CN100586966C - Bis-salicylaldehyde imine vanadium olefin polymerization catalyst as well as preparation method and application thereof - Google Patents

Bis-salicylaldehyde imine vanadium olefin polymerization catalyst as well as preparation method and application thereof Download PDF

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CN100586966C
CN100586966C CN200710056389A CN200710056389A CN100586966C CN 100586966 C CN100586966 C CN 100586966C CN 200710056389 A CN200710056389 A CN 200710056389A CN 200710056389 A CN200710056389 A CN 200710056389A CN 100586966 C CN100586966 C CN 100586966C
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hydrogen
olefin polymerization
polymerization catalyst
imine vanadium
methyl
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CN101205269A (en
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刘靖宇
李悦生
吴集钱
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to a method for preparing double salicylaldehyde imine vanadium olefin polymerization catalyst and application of the catalyst in catalyzing ethylene polymerization. Under the catalyzing effect of formic acid, condensation reaction of the salicylaldehyde or derivatives of the salicylaldehyde and aniline or derivatives of the aniline is carried out in methanol solution, and skiff base is obtained. Under the condition of no water and no oxygen and under the effect of excess triethylamine, the double salicylaldehyde imine vanadium olefin polymerization catalyst of the invention is obtained by complexation reaction of the skiff base and vanadium trichloride with an equivalent weight. Under the effect of diethyl aluminium chloride, the catalyst of the invention can be usedfor catalyzing ethylene polymerization. The invention has the advantages of easy preparation, high catalyzing activity and good thermal stability.

Description

A kind of double salicylaldehyde imine vanadium olefin polymerization catalyst and preparation method and application
Technical field
The present invention relates to a kind of double salicylaldehyde imine vanadium olefin polymerization catalyst and preparation method.
The invention still further relates to the application of above-mentioned double salicylaldehyde imine vanadium olefin polymerization catalyst in catalyzed ethylene polymerization.
Background technology
Twentieth century fifties, but Ziegler and Natta find transition metal complex catalysis in olefine polymerization under the condition of gentleness separately, after this in five more than ten years, emerged big quantity research and be devoted to develop high reactivity, product structure has been had high controlled transition metal-catalyzed system.Simultaneously, the continual renovation of polyolefin products has brought revolutionary variation for people's life, and increasingly extensive is applied in industry, agricultural, national defence, communications and transportation and the daily life.Therefore, organic ligand is carried out effective Molecular Structure Design, improve catalyst performance and in catalyzer research and development field, occupy core status.The fifties in last century, Carrick just once report utilize transition metal vanadium catalysis in olefine polymerization (JACS J.Am.Chem.Soc., 1958,80:6455).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 active low reason 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.
Recently, people such as Canada scientist Gambarotta have reported to be single main vanadium catalyst (the German applied chemistry Angewandte Chemie-international Edition 2007 that divides of assistant ligand with pyrroles, 46,6119-6122), but the activity of its catalyzed ethylene polymerization is not high.
Summary of the invention
For overcoming the shortcoming of low, the easy inactivation of catalytic activity, resistance to elevated temperatures difference, one of purpose of the present invention has provided a kind of double salicylaldehyde imine vanadium olefin polymerization catalyst.It has easy to prepare, advantages such as catalytic activity is high, Heat stability is good.
Another purpose of the present invention provides the preparation method of above-mentioned double salicylaldehyde imine vanadium olefin polymerization catalyst.
The 3rd purpose of the present invention provides the application of above-mentioned double salicylaldehyde imine vanadium olefin polymerization catalyst in catalyzed ethylene polymerization.
The structural formula of salicylic alidehyde imine vanadium olefin poly catalyst provided by the invention is as follows:
Figure C20071005638900061
In the formula, R 1Be hydrogen, the tertiary butyl or bromine; R 2Be hydrogen, the tertiary butyl or bromine; R 3Be hydrogen, methyl or sec.-propyl; R 4Be hydrogen, methyl or trifluoromethyl; R 5Be hydrogen, methyl or sec.-propyl;
Preferably: R 1～R 5All be hydrogen; R 1Be the tertiary butyl, R 2～R 5All be hydrogen; R 4Be trifluoromethyl, R 1, R 2, R 3And R 5All be hydrogen; R 4Be methyl, R 1, R 2, R 3And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3, R 4And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3And R 5Be sec.-propyl, R 4Be hydrogen; R 1And R 2Be bromine, R 3, R 4And R 5All be hydrogen; R 3And R 5Be methyl, R 1, R 2And R 4All be hydrogen or R 3And R 5Be sec.-propyl, R 1, R 2And R 4All be hydrogen.
The invention provides the preparation method of above-mentioned salicylic alidehyde imine vanadium olefin poly catalyst, be divided into two steps:
Step 1-prepares western Buddhist alkali: the derivative, methyl alcohol and the formic acid that add derivative, aniline or the aniline of salicylic aldehyde or salicylic aldehyde in the exsiccant reactor, wherein, the derivative of salicylic aldehyde or salicylic aldehyde (mmol): the derivative of aniline or aniline (mmol): methyl alcohol (ml): the proportioning of formic acid (ml) is (40-80): (40-80): (30-60): (1-2), 25 ℃ of reaction 12-48h, steam solvent methanol with Rotary Evaporators, with ethyl acetate and sherwood oil volume ratio 1: 100 solution, resistates is carried out column chromatography, obtains western Buddhist alkali as follows:
Figure C20071005638900071
In the formula, R 1Be hydrogen, the tertiary butyl or bromine; R 2Be hydrogen, the tertiary butyl or bromine; R 3Be hydrogen, methyl or sec.-propyl; R 4Be hydrogen, methyl or trifluoromethyl; R 5Be hydrogen, methyl or sec.-propyl;
Preferably: R 1～R 5All be hydrogen; R 1Be the tertiary butyl, R 2～R 5All be hydrogen; R 4Be trifluoromethyl, R 1, R 2, R 3And R 5All be hydrogen; R 4Be methyl, R 1, R 2, R 3And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3, R 4And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3And R 5Be sec.-propyl, R 4Be hydrogen; R 1And R 2Be bromine, R 3, R 4And R 5All be hydrogen; R 3And R 5Be methyl, R 1, R 2And R 4All be hydrogen or R 3And R 5Be sec.-propyl, R 1, R 2And R 4All be hydrogen.
Step 2 preparation salicylic alidehyde imine vanadium olefin poly catalyst:
Under nitrogen atmosphere, the western Buddhist alkali and the anhydrous tetrahydro furan that obtain above in the exsiccant reactor, adding, stirring at room reaction 10min makes the solid dissolving, and wherein, western Buddhist alkali (mmol) and anhydrous tetrahydro furan (ml) mixing ratio are 4: (10-20); In another exsiccant Schlenk reactor, add tetrahydrofuran (THF) title complex VCl with the equimolar vanadium trichloride of western Buddhist alkali 33THF and anhydrous tetrahydro furan, wherein VCl 33THF (mmol) and anhydrous tetrahydro furan (ml) proportioning are 2: (5-20), stir and make the solid dissolving, then at 25～30min, the western Buddhist alkaline solution that obtains is above added in the Schlenk reactor, add Et again 3N, stirring reaction 12-24h, solvent removed in vacuo gets black solid and adds the anhydrous tetrahydro furan dissolving and stir 10-30min, after the vacuum filtration, filtrate is concentrated adding anhydrous n-hexane, described Et 3The proportioning of N (mmol), anhydrous tetrahydro furan (ml) and anhydrous n-hexane (ml) is 4.5: (5-20): (10-40), separate out brown crystalline compound, obtain a kind of double salicylaldehyde imine vanadium olefin polymerization catalyst at last.
The 3rd purpose of the present invention provides above-mentioned double salicylaldehyde imine vanadium olefin polymerization catalyst under the effect of diethyl aluminum chloride (DEAC), the application in the catalyzed ethylene polymerization.
Concrete application method is as follows:
Under the ethene atmosphere, in the exsiccant polymerization reactor, add dry toluene successively, the toluene solution of the diethyl aluminum chloride of 2M, 0.5M the toluene solution of three chloro ethyl acetate, after stirring 5 minutes under 25-70 ℃, the toluene solution that adds the salicylic alidehyde imine vanadium olefin poly catalyst of above-mentioned preparation, its concentration is 0.5 μ mol/ml, wherein, dry toluene: the toluene solution of diethyl aluminum chloride: the toluene solution of ethyl trichloroacetate: the volume proportion of the toluene solution of salicylic alidehyde imine vanadium olefin poly catalyst is 100: 1: 0.6: 2, stir the following polyreaction specified time, reactant is poured in the ethanolic soln that concentration is 0.5% hydrochloric acid, filter, with concentration is the ethanolic soln washing 2 times of 0.5% hydrochloric acid, washing with alcohol 3 times, vacuum-drying obtains polyethylene.
Beneficial effect of the present invention: under the effect of diethyl aluminum chloride (DEAC), 25 ℃ of following double salicylaldehyde imine vanadium olefin polymerization catalyst catalyzed ethylene polymerization activity: 1.20-16.1 * 10 6GPE/mol VH, gained polyethylene viscosity-average molecular weight: 8.30-20.3 * 10 4G/mol.The salicylic alidehyde imine vanadium olefin poly catalyst is examined or check the activity when polymerization activity all is higher than polymerized at normal temperature in the time of 50 ℃, polymerization activity best result Bie Keda 16.8 * 10 when 50 ℃ and 70 ℃ at 50 ℃ and 70 ℃ of following catalyzed ethylene polymerizations 6GPE/mol VH and 18.2 * 10 6GPE/mol VH.
Embodiment
Embodiment 1
Adding salicylic aldehyde 9.77g is equivalent to 80mmol, aniline 7.45g and is equivalent to 80mmol, methyl alcohol 50ml, formic acid 2ml in the exsiccant reactor, 25 ℃ of reaction 24h.Steaming solvent methanol with Rotary Evaporators, is that 1: 100 solution 1000ml makes eluent with ethyl acetate and sherwood oil volume ratio, and resistates is carried out column chromatography, yellow solid shape west Buddhist alkali 15.0g, yield 95%. 1H?NMR(300MHz，DMSO)：δ6.93-7.68(m，9H，Ar-H)，8.97(s，1H，CH＝N)，13.07(s，1H，OH)。Mass spectroscopy, molecular ion peak m/e is 197.Ultimate analysis measured value: C, 79.30%; H, 5.64%; N, 7.05%; Theoretical value (C 13H 11NO): C, 79.16%; H, 5.62%; N, 7.10%.
Under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 0.78g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 20ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF2.0mmol, stir and make the solid dissolving (0.75g) with anhydrous tetrahydro furan 20ml, then in 30min, the western Buddhist alkaline solution that obtains is above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, adds anhydrous tetrahydro furan 20ml dissolving and also stirs 10min, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 20ml separates out the crystalline compound of dark red and gets title complex 0.71g, yield 65%.Mass spectroscopy, molecular ion peak m/e is 549.Ultimate analysis measured value: C, 64.89%; H, 4.87%; N, 5.14%; Theoretical value (C 30H 27ClN 2O 3V): C, 65.52%; H, 4.95%; N, 5.09%.
Under the ethene atmosphere, in exsiccant 100ml polymerization bottle, add dry toluene 50ml successively, the toluene solution 0.5ml of the diethyl aluminum chloride of 2M, 0.5mol/L the toluene solution 0.3ml of chloracetic acid ethyl ester, after stirring 5 minutes under 25 ℃, the double salicylaldehyde imine vanadium olefin polymerization catalyst 0.27mg that adds above-mentioned preparation, be equivalent to 0.5 μ mol, it is dissolved in the 1ml toluene, stir polyreaction 5min down, reactant is poured in the ethanolic soln of 300ml 0.5% hydrochloric acid, filtered, the ethanolic soln washing of 0.5% hydrochloric acid 2 times, washing with alcohol 3 times, vacuum-drying gets polyethylene 0.35g, and catalytic activity is 8.4 * 10 6GPE/mol VH, poly melt temperature is 136.5 ℃, viscosity-average molecular weight is 119kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 1, operate the same, must polyethylene 0.43g, catalytic activity is 10.32 * 10 6GPolym/mol VH, 131.7 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 22kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 1, operate the same, must polyethylene 0.41g, catalytic activity is 9.84 * 10 6GPolym/mol VH, 130.6 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 13kg/mol.
Embodiment 2
Be equivalent to 40mmol, be equivalent to aniline, methyl alcohol 60ml, formic acid 1ml in the 40mmol alternate embodiment 1 with salicylic aldehyde 4.89g with p-trifluoromethylaniline 6.44g, 25 ℃ of reaction 12h, experimental implementation gets yellow solid shape west Buddhist alkali 9.76g, yield 92% with embodiment 1. 1H?NMR(300MHz，DMSO)：δ6.98-7.83(m，8H，Ar-H)，9.00(s，1H，CH＝N)，12.62(s，1H，OH)。Mass spectroscopy, molecular ion peak m/e is 265.Ultimate analysis measured value: C, 63.25%; H, 3.83%; N, 5.30%; Theoretical value (C 14H 10F 3NO): C, 63.40%; H, 3.80%; N, 5.28%.
Under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 1.06g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 20ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF2.0mmol, stir and make the solid dissolving (0.75g) with anhydrous tetrahydro furan 15ml, then in 30min, the western Buddhist alkaline solution that obtains is above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 10ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 20ml gets dark red title complex 0.70g, yield 51%.Mass spectroscopy, molecular ion peak m/e is 685.Ultimate analysis measured value: C, 56.25%; H, 3.71%; N, 4.01%; Theoretical value (C 32H 25ClF 6N 2O 3V): C, 56.03%; H, 3.67%; N, 4.08%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.34mg with embodiment 2 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.67g with embodiment 1, and catalytic activity is 16.08 * 10 6GPE/mol VH, poly melt temperature is 136.1 ℃, viscosity-average molecular weight is 111kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 2, operation gets polyethylene 0.70g with embodiment 1, and catalytic activity is 16.80 * 10 6GPolym/mol VH, 134.1 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 44kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 2, operation gets polyethylene 0.76g with embodiment 1, and catalytic activity is 18.24 * 10 6GPolym/mol VH, 132.1 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 24kg/mol.
Embodiment 3
Be equivalent to 40mmol, use monomethylaniline 4.28g is equivalent to aniline, methyl alcohol 30ml, formic acid 1ml in the 40mmol alternate embodiment 1 with salicylic aldehyde 4.89g, 25 ℃ of reaction 12h, experimental implementation is with embodiment 1, yellow solid shape west Buddhist alkali 7.85g, yield 93%. 1H?NMR(300MHz，CDCl 3)：δ2.44(s，3H，CH 3)，6.94-7.65(m，8H，Ar-H)，8.96(s，1H，CH＝N)，13.22(s，1H，OH)。Mass spectroscopy, molecular ion peak m/e is 211.Ultimate analysis measured value: C, 79.63%; H, 6.25%; N, 6.71%; Theoretical value (C 14H 13NO): C, 79.59%; H, 6.20%; N, 6.63%.
Be equivalent to the western Buddhist alkali that obtains in the 4mmol alternate embodiment 1 with the western Buddhist alkali g of embodiment 3 preparation, experimental implementation is with embodiment 1, under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 0.85g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 20ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF 2.0mmol (0.75g) and anhydrous tetrahydro furan 15ml stir and make the solid dissolving, then in 30min, the western Buddhist alkaline solution that obtains are above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 10ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 10ml gets dark red title complex 0.80g, yield 69%.Mass spectroscopy, molecular ion peak m/e is 577.Ultimate analysis measured value: C, 66.68%; H, 5.48%; N, 4.79%; Theoretical value (C 32H 31ClN 2O 3V): C, 66.50%; H, 5.41%; N, 4.85%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.29mg with embodiment 3 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.25g with embodiment 1, and catalytic activity is 6.00 * 10 6GPE/mol VH, poly melt temperature is 135.8 ℃, viscosity-average molecular weight is 122kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 3, operation gets polyethylene 0.35g with embodiment 1, and catalytic activity is 8.40 * 10 6GPolym/mol VH, 134.0 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 48kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 3, operation gets polyethylene 0.32g with embodiment 1, and catalytic activity is 7.68 * 10 6GPolym/mol VH, 130.0 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 17kg/mol.
Embodiment 4
With salicylic aldehyde 4.89g be equivalent to 60mmol, with 2,6-xylidine 7.26g is equivalent to aniline, methyl alcohol 40ml, the formic acid 1ml in the 60mmol alternate embodiment 1,25 ℃ of reaction 24h, and experimental implementation is with embodiment 1, get yellow liquid west Buddhist alkali 12.01g, yield 89%. 1H?NMR(300MHz，CDCl 3)：δ1.11(s，6H，CH 3)，6.96-7.74(m，7H，Ar-H)，8.58(s，1H，CH＝N)，12.66(s，1H，OH)。Mass spectroscopy, molecular ion peak m/e is 225.Ultimate analysis measured value: C, 79.91%; H, 6.69%; N, 6.25%; Theoretical value (C 15H 15NO): C, 79.97%; H, 6.71%; N, 6.22%.
Under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 0.90g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 10ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF2.0mmol, stir and make the solid dissolving (0.75g) with anhydrous tetrahydro furan 5ml, then in 30min, the western Buddhist alkaline solution that obtains is above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 5ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 40ml gets dark red title complex 0.36g, yield 30%.Mass spectroscopy, molecular ion peak m/e is 605.Ultimate analysis measured value: C, 67.55%; H, 5.87%; N, 5.80%; Theoretical value (C 34H 35ClN 2O 3V): C, 67.38%; H, 5.82%; N, 4.62%.
Be equivalent to the western Buddhist alkali that obtains in the 4mmol alternate embodiment 1 with the western Buddhist alkali 0.85g of embodiment 4 preparation, experimental implementation is with embodiment 1, dark red title complex 0.80g, yield 69%.Mass spectroscopy, molecular ion peak m/e is 577.Ultimate analysis measured value: C, 66.68%; H, 5.48%; N, 4.79%; Theoretical value (C 32H 31ClN 2O 3V): C, 66.50%; H, 5.41%; N, 4.85%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.30mg with embodiment 4 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.59g with embodiment 1, and catalytic activity is 14.16 * 10 6GPE/mol VH, poly melt temperature is 136.8 ℃, viscosity-average molecular weight is 98kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 4, operation gets polyethylene 0.62g with embodiment 1, and catalytic activity is 14.88 * 10 6GPolym/mol VH, 135.0 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 55kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 4, operation gets polyethylene 0.57g with embodiment 1, and catalytic activity is 13.68 * 10 6GPolym/mol VH, 131.1 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 15kg/mol.
Embodiment 5
With salicylic aldehyde 4.89g be equivalent to 40mmol, with 2,6-diisopropyl aniline 7.09g is equivalent to aniline, methyl alcohol 60ml, the formic acid 1ml in the 40m mol alternate embodiment 1,25 ℃ of reaction 48h, and experimental implementation is with embodiment 1, get yellow solid shape west Buddhist alkali 10.23g, yield 91%. 1H?NMR(300MHz，CDCl 3)：δ1.21(d，12H，CH(CH 3) 2)，2.91(sept，2H，CH(CH 3) 2)，7.01-7.69(m，7H，Ar-H)，8.58(s，1H，CH＝N)，12.68(s，1H，OH)。Mass spectroscopy, molecular ion peak m/e is 281.Ultimate analysis measured value: C, 81.25%; H, 8.28%; N, 4.95%; Theoretical value (C 19H 23NO): C, 81.10%; H, 8.24%; N, 4.98%.
Be equivalent to the western Buddhist alkali that obtains in the 4mmol alternate embodiment 1 with the western Buddhist alkali g of embodiment 5 preparation, experimental implementation is with embodiment 1, under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 1.12g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 10ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF 2.0mmol (0.75g) and anhydrous tetrahydro furan 15ml stir and make the solid dissolving, then in 30min, the western Buddhist alkaline solution that obtains are above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 5ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 40ml gets dark red title complex 0.95g, yield 66%.Mass spectroscopy, molecular ion peak m/e is 717.Ultimate analysis measured value: C, 70.89%; H, 7.22%; N, 3.96%; Theoretical value (C 42H 51ClN 2O 3V :): C, 70.23%; H, 7.16%; N, 3.90%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.36mg with embodiment 5 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.55g with embodiment 1, and catalytic activity is 13.20 * 10 6GPE/mol VH, poly melt temperature is 135.5 ℃, viscosity-average molecular weight is 91kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 5, operation gets polyethylene 0.59g with embodiment 1, and catalytic activity is 14.16 * 10 6GPolym/mol VH, 135.0 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 62kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 5, operation gets polyethylene 0.56g with embodiment 1, and catalytic activity is 13.44 * 10 6GPolym/mol VH, 131.1 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 13kg/mol.
Embodiment 6
With 2,4-di-tert-butyl salicylaldehyde 9.37g is equivalent to 40mmol, with 2, and 6-diisopropyl aniline 7.09g is equivalent to the aniline in the 40mmol alternate embodiment 1, methyl alcohol 40ml, formic acid 1.5ml, 25 ℃ of reaction 48h, experimental implementation is with embodiment 1, De Xifo alkali 14.22g, yield 90%.Mass spectroscopy, molecular ion peak m/e is 393. 1H?NMR(300MHz，CDCl 3)：δ1.16-1.19(d，12H，CH(CH 3) 2)，1.34(s，9H，C(CH 3) 3)，1.50(s，9H，C(CH 3) 3)，3.02(sept，2H，CH(CH 3) 2)，7.15-7.51(m，5H，Ar-H)，8.29(s，1H，CH＝N)。Ultimate analysis measured value: C, 82.46%; H, 10.03%; N, 3.53%; Theoretical value (C 27H 39NO): C, 82.39%; H, 9.99%; N, 3.56%.
Be equivalent to the western Buddhist alkali that obtains in the 4mmol alternate embodiment 1 with the western Buddhist alkali g of embodiment 6 preparation, experimental implementation is with embodiment 1, under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 1.58g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 20ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF 2.0mmol (0.75g) and anhydrous tetrahydro furan 5ml stir and make the solid dissolving, then in 30min, the western Buddhist alkaline solution that obtains are above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 15ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 20ml gets dark red title complex 0.85g, yield 45%.Mass spectroscopy, molecular ion peak m/e is 942.Ultimate analysis measured value: C, 73.85%; H, 8.83%; N, 2.99%; Theoretical value (C 58H 84Cl 2N 2O 3V): C, 73.90%; H, 8.87%; N, 2.97%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.47mg with embodiment 6 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.08g with embodiment 1, and catalytic activity is 1.92 * 10 6GPE/mol VH, poly melt temperature is 135.2 ℃, viscosity-average molecular weight is 20.3kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 6, operation gets polyethylene 0.05g with embodiment 1, and catalytic activity is 1.20 * 10 6GPolym/mol VH, 134.2 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 94kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 6, operation gets polyethylene 0.56g with embodiment 1, and catalytic activity is 13.44 * 10 6GPolym/mol VH, 131.1 ℃ of the melt temperatures of polymkeric substance, viscosity-average molecular weight are 19kg/mol.
Embodiment 7
With 2,4-Dibromosalicylaldehyde 11.11g is equivalent to 40mmol, aniline 3.73g is equivalent to 40mmol, methyl alcohol 40ml, and formic acid 1.5ml, 25 ℃ of reaction 48h, experimental implementation is with embodiment 1, De Xifo alkali 13.92g, yield 98%.Mass spectroscopy, molecular ion peak m/e is 355. 1H?NMR(300MHz，CDCl 3)：δ7.31-7.76(m，7H，Ar-H)，8.55(s，1H，CH＝N)。Ultimate analysis measured value: C, 43.96%; H, 2.58%; N, 3.93%; Theoretical value (C 13H 9Br 2NO): C, 43.98%; H, 2.56%; N, 3.95%.
Under nitrogen atmosphere, in exsiccant device reactor, add the above-mentioned western Buddhist alkali 1.42g that obtains and be equivalent to 4.0mmol and anhydrous tetrahydro furan 20ml, stirring at room reaction 10min makes the solid dissolving, adds the tetrahydrofuran (THF) title complex VCl of vanadium trichloride in another exsiccant Schlenk reactor 33THF2.0mmol, stir and make the solid dissolving (0.75g) with anhydrous tetrahydro furan 20ml, then in 30min, the western Buddhist alkaline solution that obtains is above joined in the Schlenk reactor, add Et again 3N 4.5mmol, stirring reaction 12h.Solvent removed in vacuo gets black solid, and 10min is also stirred in adding anhydrous tetrahydro furan 10ml dissolving, after the vacuum filtration, filtrate is concentrated, and adding anhydrous n-hexane 30ml gets dark red title complex 0.97g, yield 56%.Mass spectroscopy, molecular ion peak m/e is 865.Ultimate analysis measured value: C, 41.55%; H, 2.66%; N, 3.27%; Theoretical value (C 30H 23Br 4ClN 2O 3V): C, 41.63%; H, 2.68%; N, 3.24%.
Salicylic alidehyde imine vanadium olefin poly catalyst 0.43mg with embodiment 7 preparations is equivalent to 0.5 μ mol, and it is dissolved in the 1ml toluene, the salicylic alidehyde imine vanadium olefin poly catalyst of using in the alternate embodiment 1, experimental implementation gets polyethylene 0.45g with embodiment 1, and catalytic activity is 10.80 * 10 6GPE/mol VH, poly melt temperature is 134.9 ℃, viscosity-average molecular weight is 108kg/mol.
With 50 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 7, operation gets polyethylene 0.56g with embodiment 1, and catalytic activity is 13.44 * 10 6GPolym/mol VH, 133.5 ℃ of the second-order transition temperatures of polymkeric substance, viscosity-average molecular weight are 98kg/mol.
With 70 ℃ of 25 ℃ of polymerization temperatures that replace among the embodiment 7, operation gets polyethylene 0.57g with embodiment 1, and catalytic activity is 13.68 * 10 6GPolym/mol VH, 130.1 ℃ of the second-order transition temperatures of polymkeric substance, viscosity-average molecular weight are 17kg/mol.

Claims (13)

1. a double salicylaldehyde imine vanadium olefin polymerization catalyst is characterized in that, it has following structure:
Figure C2007100563890002C1
R in the formula 1Be hydrogen, the tertiary butyl or bromine; R 2Be hydrogen, the tertiary butyl or bromine; R 3Be hydrogen, methyl or sec.-propyl; R 4Be hydrogen, methyl or trifluoromethyl; R 5Be hydrogen, methyl or sec.-propyl.
2. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 1～R 5All be hydrogen.
3. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 1Be the tertiary butyl, R 2～R 5All be hydrogen.
4. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 4Be trifluoromethyl, R 1, R 2, R 3And R 5All be hydrogen.
5. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 4Be methyl, R 1, R 2, R 3And R 5All be hydrogen.
6. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 1And R 2Be the tertiary butyl, R 3, R 4And R 5All be hydrogen.
7. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 1And R 2Be the tertiary butyl, R 3And R 5Be sec.-propyl, R 4Be hydrogen.
8. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 1And R 2Be bromine, R 3, R 4And R 5All be hydrogen.
9. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 3And R 5Be methyl, R 1, R 2And R 4All be hydrogen.
10. according to the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that said R 3And R 5Be sec.-propyl, R 1, R 2And R 4All be hydrogen.
As the preparation method of the said double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that 11, step and condition are as follows:
Step 1-prepares western Buddhist alkali: the derivative that adds salicylic aldehyde or salicylic aldehyde in the exsiccant reactor is 2, the 4-di-tert-butyl salicylaldehyde, 2, the 4-Dibromosalicylaldehyde, the derivative of aniline or aniline is a p-trifluoromethylaniline, to monomethylaniline, 2, the 6-xylidine, 2, the 6-diisopropyl aniline, methyl alcohol and formic acid, wherein, the derivative of salicylic aldehyde or salicylic aldehyde (mmol): the derivative of aniline or aniline (mmol): methyl alcohol (ml): the proportioning of formic acid (ml) is (40-80): (40-80): (30-60): (1-2), 25 ℃ of reaction 12-48h, steam solvent methanol with Rotary Evaporators, with ethyl acetate and sherwood oil volume ratio 1: 100 solution, resistates is carried out column chromatography, obtains western Buddhist alkali as follows:
In the formula, R 1Be hydrogen, the tertiary butyl or bromine; R 2Be hydrogen, the tertiary butyl or bromine; R 3Be hydrogen, methyl or sec.-propyl; R 4Be hydrogen, methyl or trifluoromethyl; R 5Be hydrogen, methyl or sec.-propyl;
Step 2 preparation salicylic alidehyde imine vanadium olefin poly catalyst:
Under nitrogen atmosphere, the western Buddhist alkali and the anhydrous tetrahydro furan that obtain above in the exsiccant reactor, adding, stirring at room reaction 10min makes the solid dissolving, and wherein, western Buddhist alkali (mmol) and anhydrous tetrahydro furan (ml) proportioning are 4: (10-20); In another exsiccant Schlenk reactor, add tetrahydrofuran (THF) title complex VCl with the equimolar vanadium trichloride of western Buddhist alkali 33THF and anhydrous tetrahydro furan, wherein VCl 33THF (mmol) and anhydrous tetrahydro furan (ml) proportioning are 2: (5-20), stir and make the solid dissolving, then at 25～30min, the western Buddhist alkaline solution that obtains is above added in the Schlenk reactor, add Et again 3N, stirring reaction 12-24h, solvent removed in vacuo gets black solid and adds the anhydrous tetrahydro furan dissolving and stir 10-30min, after the vacuum filtration, filtrate is concentrated adding anhydrous n-hexane, described Et 3The proportioning of N (mmol), anhydrous tetrahydro furan (ml) and anhydrous n-hexane (ml) is 4.5: (5-20): (10-40), separate out brown crystalline compound, obtain a kind of double salicylaldehyde imine vanadium olefin polymerization catalyst at last.
12, as the preparation method of the said double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 11, it is characterized in that the R in the described western Buddhist alkali that obtains 1～R 5All be hydrogen; R 1Be the tertiary butyl, R 2～R 5All be hydrogen; R 4Be trifluoromethyl, R 1, R 2, R 3And R 5All be hydrogen; R 4Be methyl, R 1, R 2, R 3And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3, R 4And R 5All be hydrogen; R 1And R 2Be the tertiary butyl, R 3And R 5Be sec.-propyl, R 4Be hydrogen; R 1And R 2Be bromine, R 3, R 4And R 5All be hydrogen; R 3And R 5Be methyl, R 1, R 2And R 4All be hydrogen or R 3And R 5Be sec.-propyl, R 1, R 2And R 4All be hydrogen.
13, according to the application of the described double salicylaldehyde imine vanadium olefin polymerization catalyst of claim 1, it is characterized in that, under the effect of diethyl aluminum chloride, be used for catalyzed ethylene polymerization.
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