.19%; Theoretical value (C19H18F3NO): C, 68.46%; H, 5.44%; N, 4.20%.

With the western Buddhist alkali 0.67g of embodiment 10 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.61g that contains trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 598.Ultimate analysis measured value: C, 54.10%; H, 5.52%; N, 2.39%; Theoretical value (C27H33Cl2F3NO3V): C, 54.19%; H, 5.56%; N, 2.34%.

Embodiment 11

With 2,6-Diethyl Aniline 2.98g is equivalent to the aniline in the 20mmol alternate embodiment 9, and experimental implementation gets white solid shape west Buddhist alkali 3.54g, yield 51% with embodiment 9.Mass spectroscopy, molecular ion peak m/e is 347.Ultimate analysis measured value: C, 69.01%; H, 5.82%; N, 4.06%; Theoretical value (C20H20F3NO): C, 69.15%; H, 5.80%; N, 4.03%.

With the western Buddhist alkali 0.69g of embodiment 11 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.65g that contains trifluoromethyl, yield 53%.Mass spectroscopy, molecular ion peak m/e is 612.Ultimate analysis measured value: C, 54.78%; H, 5.72%; N, 2.25%; Theoretical value (C28H35Cl2F3NO3V): C, 54.91%; H, 5.76%; N, 2.29%.

Embodiment 12

With 2,6-diisopropyl aniline 3.55g is equivalent to the aniline in the 20mmol alternate embodiment 9, and experimental implementation gets white solid shape west Buddhist alkali 3.45g, yield 46% with embodiment 9.Mass spectroscopy, molecular ion peak m/e is 375.Ultimate analysis measured value: C, 70.23%; H, 6.49%; N, 3.75%; Theoretical value (C22H24F3NO): C, 70.38%; H, 6.44%; N, 3.73%.

Embodiment 13

With 2-methyl-6-isopropyl aniline 2.98g, be equivalent to the aniline in the 20mmol alternate embodiment 9, experimental implementation gets white solid shape west Buddhist alkali 2.99g, yield 43% with embodiment 9.Mass spectroscopy, molecular ion peak m/e is 347.Ultimate analysis measured value: C, 69.31%; H, 5.76%; N, 4.00%; Theoretical value (C20H20F3NO): C, 69.15%; H, 5.80%; N, 4.03%.

With the western Buddhist alkali 0.65g of embodiment 13 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.50g that contains trifluoromethyl, yield 41%.Mass spectroscopy, molecular ion peak m/e is 612.Ultimate analysis measured value: C, 54.75%; H, 5.72%; N, 2.25%; Theoretical value (C28H35Cl2F3NO3V): C, 54.91%; H, 5.76%; N, 2.29%.

Embodiment 14

In exsiccant 100mL reaction flask, add 4,4, aminomethyl phenyl-1 between 4-three fluoro-1-, 3-dimethyl diketone 4.60g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.18g, yield 52% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 305.Ultimate analysis measured value: C, 66.73%; H, 4.67%; N, 4.55%; Theoretical value (C17H14F3NO): C, 66.88%; H, 4.62%; N, 4.59%.

With the western Buddhist alkali 0.61g of embodiment 14 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.58g that contains trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 570.Ultimate analysis measured value: C, 52.79%; H, 5.18%; N, 2.42%; Theoretical value (C25H29Cl2F3NO3V): C, 52.65%; H, 5.13%; N, 2.46%.

Embodiment 15

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-o-methyl-phenyl-s-1,3-dimethyl diketone 4.60g, be equivalent to 20mmol, 23 dimethyl aniline 2.42g, be equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.27g, yield 49% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 333.Ultimate analysis measured value: C, 68.24%; H, 5.49%; N, 4.23%; Theoretical value (C19H18F3NO): C, 68.46%; H, 5.44%; N, 4.20%.

With the western Buddhist alkali 0.67g of embodiment 15 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.68g that contains trifluoromethyl, yield 57%.Mass spectroscopy, molecular ion peak m/e is 598.Ultimate analysis measured value: C, 54.01%; H, 5.51%; N, 2.32%; Theoretical value (C27H33Cl2F3NO3V): C, 54.19%; H, 5.56%; N, 2.34%.

Embodiment 16

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-p-methylphenyls-1,3-dimethyl diketone 4.60g is equivalent to 20mmol, o ethyl aniline 2.42g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.00g, yield 45% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 333.Ultimate analysis measured value: C, 68.59%; H, 5.41%; N, 4.25%; Theoretical value (C19H18F3NO): C, 68.46%; H, 5.44%; N, 4.20%.

With the western Buddhist alkali 0.67g of embodiment 16 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.63g that contains trifluoromethyl, yield 53%.Mass spectroscopy, molecular ion peak m/e is 598.Ultimate analysis measured value: C, 54.32%; H, 5.52%; N, 2.37%; Theoretical value (C27H33Cl2F3NO3V): C, 54.19%; H, 5.56%; N, 2.34%.

Embodiment 17

With 2,6-diisopropyl aniline 3.55g is equivalent to the aniline in the 20mmol alternate embodiment 16, and experimental implementation gets white solid shape west Buddhist alkali 3.66g, yield 47% with embodiment 16.Mass spectroscopy, molecular ion peak m/e is 389.Ultimate analysis measured value: C, 70.76%; H, 6.78%; N, 3.55%; Theoretical value (C23H26F3NO): C, 70.93%; H, 6.73%; N, 3.60%.

With the western Buddhist alkali 0.78g of embodiment 17 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.68g that contains trifluoromethyl, yield 52%.Mass spectroscopy, molecular ion peak m/e is 654.Ultimate analysis measured value: C, 56.72%; H, 6.27%; N, 2.10%; Theoretical value (C31H41Cl2F3NO3V): C, 56.89%; H, 6.31%; N, 2.14%.

Embodiment 18

Use m-anisidine 2.46g, be equivalent to the aniline in the 20mmol alternate embodiment 15, experimental implementation gets white solid shape west Buddhist alkali 3.55g, yield 53% with embodiment 15.Mass spectroscopy, molecular ion peak m/e is 335.Ultimate analysis measured value: C, 64.40%; H, 4.79%; N, 4.19%; Theoretical value (C18H16F3NO2): C, 64.47%; H, 4.81%; N, 4.18%.

With the western Buddhist alkali 0.67g of embodiment 18 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.52g that contains trifluoromethyl, yield 43%.Mass spectroscopy, molecular ion peak m/e is 600.Ultimate analysis measured value: C, 51.85%; H, 5.15%; N, 2.36%; Theoretical value (C26H31Cl2F3NO4V): C, 52.01%; H, 5.20%; N, 2.33%.

Embodiment 19

In exsiccant 100mL reaction flask, add 4,4, the adjacent ethylphenyl-1 of 4-three fluoro-1-, 3-dimethyl diketone 4.48g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.87g, yield 45% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 319.Ultimate analysis measured value: C, 67.52%; H, 5.09%; N, 4.35%; Theoretical value (C18H16F3NO): C, 67.70%; H, 5.05%; N, 4.39%.

With the western Buddhist alkali 0.64g of embodiment 19 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.54g that contains trifluoromethyl, yield 46%.Mass spectroscopy, molecular ion peak m/e is 584.Ultimate analysis measured value: C, 53.28%; H, 5.38%; N, 2.42%; Theoretical value (C26H31Cl2F3NO3V): C, 53.44%; H, 5.35%; N, 2.40%.

Embodiment 20

Add 4,4 in exsiccant 100mL reaction flask, 4-three fluoro-1-are to ethylphenyl-1,3-dimethyl diketone 4.48g, be equivalent to 20mmol, 2,6-xylidine 2.42g is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.99g, yield 43% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 347.Ultimate analysis measured value: C, 69.32%; H, 5.83%; N, 3.98%; Theoretical value (C20H20F3NO): C, 69.15%; H, 5.80%; N, 4.03%.

With the western Buddhist alkali 0.69g of embodiment 20 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.50g that contains trifluoromethyl, yield 41%.Mass spectroscopy, molecular ion peak m/e is 612.Ultimate analysis measured value: C, 54.73%; H, 5.72%; N, 2.25%; Theoretical value (C28H35Cl2F3NO3V): C, 54.91%; H, 5.76%; N, 2.29%.

Embodiment 21

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(2, the 5-3,5-dimethylphenyl)-1,3-dimethyl diketone 4.88g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.45g, yield 54% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 319.Ultimate analysis measured value: C, 67.53%; H, 5.08%; N, 4.36%; Theoretical value (C18H16F3NO): C, 67.70%; H, 5.05%; N, 4.39%.

With the western Buddhist alkali 0.64g of embodiment 21 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.61g that contains trifluoromethyl, yield 52%.Mass spectroscopy, molecular ion peak m/e is 584.Ultimate analysis measured value: C, 53.25%; H, 5.38%; N, 2.36%; Theoretical value (C26H31Cl2F3NO3V): C, 53.44%; H, 5.35%; N, 2.40%.

Embodiment 22

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(3, the 4-3,5-dimethylphenyl)-1,3-dimethyl diketone 4.88g is equivalent to 20mmol, to monomethylaniline 2.14g, be equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.93g, yield 44% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 333.Ultimate analysis measured value: C, 68.32%; H, 5.49%; N, 4.23%; Theoretical value (C19H18F3NO): C, 68.46%; H, 5.44%; N, 4.20%.

With the western Buddhist alkali 0.67g of embodiment 22 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.63g that contains trifluoromethyl, yield 53%.Mass spectroscopy, molecular ion peak m/e is 598.Ultimate analysis measured value: C, 54.30%; H, 5.52%; N, 2.36%; Theoretical value (C27H33Cl2F3NO3V): C, 54.19%; H, 5.56%; N, 2.34%.

Embodiment 23

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-(2, the 4-3,5-dimethylphenyl)-1,3-dimethyl diketone 4.88g is equivalent to 20mmol, P-nethoxyaniline 2.46g, be equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.42g, yield 49% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 349.Ultimate analysis measured value: C, 65.18%; H, 5.15%; N, 4.05%; Theoretical value (C19H18F3NO2): C, 65.32%; H, 5.19%; N, 4.01%.

With the western Buddhist alkali 0.70g of embodiment 23 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.61g that contains trifluoromethyl, yield 50%.Mass spectroscopy, molecular ion peak m/e is 614.Ultimate analysis measured value: C, 52.59%; H, 5.37%; N, 2.16%; Theoretical value (C27H33Cl2F3NO4V): C, 52.78%; H, 5.41%; N, 2.28%.

Embodiment 24

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-o-methoxyphenyls-1,3-dimethyl diketone 4.92g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.34g, yield 52% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 321.Ultimate analysis measured value: C, 63.32%; H, 4.36%; N, 4.38%; Theoretical value (C17H14F3NO2): C, 63.55%; H, 4.39%; N, 4.36%.

With the western Buddhist alkali 0.64g of embodiment 24 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.55g that contains trifluoromethyl, yield 47%.Mass spectroscopy, molecular ion peak m/e is 586.Ultimate analysis measured value: C, 0.51.05%; H, 4.95%; N, 2.42%; Theoretical value (C25H29Cl2F3NO4V): C, 51.21%; H, 4.99%; N, 2.39%.

Embodiment 25

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-m-methoxyphenyls-1,3-dimethyl diketone 4.92g is equivalent to 20mmol, Ortho Toluidine 2.14g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.29g, yield 49% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 335.Ultimate analysis measured value: C, 64.36%; H, 4.83%; N, 4.22%; Theoretical value (C18H16F3NO2): C, 64.47%; H, 4.81%; N, 4.18%.

With the western Buddhist alkali 0.67g of embodiment 25 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.53g that contains trifluoromethyl, yield 44%.Mass spectroscopy, molecular ion peak m/e is 600.Ultimate analysis measured value: C, 51.85%; H, 5.16%; N, 2.29%; Theoretical value (C26H31Cl2F3NO4V): C, 52.01%; H, 5.20%; N, 2.33%.

Embodiment 26

In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-p-methoxyphenyls-1,3-dimethyl diketone 4.92g, be equivalent to 20mmol, 2,5-xylidine 2.42g is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.56g, yield 51% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 349.Ultimate analysis measured value: C, 65.53%; H, 5.22%; N, 4.06%; Theoretical value (C19H18F3NO2): C, 65.32%; H, 5.19%; N, 4.01%.

With the western Buddhist alkali 0.70g of embodiment 26 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.69g that contains trifluoromethyl, yield 56%.Mass spectroscopy, molecular ion peak m/e is 614.Ultimate analysis measured value: C, 52.89%; H, 5.45%; N, 2.24%; Theoretical value (C27H33Cl2F3NO4V): C, 52.78%; H, 5.41%; N, 2.28%.

Embodiment 27

With 2,6-Diethyl Aniline 2.98g is equivalent to the aniline in the 20mmol alternate embodiment 25, and experimental implementation gets white solid shape west Buddhist alkali 3.47g, yield 46% with embodiment 25.Mass spectroscopy, molecular ion peak m/e is 377.Ultimate analysis measured value: C, 66.97%; H, 5.90%; N, 3.66%; Theoretical value (C21H22F3NO2): C, 66.83%; H, 5.88%; N, 3.71%.

With the western Buddhist alkali 0.75g of embodiment 27 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.66g that contains trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 642.Ultimate analysis measured value: C, 54.05%; H, 5.76%; N, 2.16%; Theoretical value (C29H37Cl2F3NO4V): C, 54.22%; H, 5.80%; N, 2.18%.

Embodiment 28

With 2-methyl-6-isopropyl aniline 2.98g, be equivalent to the aniline in the 20mmol alternate embodiment 24, experimental implementation gets white solid shape west Buddhist alkali 3.85g, yield 51% with embodiment 24.Mass spectroscopy, molecular ion peak m/e is 377.Ultimate analysis measured value: C, 66.65%; H, 5.84%; N, 3.74%; Theoretical value (C21H22F3NO2): C, 66.83%; H, 5.88%; N, 3.71%.

With the western Buddhist alkali 0.75g of embodiment 28 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.71g that contains trifluoromethyl, yield 55%.Mass spectroscopy, molecular ion peak m/e is 642.Ultimate analysis measured value: C, 54.06; H, 5.76; N, 2.19; Theoretical value (C29H37Cl2F3NO4V): C, 54.22; H, 5.80; N, 2.18.

Embodiment 29

In exsiccant 100mL reaction flask, add 4,4, fluorophenyl-1 between 4-three fluoro-1-, 3-dimethyl diketone 4.68g is equivalent to 20mmol, aniline 1.86g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 2.60g, yield 42% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 309.Ultimate analysis measured value: C, 62.26%; H, 3.62%; N, 4.59%; Theoretical value (C16H11F4NO): C, 62.14%; H, 3.59%; N, 4.53%.

With the western Buddhist alkali 0.62g of embodiment 29 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.56g that contains trifluoromethyl, yield 49%.Mass spectroscopy, molecular ion peak m/e is 574.Ultimate analysis measured value: C, 50.02%; H, 4.51%; N, 2.39%; Theoretical value (C24H26Cl2F4NO3V): C, 50.19%; H, 4.56%; N, 2.44%.

Embodiment 30

Add 4,4 in exsiccant 100mL reaction flask, 4-three fluoro-1-are to fluorophenyl-1,3-dimethyl diketone 4.68g is equivalent to 20mmol, a monomethylaniline 2.14g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.30g, yield 51% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 323.Ultimate analysis measured value: C, 62.97%; H, 4.08%; N, 4.30%; Theoretical value (C17H13F4NO): C, 63.16%; H, 4.05%; N, 4.33%.

With the western Buddhist alkali 0.65g of embodiment 30 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.51g that contains trifluoromethyl, yield 43%.Mass spectroscopy, molecular ion peak m/e is 588.Ultimate analysis measured value: C, 50.82%; H, 4.75%; N, 2.32%; Theoretical value (C25H28Cl2F4NO3V): C, 51.04%; H, 4.80%; N, 2.38%.

Embodiment 31

In exsiccant 100mL reaction flask, add 4,4, the adjacent fluorophenyl-1 of 4-three fluoro-1-, 3-dimethyl diketone 4.68g is equivalent to 20mmol, o ethyl aniline 2.42g, is equivalent to 20mmol, methyl alcohol 15mL, formic acid 1mL, other gets white solid shape west Buddhist alkali 3.10g, yield 46% with embodiment 1.Mass spectroscopy, molecular ion peak m/e is 337.Ultimate analysis measured value: C, 64.27%; H, 4.43%; N, 4.12%; Theoretical value (C18H15F4NO): C, 64.09%; H, 4.48%; N, 4.15%.

With the western Buddhist alkali 0.67g of embodiment 31 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.48g that contains trifluoromethyl, yield 40%.Mass spectroscopy, molecular ion peak m/e is 602.Ultimate analysis measured value: C, 51.60; H, 4.96; N, 2.36; Theoretical value (C26H30Cl2F4NO3V): C, 51.84; H, 5.02; N, 2.33.

Embodiment 32

With o-isopropyl aniline 2.70g, be equivalent to the aniline in the 20mmol alternate embodiment 29, experimental implementation gets white solid shape west Buddhist alkali 2.88g, yield 41% with embodiment 29.Mass spectroscopy, molecular ion peak m/e is 351.Ultimate analysis measured value: C, 64.76%; H, 4.90%; N, 3.95%; Theoretical value (C19H17F4NO): C, 64.95%; H, 4.88%; N, 3.99%.

With the western Buddhist alkali 0.70g of embodiment 32 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.60g that contains trifluoromethyl, yield 49%.Mass spectroscopy, molecular ion peak m/e is 616.Ultimate analysis measured value: C, 52.54%; H, 5.20%; N, 2.29%; Theoretical value (C27H32Cl2F4NO3V): C, 52.61%; H, 5.23%; N, 2.27%.

Embodiment 33

Use ORTHO ANISIDINE 2.46g, be equivalent to the aniline in the 20mmol alternate embodiment 30, experimental implementation gets white solid shape west Buddhist alkali 3.53g, yield 52% with embodiment 30.Mass spectroscopy, molecular ion peak m/e is 339.Ultimate analysis measured value: C, 60.31%; H, 3.89%; N, 4.09%; Theoretical value (C17H13F4NO2): C, 60.18%; H, 3.86%; N, 4.13%.

With the western Buddhist alkali 0.68g of embodiment 33 preparation, be equivalent to the western Buddhist alkali that obtains in the 2mmol alternate embodiment 1, experimental implementation is with embodiment 1, the brown beta-diketo mono imine vanadium olefinic polymerization catalyst 0.62g that contains trifluoromethyl, yield 51%.Mass spectroscopy, molecular ion peak m/e is 604.Ultimate analysis measured value: C, 49.47%; H, 4.62%; N, 2.30%; Theoretical value (C25H28Cl2F4NO4V): C, 49.69%; H, 4.67%; N, 2.32%.

Embodiment 34

Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add dry toluene 30mL successively, concentration is the n-heptane solution 2.5mL of the modified methylaluminoxane (MMAO) of 2.0M, stir after 5 minutes, the beta-diketo mono imine vanadium olefinic polymerization catalyst 2.68mg that contains trifluoromethyl that adds embodiment 1 preparation, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 0.5% hydrochloric acid, filtered, 0.5% ethanol solution hydrochloride washing 2 times, washing with alcohol 2 times, vacuum-drying gets polyethylene 0.10g, and catalytic activity is 1.20 * 105gPE/molVh.Poly melt temperature is 128.7 ℃, and viscosity-average molecular weight is 413kg/mol.

Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add dry toluene 30mL successively, concentration is the toluene solution 2.86mL of 0.7mol/L diethyl aluminum chloride, concentration is the toluene solution 0.3mL of 0.5mol/L chloracetic acid ethyl ester, stir after 5 minutes, the beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl that adds embodiment 1 preparation, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, stir polyreaction 5min down, reactant is poured in the ethanolic soln of 300mL 1% hydrochloric acid, filter, 0.5% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying, get polyethylene 0.72g, catalytic activity is 1.73 * 107gPE/molVh, and poly melt temperature is 137.0 ℃, and viscosity-average molecular weight is 328kg/mol.

Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add dry toluene 25mL successively, norbornylene 2.5g, concentration is the toluene solution 2.86mL of 0.7mol/L diethyl aluminum chloride, concentration is the toluene solution 0.3mL of 0.5mol/L chloracetic acid ethyl ester, stir after 5 minutes, the beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl that adds embodiment 1 preparation, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filtered, 0.5% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying gets cyclic olefine copolymer 0.72g, and catalytic activity is 8.64 * 106gPolym/molV.h, 97.8 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 43.5%.

Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add dry toluene 25mL successively, 1-hexene 1mL, concentration is the toluene solution 2.86mL of 0.7mol/L diethylaluminum chloride, concentration is the toluene solution 0.3mL of 0.5mol/L chloracetic acid ethyl ester, stir after 5 minutes, the beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl that adds embodiment 1 preparation, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, stir polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filtered, 1% ethanol solution hydrochloride washing 2 times, washing with alcohol 3 times, vacuum-drying gets new LDPE (film grade) 0.63g, and catalytic activity is 7.56 * 106gPolym/molVh, the melt temperature of polymkeric substance is 105.2 ℃, 1-hexene insertion rate 15.8%.

Embodiment 35

With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 34b, operation gets polyethylene 0.88g with embodiment 34b, and catalytic activity is 2.11 * 107gPE/molV.h, and poly melt temperature is 134.5 ℃, and viscosity-average molecular weight is 207kg/mol.

With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 34c, operation gets cyclic olefine copolymer 0.49g with embodiment 34c, catalytic activity is 5.88 * 106gPolym/molVh, 97.4 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 41.7%, norbornylene insertion rate 36.8%.

Embodiment 36

With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 34b, operation gets polyethylene 0.60g with embodiment 34b, and catalytic activity is 1.44 * 107gPE/molVh, and poly melt temperature is 134.3 ℃, and viscosity-average molecular weight is 189kg/mol.

With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 34c, operation gets cyclic olefine copolymer 0.47g with embodiment 34c, and catalytic activity is 4.29 * 106gPolym/molV.h, 97.6 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 42.8%.

Embodiment 37

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 2 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.84g with embodiment 34b, and catalytic activity is 2.02 * 107gPE/molVh, poly melt temperature is 135.9 ℃, and viscosity-average molecular weight is 378kg/mol.

Embodiment 38

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 3 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.65g with embodiment 34b, and catalytic activity is 1.56 * 107gPE/molVh, poly melt temperature is 136.1 ℃, and viscosity-average molecular weight is 328kg/mol.

Embodiment 39

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl with embodiment 4 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.78g with embodiment 34b, and catalytic activity is 1.87 * 107gPE/molVh, poly melt temperature is 135.7 ℃, and viscosity-average molecular weight is 306kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl with embodiment 4 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 34, experimental implementation gets cyclic olefine copolymer 0.55g with embodiment 34c, and catalytic activity is 6.60 * 106gPolym/molVh, 98.1 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 38.5%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.27mg that contains trifluoromethyl with embodiment 4 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 34, experimental implementation gets new LDPE (film grade) 0.51g with embodiment 34d, and catalytic activity is 6.12 * 106gPolym/molVh, the melt temperature of polymkeric substance is 106.6 ℃, 1-hexene insertion rate 17.6%.

Embodiment 40

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 5 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.69g with embodiment 34b, and catalytic activity is 1.66 * 107gPE/molVh, poly melt temperature is 136.8 ℃, and viscosity-average molecular weight is 276kg/mol.

Embodiment 41

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.79mg that contains trifluoromethyl with embodiment 6 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.11g, catalytic activity is 1.32 * 105gPE/molVh.131.0 ℃ of poly melt temperatures, viscosity-average molecular weight are 425kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 6 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.64g with embodiment 34b, and catalytic activity is 1.54 * 107gPE/molVh, poly melt temperature is 136.6 ℃, and viscosity-average molecular weight is 297kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 6 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.60g with embodiment 34c, and catalytic activity is 7.20 * 106gPolym/molVh, 98.4 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 39.5%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 6 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.63g with embodiment 34d, and catalytic activity is 7.56 * 106gPolym/molVh, the melt temperature of polymkeric substance is 106.3 ℃, 1-hexene insertion rate 7.5%.

Embodiment 42

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 7 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.90g with embodiment 34b, and catalytic activity is 2.16 * 107gPE/molVh, poly melt temperature is 136.9 ℃, and viscosity-average molecular weight is 356kg/mol.

Embodiment 43

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 8 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.70g with embodiment 34b, and catalytic activity is 1.68 * 107gPE/molVh, poly melt temperature is 135.8 ℃, and viscosity-average molecular weight is 348kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 8 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.75g with embodiment 34c, and catalytic activity is 9.00 * 106gPolym/molVh, 97.9 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 35.4%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.28mg that contains trifluoromethyl with embodiment 8 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.66g with embodiment 34d, and catalytic activity is 7.92 * 106gPolym/molVh, the melt temperature of polymkeric substance is 105.1 ℃, 1-hexene insertion rate 13.8%.

Embodiment 44

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.85mg that contains trifluoromethyl with embodiment 9 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.19g, catalytic activity is 2.28 * 105gPE/molVh.131.9 ℃ of poly melt temperatures, viscosity-average molecular weight are 423kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 9 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.73g with embodiment 34b, and catalytic activity is 1.75 * 107gPE/molVh, poly melt temperature is 137.0 ℃, and viscosity-average molecular weight is 368kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 9 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.81g with embodiment 34c, and catalytic activity is 9.72 * 106gPolym/molVh, 96.8 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 37.6%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 9 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.52g with embodiment 34d, and catalytic activity is 6.24 * 106gPolym/molVh, the melt temperature of polymkeric substance is 105.1 ℃, 1-hexene insertion rate 16.3%.

Embodiment 45

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 10 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.80g with embodiment 34b, and catalytic activity is 1.92 * 107gPE/molV.h, poly melt temperature is 136.9 ℃, and viscosity-average molecular weight is 383kg/mol.

Embodiment 46

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 11 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.84g with embodiment 34b, and catalytic activity is 2.02 * 107gPE/molVh, poly melt temperature is 135.6 ℃, and viscosity-average molecular weight is 349kg/mol.

Embodiment 47

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.32mg that contains trifluoromethyl with embodiment 12 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.94g with embodiment 34b, and catalytic activity is 2.26 * 107gPE/molVh, poly melt temperature is 135.88 ℃, and viscosity-average molecular weight is 398kg/mol.

Embodiment 48

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 13 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 1.02g with embodiment 34b, and catalytic activity is 2.45 * 107gPE/molVh, poly melt temperature is 137.6 ℃, and viscosity-average molecular weight is 378kg/mol.

Embodiment 49

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.85mg that contains trifluoromethyl with embodiment 14 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.12g, catalytic activity is 1.44 * 105gPE/molVh.134.3 ℃ of poly melt temperatures, viscosity-average molecular weight are 428kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 14 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.76g with embodiment 34b, and catalytic activity is 1.82 * 107gPE/molVh, poly melt temperature is 136.8 ℃, and viscosity-average molecular weight is 313kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 14 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.92g with embodiment 34c, and catalytic activity is 1.10 * 107gPolym/molVh, 98.1 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 41.8%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 14 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.51g with embodiment 34d, and catalytic activity is 6.12 * 106gPolym/molVh, the melt temperature of polymkeric substance is 104.5 ℃, 1-hexene insertion rate 10.9%.

Embodiment 50

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 15 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.78g with embodiment 34b, and catalytic activity is 1.87 * 107gPE/molVh, poly melt temperature is 135.9 ℃, and viscosity-average molecular weight is 343kg/mol.

Embodiment 51

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 16 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 1.00g with embodiment 34b, and catalytic activity is 2.40 * 107gPE/molVh, poly melt temperature is 136.6 ℃, and viscosity-average molecular weight is 388kg/mol.

Embodiment 52

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.33mg that contains trifluoromethyl with embodiment 17 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.72g with embodiment 34b, and catalytic activity is 1.73 * 107gPE/molVh, poly melt temperature is 136.8 ℃, and viscosity-average molecular weight is 321kg/mol.

Embodiment 53

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 18 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.96g with embodiment 34b, and catalytic activity is 2.30 * 107gPE/molVh, poly melt temperature is 135.7 ℃, and viscosity-average molecular weight is 368kg/mol.

Embodiment 54

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.92mg that contains trifluoromethyl with embodiment 19 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.15g, catalytic activity is 1.80 * 105gPE/molVh.129.0 ℃ of poly melt temperatures, viscosity-average molecular weight are 436kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 19 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.78g with embodiment 34b, and catalytic activity is 1.87 * 107gPE/molVh, poly melt temperature is 135.8 ℃, and viscosity-average molecular weight is 317kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 19 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.93g with embodiment 34c, and catalytic activity is 1.12 * 107gPolym/molVh, 97.3 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 40.7%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 19 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.68g with embodiment 34d, and catalytic activity is 8.16 * 106gPolym/molVh, the melt temperature of polymkeric substance is 108.2 ℃, 1-hexene insertion rate 14.7%.

Embodiment 55

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 20 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.75g with embodiment 34b, and catalytic activity is 1.80 * 107gPE/molVh, poly melt temperature is 135.6 ℃, and viscosity-average molecular weight is 328kg/mol.

Embodiment 56

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.92mg that contains trifluoromethyl with embodiment 21 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.11g, catalytic activity is 1.32 * 105gPE/molVh.128.9 ℃ of poly melt temperatures, viscosity-average molecular weight are 418kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 21 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.97g with embodiment 34b, and catalytic activity is 2.33 * 107gPE/molVh, poly melt temperature is 136.9 ℃, and viscosity-average molecular weight is 378kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 21 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.60g with embodiment 34d, and catalytic activity is 7.20 * 106gPolym/molVh, the melt temperature of polymkeric substance is 103.8 ℃, 1-hexene insertion rate 16.2%.

Embodiment 57

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 22 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.78g with embodiment 34b, and catalytic activity is 1.87 * 107gPE/molVh, poly melt temperature is 137.0 ℃, and viscosity-average molecular weight is 309kg/mol.

Embodiment 58

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 23 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.64g with embodiment 34b, and catalytic activity is 1.54 * 107gPE/molVh, poly melt temperature is 135.7 ℃, and viscosity-average molecular weight is 313kg/mol.

Embodiment 59

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.93mg that contains trifluoromethyl with embodiment 24 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.16g, catalytic activity is 1.92 * 105gPE/molVh.132.3 ℃ of poly melt temperatures, viscosity-average molecular weight are 397kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 24 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.90g with embodiment 34b, and catalytic activity is 2.16 * 107gPE/molVh, poly melt temperature is 135.5 ℃, and viscosity-average molecular weight is 367kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 24 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.78g with embodiment 34c, and catalytic activity is 9.36 * 106gPolym/molVh, 98.2 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 34.9%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 24 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.62g with embodiment 34d, and catalytic activity is 7.44 * 106gPolym/molVh, the melt temperature of polymkeric substance is 106.2 ℃, 1-hexene insertion rate 14.2%.

Embodiment 60

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 25 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.76g with embodiment 34b, and catalytic activity is 1.82 * 107gPE/molVh, poly melt temperature is 135.9 ℃, and viscosity-average molecular weight is 228kg/mol.

Embodiment 61

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 26 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.68g with embodiment 34b, and catalytic activity is 1.63 * 107gPE/molVh, poly melt temperature is 136.8 ℃, and viscosity-average molecular weight is 228kg/mol.

Embodiment 62

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.32mg that contains trifluoromethyl with embodiment 27 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.74g with embodiment 34b, and catalytic activity is 1.78 * 107gPE/molVh, poly melt temperature is 136.0 ℃, and viscosity-average molecular weight is 348kg/mol.

Embodiment 63

The beta diketone enamine vanadium olefin poly catalyst 0.32mg that contains trifluoromethyl with embodiment 28 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.91g with embodiment 34b, and catalytic activity is 2.18 * 107gPE/molVh, poly melt temperature is 135.3 ℃, and viscosity-average molecular weight is 294kg/mol.

Embodiment 64

The beta-diketo mono imine vanadium olefinic polymerization catalyst 2.87mg that contains trifluoromethyl with embodiment 29 preparations, be equivalent to 5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation is with embodiment 34a, get polyethylene 0.23g, catalytic activity is 2.76 * 105gPE/molVh.129.0 ℃ of poly melt temperatures, viscosity-average molecular weight are 428kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 29 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.86g with embodiment 34b, and catalytic activity is 2.06 * 107gPE/molVh, poly melt temperature is 136.8 ℃, and viscosity-average molecular weight is 373kg/mol.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 29 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets cyclic olefine copolymer 0.70g with embodiment 34c, and catalytic activity is 8.40 * 106gPolym/molVh, 98.2 ℃ of the second-order transition temperatures of polymkeric substance, norbornylene insertion rate 35.9%.

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 29 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets new LDPE (film grade) 0.58g with embodiment 34d, and catalytic activity is 6.96 * 106gPolym/molVh, the melt temperature of polymkeric substance is 105.8 ℃, 1-hexene insertion rate 11.8%.

Embodiment 65

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.29mg that contains trifluoromethyl with embodiment 30 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 1.12g with embodiment 34b, and catalytic activity is 2.69 * 107gPE/molVh, poly melt temperature is 137.1 ℃, and viscosity-average molecular weight is 393kg/mol.

Embodiment 66

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 31 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.70g with embodiment 34b, and catalytic activity is 1.68 * 107gPE/molVh, poly melt temperature is 1352 ℃, and viscosity-average molecular weight is 318kg/mol.

Embodiment 67

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.31mg that contains trifluoromethyl with embodiment 32 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 0.78g with embodiment 34b, and catalytic activity is 1.87 * 107gPE/molVh, poly melt temperature is 137.6 ℃, and viscosity-average molecular weight is 767kg/mol.

Embodiment 68

The beta-diketo mono imine vanadium olefinic polymerization catalyst 0.30mg that contains trifluoromethyl with embodiment 33 preparations, be equivalent to 0.5 μ mol, be dissolved in the 1mL toluene, the beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl that obtains in the alternate embodiment 1, experimental implementation gets polyethylene 1.20g with embodiment 34b, and catalytic activity is 2.88 * 107gPE/molVh, poly melt temperature is 136.9 ℃, and viscosity-average molecular weight is 428kg/mol.

Claims

1. a beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl is characterized in that, it has following structure:

R in the formula ₁Be the tertiary butyl, furyl, thienyl, pyridyl, phenyl, tolyl, ethylbenzene base, 3,5-dimethylphenyl, p-methoxy-phenyl or fluorophenyl; R ₂Be hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R ₃Be hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R ₄Be hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R ₅Be hydrogen, methyl, ethyl, sec.-propyl or methoxyl group; R ₆Be hydrogen, methyl, ethyl, sec.-propyl or methoxyl group.

2. according to the described beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl of claim 1, it is characterized in that, wherein, R ₃Be hydrogen, methyl or methoxy; R ₄Be hydrogen, methyl, ethyl or methoxyl group; R ₅Be hydrogen, methyl or methoxy.

3. according to the described beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl of claim 1, it is characterized in that, wherein, R ₁Be the tertiary butyl, phenyl, tolyl, ethylbenzene base, 3,5-dimethylphenyl, p-methoxy-phenyl or fluorophenyl; R ₃Be hydrogen, methyl or methoxy; R ₄Be hydrogen, methyl or methoxy; R ₅Be hydrogen, methyl or methoxy.

4. according to the described beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl of claim 1, it is characterized in that, wherein, R ₁Be the tertiary butyl, phenyl, tolyl or p-methoxy-phenyl; R ₃Be hydrogen, methyl or methoxy; R ₄Be hydrogen, methyl or methoxy; R ₅Be hydrogen, methyl or methoxy.

5. according to the described beta-diketo mono imine vanadium olefinic polymerization catalyst that contains trifluoromethyl of claim 1, it is characterized in that, wherein, R ₁Be the tertiary butyl, phenyl, tolyl or p-methoxy-phenyl; R ₂Hydrogen, methyl, ethyl or sec.-propyl; R ₃Be hydrogen or methyl; R ₄Be hydrogen or methyl; R ₅Be hydrogen or methyl; R ₆Hydrogen, methyl, ethyl or sec.-propyl.

6. one kind as the described preparation method who contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl of 1 to 5 any one claim: it is characterized in that

The western Buddhist alkali of step 1 preparation: the derivative, methyl alcohol, the formic acid that in the exsiccant reactor, add the beta-diketone compounds, aniline or the aniline that contain trifluoromethyl, its ratio range is 20-40mmol: 20-40mmol: 15-30mL: 1-2mL, heating reflux reaction 24-48h, steam solvent methanol with Rotary Evaporators, make eluent with the sherwood oil that contains 1% ethyl acetate, resistates is carried out column chromatography, obtains the western Buddhist alkali shown in the following formula:

Step 2 preparation contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl: under nitrogen atmosphere, adding mol number and volume proportion are 1mol in the exsiccant reactor: the western Buddhist alkali and the anhydrous tetrahydro furan that obtain above the 10L, stirring at room reaction 10min is cooled to-78 ℃; Within 5min, be that the hexane solution of 1.60mol/L n-Butyl Lithium joins in the reaction flask with concentration, the mol proportioning of n-Butyl Lithium and western Buddhist alkali is 1: 1.1, obtains negative ion part as follows:

Slowly rise to room temperature again, restir reaction 4h; In exsiccant Schlenk reactor, add title complex VCl33THF, the mol proportioning of title complex VCl33THF and western Buddhist alkali is 1: 1, be chilled to-78 ℃ under stirring, then in 30min, the lithium salt solution that obtains is above joined in the Schlenk reactor, and stirring reaction 1h slowly rises to room temperature, continue stirring reaction 12h, solvent removed in vacuo gets black solid, adds the dry toluene dissolving and also stirs 20min, the volume ratio of west Buddhist alkali mol number and dry toluene is 1mol: 10L, after the vacuum filtration, filtrate is concentrated, add anhydrous hexane, separate out brown crystalline compound, obtain containing the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl at last.

7. according to the described application that contains the beta-diketo mono imine vanadium olefinic polymerization catalyst of trifluoromethyl of claim 1, it is characterized in that, under the effect of diethyl aluminum chloride or modified methylaluminoxane, catalyzed ethylene polymerization, ethene and norbornylene copolymerization or ethene and alpha-olefin copolymer close.