CN1243030C - IVB family schiff base olefin polymerization catalyst and its preparing method - Google Patents
IVB family schiff base olefin polymerization catalyst and its preparing method Download PDFInfo
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Abstract
The present invention relates to an IVB family Schiff base catalyst for olefin polymerization and a preparing method thereof. The catalyst is the research emphasis of people at present due to the characteristic of high activity. In the present invention, After Schiff base ligand is made from fatty amine and 3-alkyl salicyl aldehyde, the Schiff base ligand reacts with n-Butyl Lithium or KH, and salt is generated. The Schiff base catalyst for olefin polymerization is obtained after the reaction of MCl4 dropped in salt solution with the salt solution. A high molecular Schiff base catalyst for olefin polymerization is obtained after copolymerization of the catalyst with olefin monomers. The catalyst has the advantages of mild preparation conditions and good catalysis effect.
Description
Technical field
The present invention is that western Buddhist alkali is all joined type IVB group 4 transition metal olefin polymerization catalysis and preparation method thereof.
Background technology
It uses the deeply all respects of society to macromolecular compound as material, just because of its diversity structure and incident with it multifarious performance, make macromolecular compound in the ascendant always in fundamental research, applied research and industrial production exploitation.At home according to the Sinopec corporate statistics: the present poly throughput of China is 1,000,000 tons/year, demand is 2,000,000 tons/year, along with social development, by 2010 years, China will need 1,000 ten thousand tons polyethylene product every year, increase manufacturing facilities merely and can not satisfy this demand.It is significant to develop efficient olefin polymerization catalysis.
Organometallic Chemistry and in the catalysis in olefine polymerization Application for Field has been opened up the New Times of polymer science.Since the application of the fifties Ziegler/Natta catalyst for olefinic polymerization, Organometallic Chemistry and olefinic polymerization theoretical developments are rapid, Organometallic Chemistry has been developed into rational design by simple trial, not only synthesized ten hundreds of novel cpds, more solve and set up many new notions, in fundamental research and practical application, all obtained brilliant achievement.The focus of current new olefine polymerization catalyst research is: rear transition metal (mainly being VIII family element) compound is as the research of olefin polymerization catalysis, and wherein nickel compound has high reactivity as olefin polymerization catalysis; Early stage, transistion metal compound mainly concentrated on the IVB compounds of group as the research of olefin polymerization catalysis, the western Buddhist alkali that metallocene catalyst that what wherein have decisive significance is Ziegler/Natta catalyst for olefinic polymerization of developing of the fifties, the eighties is developed and the nineties are developed is all joined type IVB group 4 transition metal olefin polymerization catalysis, and western Buddhist alkali all to join type IVB group 4 transition metal olefin polymerization catalysis be the highest catalyzer of catalytic activity up to now, be named as the FI catalyzer.It is the focus and emphasis of current research.
Summary of the invention
The purpose of this invention is to provide western Buddhist alkali and all join type IVB group 4 transition metal olefin polymerization catalysis and preparation method thereof.
This method adopts western Buddhist alkali [N-, O] and [Cl-] and IVB family zirconium coordination formation octahedral complex, and wherein two chlorine atoms are in cis position, constitute olefin polymerization catalysis; This catalyzer is by the catalyzer of olefin-copolymerization formation high molecular, and this two classes olefin polymerization catalysis has high reactivity.
Catalyzer concrete structure of the present invention is as follows:
Or
They are promotor by methylaluminoxane (MMAO).Component is same as the prior art.The IVB family west Buddhist alkali olefin polymerization catalysis structural formula of high molecular of the present invention is as follows:
M=10-1000 wherein, n=10-1000.
Preparation of catalysts method of the present invention is as follows:
(1) with allyl amine or isobutylamine and 3-tertiary butyl salicylic aldehyde at room temperature stirring reaction 15-20 hour, filter, evaporation removes and desolvates, Schiff base ligand;
(2) under anhydrous and oxygen-free high purity inert gas atmosphere, be solvent with the tetrahydrofuran (THF), Schiff base ligand solution is reacted 1.5-2.5hr with n-Butyl Lithium or KH under-72 ℃-room temperature, drop to MCl then
4Solution in stirring at room reaction 12-18 hour, aftertreatment gets final product, wherein MCl
4M be IVB family metal, the reactant ratio is:
Allyl amine or isobutylamine and 3-tertiary butyl salicylic aldehyde mol ratio are: (1-3): 1.
Schiff base ligand and MCl
4Mol ratio is: (2.0-2.5): 1.
Among the present invention, it is better that Schiff base ligand and n-Butyl Lithium generate lithium salts.
Among the present invention, with western Buddhist alkali olefin polymerization catalysis, olefinic monomer, go out basic initiator certainly and in solvent, mix copolyreaction, temperature of reaction 75-85 ℃, time 55-65 hour, western Buddhist alkali olefin polymerization catalysis/styrene monomer/radical initiator mol ratio: 10/100-10000/1.
Among the present invention, olefinic monomer is vinylbenzene or ethene.
Preparation method of the present invention is further described below:
1) preparation of 3-alkyl salicylic aldehyde
Its structural formula is:
The preparation of Grignard reagent: in there-necked flask, add MAGNESIUM METAL and the magnetic stir bar that takes by weighing metering; the fit on constant pressure funnel; reflux condensing tube and protection airbag; under vacuum, eliminate the moisture content in the device; in constant pressure funnel, add the about 50ml of anhydrous diethyl ether; in there-necked flask, add about 30ml anhydrous diethyl ether by constant pressure funnel then; in constant pressure funnel, add anhydrous monobromethane again; shaking constant pressure funnel makes the diethyl ether solution of monobromethane evenly mixed; open reflux condensation mode water; start magnetic agitation; the rate of addition of the diethyl ether solution of control monobromethane makes reaction keep gentle reflux, keeps 30min after being added dropwise to complete.
The preparation of 3-alkyl salicylic aldehyde: in there-necked flask, add the vicinal alkylene phenol that takes by weighing metering; add magnetic stir bar; assembling constant pressure funnel, reflux condensing tube and protection airbag; there-necked flask is the oil bath of assembling white oil down; open magnetic agitation, under vacuum, eliminate the moisture in the device and charge into argon gas.Add anhydrous tetrahydro furan (THF) 40ml, shift prepared Grignard reagent supernatant liquor in constant pressure funnel, and be transferred in the constant pressure funnel equally with about 20ml anhydrous diethyl ether washing, supernatant liquor by steel pipe.Open reflux condensation mode water, at room temperature drip Grignard reagent by constant pressure funnel, about 45min adds, and keeps reaction 2hr again.In reaction system, add dry toluene 100ml then, under vacuum, remove low-boiling point materials such as tetrahydrofuran (THF), ether.The Paraformaldehyde 96, triethylamine and the 50ml toluene that add metering, the oil bath about 8hr of backflow are down finished reaction.Prepare 10% aqueous solution 350ml of 36.5% concentrated hydrochloric acid, under the ice-water bath cooling, slowly add above-mentioned reaction mixture and fully stirring.The upper strata organic layer is collected in the mixture phase-splitting, again with the organic layer of extracted with diethyl ether to the phase-splitting colourless till.Merge organic layer, eliminate solvent with anhydrous sodium sulfate drying, filtration, evaporation and get 3-alkyl salicylic aldehyde crude product, get pure product with SiO2 post/sherwood oil wash-out.
2) preparation of Schiff base ligand
Its structural formula is:
The dehydrated alcohol that can handle through 4 molecular sieves with 20-30ml is solvent, 4 molecular sieve catalytics, C
1-C
15Fatty amine and 3-alkyl salicylic aldehyde be stirring reaction 15-20hr at room temperature, filters, and washs filter residue with ethyl acetate, evaporation remove desolvate crude product, use SiO
2Post, sherwood oil/ethyl acetate (10: 1) wash-out get the pure product of Schiff base ligand.
3) western Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
Its structural formula is:
Or
Preparation of catalysts is carried out under anhydrous and oxygen-free and high-purity inert gas such as argon shield condition.Can be solvent with the 30-40ml tetrahydrofuran (THF), Schiff base ligand and MCl
4By 1.5-2.5: 1 (mol) feeds intake, and Schiff base ligand solution becomes lithium salts with n-Butyl Lithium or KH reaction 1.5-2.5hr under-72 ℃-room temperature, drop to MCl then
4Solution in stirring at room reaction 12-18 hour, vacuum concentration adds methylene chloride and stirs 15min to doing, vacuum concentration is to doing again, with dichloromethane extraction and centrifugation lithium salts, concentrated extract gets catalyzer with the normal hexane chromatography, productive rate 92-96%.
4) high molecular Preparation of catalysts
Its structural formula is:
M=10-1000 wherein, n=10-1000.
Under the anhydrous and oxygen-free condition, the western Buddhist alkali that contains olefin group all can be joined type IVB group 4 transition metal olefin polymerization catalysis 2-10mmol, vinylbenzene 5-10ml, Diisopropyl azodicarboxylate (AIBN) 0.3-0.5g, join successively in the 30-50ml toluene and mix, in 75-85 ℃ oil bath copolymerization 55-65 hour then.Be cooled to room temperature, vacuum concentration is removed most of solvent, adds hexane and stirs, and is centrifugal, tells supernatant liquid, and solid is with toluene dissolving, normal hexane precipitation, centrifugal, remove supernatant liquid, and it is colourless to the upper strata clear liquid to repeat this process.The pressed powder of gained drying under vacuum is the high molecular catalyzer.
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in ethene atmosphere downhill reaction system, add toluene 50-100ml, methylaluminoxane, catalyzer according to this, under assigned temperature, react the fixed time, use the acid ethanol solution termination reaction, products therefrom is filtered, use washing with alcohol, and got polyethylene in 24 hours in 40 ℃ of vacuum-dryings.
Catalyst structure novelty of the present invention, the preparation condition gentleness, the catalytic activity height has very good prospects for application.
Description of drawings
Fig. 1 is the molecular structure of catalyzer.
Embodiment
The preparation of embodiment 1:3-tertiary butyl salicylic aldehyde
The preparation of Grignard reagent: the MAGNESIUM METAL that takes by weighing 1.848g (0.077mol); join in the 100ml there-necked flask; and in there-necked flask, adding a magnetic stir bar, fit on constant pressure funnel, reflux condensing tube and protection airbag eliminate the moisture in the device under vacuum.In constant pressure funnel, add the 50ml anhydrous diethyl ether then, in there-necked flask, add wherein about 30ml anhydrous diethyl ether by constant pressure funnel again.(5.2ml, 0.070mol) anhydrous monobromethane shake constant pressure funnel and make the diethyl ether solution of monobromethane evenly mixed to add 7.63g again in constant pressure funnel.Start magnetic agitation, open reflux condensation mode water, the rate of addition of diethyl ether solution of control monobromethane makes reaction keep gentle reflux, keeps 30min after being added dropwise to complete and makes and react completely.
The preparation of 3-tertiary butyl salicylic aldehyde: take by weighing 9.000g (0.060mol) o-tert-butylphenol with the 250ml there-necked flask; add magnetic stir bar; assembling constant pressure funnel, reflux condensing tube and protection airbag; there-necked flask is the oil bath of assembling white oil down; open magnetic agitation, under vacuum, eliminate the moisture in the device and charge into argon gas.Add 40ml anhydrous tetrahydro furan (THF) to there-necked flask, shift prepared Grignard reagent supernatant liquor in constant pressure funnel by steel pipe, and wash with the 20ml anhydrous diethyl ether, supernatant liquor is transferred in the constant pressure funnel equally.Open reflux condensation mode water, at room temperature drip Grignard reagent to there-necked flask by constant pressure funnel, about 45min adds, and keeps reaction 2hr again, will discharge the gas that is produced pitch time in this reinforced process.In reaction system, add the 100ml dry toluene then, under vacuum, remove low-boiling point materials such as tetrahydrofuran (THF), ether.(95%, 0.150mol) (about 8hr that refluxes in the 100-110 ℃ of oil bath finishes reaction for 12.5ml, 0.090mol) triethylamine and 50ml toluene for Paraformaldehyde 96,9.090g to add 4.700g in there-necked flask.Prepare 10% aqueous solution 300ml of 36.5% concentrated hydrochloric acid, under the ice-water bath cooling, slowly add above-mentioned reaction mixture and fully stirring.The upper strata organic layer is collected in the mixed system phase-splitting, again with the organic layer of extracted with diethyl ether to the phase-splitting colourless till.Merge organic layer, eliminate solvent with anhydrous sodium sulfate drying, filtration, evaporation and get crude product, with SiO2 post/sherwood oil wash-out, collect the solution of the orange band of the first layer, evaporating solvent gets orange red colour purity product 3-tertiary butyl salicylic aldehyde 9.078g (0.051mol), productive rate 85%,, C11H14NO, EI-MS:178.
Embodiment 2: the preparation of western Buddhist alkali 3-tertiary butyl salicylidene allyl amine part
Take by weighing 3.560g (0.020mol) 3-tertiary butyl salicylic aldehyde with the 100ml there-necked flask, add magnetic stir bar, assembling constant pressure funnel and protection airbag are opened magnetic agitation, fill exhaust three times with the vacuum argon system.Add the dehydrated alcohol that exsiccant 4 molecular sieve 3.077g, 30ml handled through 4 molecular sieves.Add dehydrated alcohol and the allyl amine that 20ml handles through 4 molecular sieves in constant pressure funnel, at room temperature drop in the there-necked flask, about 30min adds.Stirring reaction 15hr at room temperature filters then, washs filter residue with ethyl acetate, collects filtrate and washing lotion, evaporation remove desolvate crude product, use SiO
2Post, sherwood oil/ethyl acetate (15: 1) wash-out are collected the solution of the orange colour band of the first layer, evaporation remove desolvate the red western Buddhist alkali 3-tertiary butyl salicylidene allyl amine pure product 3.993g of part (0.018mol), productive rate 92%, C14H19NO, EI-MS217.
Embodiment 3: the preparation of western Buddhist alkali 3-tertiary butyl salicylidene isobutylamine part
Take by weighing 3.560g (0.020mol) 3-tertiary butyl salicylic aldehyde with the 100ml there-necked flask, add magnetic stir bar, assembling constant pressure funnel and protection airbag are opened magnetic agitation, fill exhaust three times with the vacuum argon system.Add the dehydrated alcohol that exsiccant 4 molecular sieve 3.077g, 30ml handle through 4 molecular sieves.Add dehydrated alcohol and the isobutylamine that 20ml handles through 4 molecular sieves in constant pressure funnel, at room temperature drop in the there-necked flask, about 30min adds.Stirring reaction 15hr at room temperature filters then, washs filter residue with ethyl acetate, collects filtrate and washing lotion, evaporation remove desolvate crude product, use SiO
2Post, petrol ether/ethyl acetate (15: 1) wash-out are collected the solution of the orange colour band of the first layer, evaporation remove desolvate the red western Buddhist alkali 3-tertiary butyl salicylidene isobutylamine pure product 4.427g of part (0.019mol), productive rate 95%, C
15H
23NO, EI-MS233.
Embodiment 4: western Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
Under anhydrous and oxygen-free and high-purity argon gas protective condition, take by weighing 3-tertiary butyl salicylidene allyl amine ligand 1 .302g (6.00mmol), add 20ml tetrahydrofuran (THF) (THF) with the magnetic agitation dissolving, be cooled to-72 ℃ with ethanol/the dry ice bath.Measure the hexane solution 3.83ml (6.12mmol, 1.02 times) of 1.6M n-Butyl Lithium then with syringe, slowly be injected under-72 ℃ in the THF solution of 3-tertiary butyl salicylidene allyl amine part, have gas to emit this moment.Remove dry ice/ethanol bath after adding, at room temperature the about 2.5hr of reaction becomes lithium salts, and this process produces the gas of expanded by heating.Have to an exsiccant and to add the anhydrous and oxygen-free THF20ml that handles through sodium Metal 99.5 in the reaction flask of magnetic stir bar, take by weighing zirconium tetrachloride (ZrCl
4) white powder 0.713g (and 98%, 3mmol), under agitation slowly be added among the THF by the glass Y-tube, this moment ZrCl4 dissolve colourless solution, be cooled to-72 ℃ with ethanol/the dry ice bath, above-mentioned lithium salt solution is dropped to ZrCl
4In the solution, remove dry ice/ethanol bath after being added dropwise to complete, stirring at room 15hr hour.Under vacuum, be concentrated into driedly then, add the 20ml methylene dichloride, restir 15min, vacuum concentration is to doing then.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrate this extraction liquid, get catalyst solid thing 0.891g-1.069g, productive rate 50-60%, EI-MS594, C28H36N202C12Zr with the normal hexane chromatography.
Embodiment 5: western Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
Under anhydrous and oxygen-free and high-purity argon gas protective condition, take by weighing 3-tertiary butyl salicylidene isobutylamine ligand 1 .398g (6.00mmol), add 20ml tetrahydrofuran (THF) (THF) with the magnetic agitation dissolving, be cooled to-72 ℃ with ethanol/the dry ice bath.Measure the hexane solution 3.83ml (6.12mmol, 1.02 times) of 1.6M n-Butyl Lithium with syringe then and slowly be injected under-72 ℃ in the THF solution of part, have gas to emit this moment.Remove dry ice/ethanol bath after adding, at room temperature the about 2.5hr of reaction becomes lithium salts, and this process produces the gas of expanded by heating.Have to an exsiccant and to add the anhydrous and oxygen-free THF20ml that handles through sodium Metal 99.5 in the reaction flask of magnetic stir bar, take by weighing zirconium tetrachloride (ZrCl4) white powder 0.713g (98%, 3mmol), under agitation slowly be added among the THF by the glass Y-tube, this moment ZrCl4 dissolve colourless solution, be cooled to-72 ℃ with ethanol/the dry ice bath, above-mentioned lithium salt solution is dropped in the ZrCl4 solution, remove dry ice/ethanol bath after being added dropwise to complete, stirring at room 15hr hour.Under vacuum, be concentrated into driedly then, add the 20ml methylene dichloride, restir 15min, vacuum concentration is to doing then.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrate this extraction liquid, get catalyst solid thing 0.939g-1.127g with the normal hexane chromatography,, productive rate 50-60%, EI-MS626, C30H44N202C12Zr.
Embodiment 6: high molecular west Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
Under the anhydrous and oxygen-free condition, the western Buddhist alkali that contains olefin group of embodiment 4 gained is all joined type IVB group 4 transition metal olefin polymerization catalysis 0.260g (0.438mmol), vinylbenzene 6ml, Diisopropyl azodicarboxylate (AIBN) 0.142g, 30ml toluene adds in the 50ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymer-1 8hr in 80 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets light yellow gluey viscous mixture, add 20ml hexane stirring, centrifugal, tell supernatant liquid, solid with toluene dissolving, normal hexane precipitation, centrifugal, remove supernatant liquid, it is colourless to the upper strata clear liquid to repeat this process.The solid of gained drying under vacuum is light yellow solid powder 1.292g.ICP-AES：Zr12.3mg/g。
Embodiment 7: the preparation of olefin polymerization catalysis solution and promotor
1) take by weighing the catalyst fines 0.0132g of embodiment 4 gained, add 20ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CAL, concentration is 1.1111umolZr/ml;
2) take by weighing the catalyst fines 0.0167g of embodiment 5 gained, add 20ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CIB, concentration is 1.3339umolZr/ml;
3) the catalyst fines 0.1648g that takes by weighing embodiment 6 gained adds 20ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CPSC4, concentration is 1.1138umolZr/ml;
Promotor is the toluene solution of methylaluminoxane (MMAO), and concentration is 2.20M.
Polymerization termination and polyethylene precipitation agent are acidic ethanol, are that the concentration that contains 36.5% hydrochloric acid is 1% industrial alcohol solution.
Embodiment 8: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.597g, and catalytic efficiency is 1.075 * 10
6GPE/molZr.hr.
Embodiment 9: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.606g, and catalytic efficiency is 1.091 * 10
6GPE/molZr.hr.
Embodiment 10: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.929g, and catalytic efficiency is 1.672 * 10
6GPE/molZr.hr.
Embodiment 11: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.958g, and catalytic efficiency is 1.724 * 10
6GPE/molZr.hr.
Embodiment 12: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 3.0mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.729g, and catalytic efficiency is 3.112 * 10
6G PE/molZr.hr.
Embodiment 13: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polymerization 15min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.093g, and catalytic efficiency is 0.335 * 10
6GPE/molZr.hr.
Embodiment 14: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polymerization 60min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.808g, and catalytic efficiency is 0.727 * 10
6GPE/molZr.hr.
Embodiment 15: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polymerization 1.5hr under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.535g, and catalytic efficiency is 0.321 * 10
6GPE/molZr.hr.
Embodiment 16: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCAL and 10ml toluene successively.Polyreaction is polymerization 2hr under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.630g, and catalytic efficiency is 0.284 * 10
6GPE/molZr.hr.
Embodiment 17: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCIB and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.888g, and catalytic efficiency is 1.332 * 10
6GPE/molZr.hr.
Embodiment 18: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.0mlMMAO, 1mlCIB and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.376g, and catalytic efficiency is 2.064 * 10
6GPE/molZr.hr.
Embodiment 19: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.5mlMMAO, 1mlCIB and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.557g, and catalytic efficiency is 2.336 * 10
6GPE/molZr.hr.
Embodiment 20: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCIB and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.120g, and catalytic efficiency is 1.680 * 10
6GPE/molZr.hr.
Embodiment 21: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 3.0mlMMAO, 1mlCIB and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.789g, and catalytic efficiency is 1.184 * 10
6GPE/molZr.hr.
Embodiment 22: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.075g, and catalytic efficiency is 0.135 * 10
6G PE/molZr.hr.
Embodiment 23: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Polyreaction is polyase 13 0min under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.163g, and catalytic efficiency is 0.293 * 10
6G PE/molZr.hr.
Embodiment 24: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.In 68 ℃ of following polyase 13 0min, stop the input of ethylene gas then, stop stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, get 0.0423g in 40 ℃ of vacuum-dryings 24 hours, catalytic efficiency is 0.075 * 10
6GPE/molZr.hr.
Embodiment 25: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Polyreaction is polymerization 2hr under room temperature, stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.513g, and catalytic efficiency is 0.230 * 10
6GPE/molZr.hr.
Embodiment 26: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 75 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 0.776g in 40 ℃ of vacuum-dryings 24 hours, catalytic efficiency is 0.697 * 10
6G PE/molZr.hr.
Embodiment 27: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, be adjusted to then to specify 60 ℃, feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 3.723g in 40 ℃ of vacuum-dryings 24 hours, catalytic efficiency is 3.343 * 10
6G PE/molZr.hr.
Embodiment 28: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, be adjusted to then to specify 45 ℃, feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene 2.0mlMMAO, 1mlCPSC4 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 4.132g in 40 ℃ of vacuum-dryings 24 hours, catalytic efficiency is 3.710 * 10
6G PE/molZr.hr.
Claims (6)
1, IVB family west Buddhist alkali olefin polymerization catalysis, its structural formula is as follows:
Promotor is methylaluminoxane or improves methylaluminoxane, i.e. MAO or MMAO.
2, IVB family west Buddhist alkali olefin polymerization catalysis is characterized in that the IVB family west Buddhist alkali olefin polymerization catalysis structural formula of high molecular is as follows:
m＝10-1000，n＝10-1000。
3, the preparation method of IVB according to claim 1 family west Buddhist alkali olefin polymerization catalysis is characterized in that:
(1) with allyl amine or isobutylamine and 3-tertiary butyl salicylic aldehyde at room temperature stirring reaction 15-20 hour, filter, evaporation removes and desolvates, Schiff base ligand;
(2) under the anhydrous and oxygen-free high purity inert gas, be solvent with the tetrahydrofuran (THF), Schiff base ligand solution is reacted the 1.5-2.5hr salify with n-Butyl Lithium or KH under-72 ℃-room temperature, drop to MCl then
4Solution in stirring at room reaction 12-18 hour, aftertreatment gets final product; MCl wherein
4M be IVB family metal, the reactant ratio is:
Allyl amine or isobutylamine and 3-tertiary butyl salicylic aldehyde mol ratio are: (1-3): 1;
Schiff base ligand and MCl
4Mol ratio is: (2.0-2.5): 1.
4, the preparation method of IVB according to claim 3 family west Buddhist alkali olefin polymerization catalysis is characterized in that Schiff base ligand and n-Butyl Lithium generation lithium salts.
5, the preparation method of IVB according to claim 2 family west Buddhist alkali olefin polymerization catalysis, it is characterized in that western Buddhist alkali olefin polymerization catalysis, styrene monomer, the radical initiator of claim 1 are mixed copolyreaction in solvent, temperature of reaction 75-85 ℃, time 55-65 hour, western Buddhist alkali olefin polymerization catalysis/styrene monomer/radical initiator mol ratio: 10/100-10000/1.
6, be applied to ethene or propylene polymerization according to the described IVB of claim 1-2 family west Buddhist alkali olefin polymerization catalysis.
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