CN1288173C - Polystyrene loaded IVB family compound and its use in ethylene polymerization - Google Patents
Polystyrene loaded IVB family compound and its use in ethylene polymerization Download PDFInfo
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- CN1288173C CN1288173C CN 200410011387 CN200410011387A CN1288173C CN 1288173 C CN1288173 C CN 1288173C CN 200410011387 CN200410011387 CN 200410011387 CN 200410011387 A CN200410011387 A CN 200410011387A CN 1288173 C CN1288173 C CN 1288173C
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Abstract
The present invention belongs to a polystyrene-loaded Schiff base IVB group complex containing alkoxy groups and a method for preparing the complex into an olefin polymerization catalyst. The Schiff base IVB group complex containing olefin oxygen groups and styrene are processed by copolymerization through free radical initiators to obtain the polystyrene loaded Schiff base IVB group complex which has high catalytic activity on the polymerization of ethylene, and the catalytic activity is 15.696*10<6>gPE/molZr. hr. The viscosity-average molecular weight of the obtained polymers is as high as millions.
Description
Technical field
The invention belongs to the IVB family title complex of a class loaded by polystyreneization and be used as vinyl polymerization.
Background technology
Polyolefine is because the diversity of its kind, structure and performance causes the strong interest and the input of industry and academia, three more than ten years in past witness the earth-shaking development that brings to polyolefin field of transistion metal compound.Catalyzed polymerization based on transistion metal compound has outstanding advantage with respect to other polymerization process, as the chain structure of accurate controlling polymers, at polymerizing condition more gentle aspect temperature and the pressure etc.Chem.Lett. the FI catalyzer of (1999) 1263-1264 report is the IVB family title complex that contains two Schiff's base ligands, and such catalyzer has the activity of high catalyzed ethylene polymerization.Chinese patent 98125651.1,00121820.4,00136190.2 discloses the preparation method of high molecular metallocene calalyst for polymerization of olefine and the preparation method of high molecular rear transition metal " luxuriant back " olefin polymerization catalysis respectively.The meaning of macromolecule loading catalyzer is that it is adapted to existing polyolefin process process, and the macromolecule loading catalyzer can not bring the ash of any inorganics form to product.Chinese patent 200310122945.2 disclosed contents mainly are catalyzer and the macromolecule loadingizations thereof that contains short-chain hydrocarbon group on the nitrogen of Schiff's base.
Summary of the invention
The preparation method who the purpose of this invention is to provide the IVB family title complex of a class loaded by polystyreneization;
Another object of the present invention provides the IVB family title complex that contains-oxyl of a class loaded by polystyreneization as vinyl polymerization.
Catalyzer of the present invention structurally adopts [N, the O of Schiff's base by the IVB family title complex of the Schiff's base that contains olefin oxy and the catalyzer styrene copolymerized and loadization that forms
-] bidentate chelating and [Cl
-] form octahedra title complex with the element coordination of IVB family, wherein two chlorine atoms are in cis position.The catalyzer of the type presents high catalytic activity to vinyl polymerization under the effect of methylaluminoxane, be the high activated catalyst of the novel olefinic polymerization of a class, and the polymkeric substance of gained possesses the molecular weight higher than FI catalyzer.
The prepared IVB family title complex of the present invention has following structure:
N=1 wherein, 2 or 3, R
1During for the tertiary butyl, R
2Be hydrogen or methyl; R
1During for phenyl, R
2Be hydrogen; M is titanium (Ti) or zirconium (Zr);
Expression polystyrene segment; They help catalysis to form the olefin polymerizating activity center by methylaluminoxane that contains triisobutyl aluminium (MMAO) or methylaluminoxane (MAO).
Preparation of catalysts
Under the anhydrous and oxygen-free condition, the title complex 0.1-0.5mmol of IVB family that will contain the Schiff's base of olefin group, Diisopropyl azodicarboxylate 0.1-0.5g, vinylbenzene 3-10ml, 30-50ml toluene joins in the reaction flask that a magnetic stir bar is housed successively, stirred 20-48 hour down at 60-80 ℃ then, through desolventize, toluene/normal hexane repeated washing, drying is the high molecular catalyzer under the vacuum.Metal content ICP-AES1.86-30.7mg/g in the high molecular catalyzer, GPC:Mn=9483-24772, PDI (Mw/Mn)=1.3384-1.6375.
Vinyl polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene, methylaluminoxane, catalyzer successively, ethylene gas under normal pressure or high pressure is depressed in room temperature to 75 ℃ following reaction 0.5-1hr, the input of termination ethene, with the ethanolic soln termination reaction that contains 2% hydrochloric acid, products therefrom is filtered, use washing with alcohol, vacuum-drying gets the polyethylene pressed powder.Catalytic activity 0.454-15.696 * 10
6G PE/molZr.hr, the viscosity-average molecular weight scope 6374-1215463 of resulting polymers, and the catalytic activity of catalyzer increasing and increase with ethene pressure.
Embodiment
Embodiment 1: the preparation (PSCZ1) of loaded by polystyrene dichloride { N-(right-allyl group oxygen base-phenyl)-3-tertiary butyl salicylic alidehyde imine } network zirconium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(to allyloxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV) 0.191g, vinylbenzene 4ml, Diisopropyl azodicarboxylate 0.186g, 30ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 20hr 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 0.610g.ICP-AES：Zr30.7mg/g。GPC：Mn＝16363，PDI(Mw/Mn)＝1.3384。
Embodiment 2: the loaded by polystyrene dichloride N-[is right-(1-alkene butyl oxygen base)-phenyl]-3-tertiary butyl salicylic alidehyde imine } preparation (PSCZ2) of network zirconium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-1-alkene butoxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV) 0.159g, vinylbenzene 6ml, Diisopropyl azodicarboxylate 0.222g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 48hr in 70 ℃ 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 4.379g.ICP-AES：Zr4.29mg/g。GPC：Mn＝14015，PDI(Mw/Mn)＝1.4912。
Embodiment 3: the loaded by polystyrene dichloride N-[is right-(4-alkene amyl group oxygen base)-phenyl]-3-tertiary butyl salicylic alidehyde imine } preparation (PSCZ3) of network zirconium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-the 1-alkene pentyloxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV) 0.109g, vinylbenzene 6ml, Diisopropyl azodicarboxylate 0.215g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 28hr in 65 ℃ 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 4.270g.ICP-AES：Zr3.08mg/g。GPC：Mn＝12994，PDI(Mw/Mn)＝1.4955。
Embodiment 4: the loaded by polystyrene dichloride N-[is right-(1-alkene butyl oxygen base)-phenyl]-5-methyl 3-tertiary butyl salicylic alidehyde imine } preparation (PSCZ4) of network zirconium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-1-alkene butoxy)-phenyl-5-methyl-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV) 0.179g, vinylbenzene 5ml, Diisopropyl azodicarboxylate 0.143g, 40ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 48hr in 60 ℃ oil bath.Solution becomes yellow-green colour by redness.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets orange red gluey dope, 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 yellow-green colour pressed powder 2.633g.ICP-AES：Zr2.02mg/g。GPC：Mn＝9483，PDI＝1.3742。
Embodiment 5: the loaded by polystyrene dichloride N-[is right-(1-allyl group oxygen base)-phenyl]-3-tertiary butyl salicylic alidehyde imine } preparation (PSCT1) of network titanium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(to allyloxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network titanium (IV) 0.368g, vinylbenzene 10ml, Diisopropyl azodicarboxylate 0.500g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 48hr in 75 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets the gluey viscous mixture of light red, 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 pale red brown solid powder 3.893g.ICP-AES：Ti3.43mg/g。GPC：Mn＝12557，PDI(Mw/Mn)＝1.5322。
Embodiment 6: the loaded by polystyrene dichloride N-[is right-(1-alkene butyl oxygen base)-phenyl]-3-tertiary butyl salicylic alidehyde imine } preparation (PSCT2) of network titanium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-1-alkene butoxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network titanium (IV) 0.153g, vinylbenzene 8ml, Diisopropyl azodicarboxylate 0.215g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 20hr in 65 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets the gluey viscous mixture of light red, 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 pale red brown solid powder 4.932g.ICP-AES：Ti1.14mg/g。GPC：Mn＝13745，PDI(Mw/Mn)＝1.6375。
Embodiment 7: the loaded by polystyrene dichloride N-[is right-(1-alkene amyl group oxygen base)-phenyl]-3-tertiary butyl salicylic alidehyde imine } preparation (PSCT3) of network titanium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-the 1-alkene pentyloxy)-phenyl-3-tertiary butyl salicylic alidehyde imine] network titanium (IV) 0.079 g, vinylbenzene 3ml, Diisopropyl azodicarboxylate 0.100g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 36hr in 70 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets the gluey viscous mixture of light red, 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 brown pressed powder 1.426g.ICP-AES：Ti1.86mg/g。GPC：Mn＝18447，PDI(Mw/Mn)＝1.4563。
Embodiment 8: the loaded by polystyrene dichloride N-[is right-(1-alkene amyl group oxygen base)-phenyl]-3-phenyl salicylic alidehyde imine } preparation (PSCT4) of network titanium (IV)
Under the anhydrous and oxygen-free condition, with dichloride [N-(right-1-alkene amyl group oxygen base)-phenyl-3-phenyl salicylic alidehyde imine] network titanium (IV) 0.166g, vinylbenzene 8ml, Diisopropyl azodicarboxylate 0.200g, 50ml toluene adds in the 100ml ampere bottle of being with magnetic stir bar successively, start magnetic agitation, copolymerization 48hr in 60 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets red 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 sorrel pressed powder 4.932g.ICP-AES：Ti2.43mg/g。GPC：Mn＝24772，PDI(Mw/Mn)＝1.3352。
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 40ml toluene then, under agitation add 0.5mlMMAO, 0.811umolPSCZ1 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.476g, and catalytic activity is 1.173 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 50709.Differential scanning calorimetric analysis (DSC): Tm=133.848 ℃, Δ Hm=212.991J/g.
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 40ml toluene then, under agitation add 2.0mlMMAO, 0.811umolPSCZ1 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 3.131g, and catalytic activity is 7.718 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 20800.
Embodiment 11: 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, 1.0mlMMAO, 0.811umolPSCZ1 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 5.796g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 7.147 * 10
6GPE/molZr.hr.Polymkeric substance is the long filament shape.The poly viscosity-average molecular weight of gained is: 621410.Differential scanning calorimetric analysis (DSC): Tm=135.010 ℃, Δ Hm=214.445J/g.
Embodiment 12: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 50 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.811umolPSCZ1 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 10.023g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 12.353 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 772374.
Embodiment 13: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 30 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.811umolPSCZ1 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 12.736g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 15.696 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 726782.Differential scanning calorimetric analysis (DSC): Tm=133.709 ℃, Δ Hm=204.902J/g.
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 40ml toluene then, under agitation add 0.5mlMMAO, 0.617umolPSCZ2 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.572g, and catalytic activity is 1.854 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 10963.
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 40ml toluene then, under agitation add 2.0mlMMAO, 0.617umolPSCZ2 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.919g, and catalytic activity is 2.979 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 6374.
Embodiment 16: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 70 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.617umolPSCZ2 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 3.322g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 5.384 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 56426.Differential scanning calorimetric analysis (DSC): Tm=129.158 ℃, Δ Hm=211.786J/g.
Embodiment 17: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 50 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.617umolPSCZ2 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 5.269g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 8.540 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 109751.Differential scanning calorimetric analysis (DSC): Tm=131.148 ℃, Δ Hm=233.727J/g.
Embodiment 18: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 30 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.617umolPSCZ2 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 acidic ethanol of impouring 200ml 2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 6.598g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 10.694 * 10
6GPE/mol Zr.hr.The poly viscosity-average molecular weight of gained is: 103727.Differential scanning calorimetric analysis (DSC): Tm=128.681, Δ Hm=212.697J/g.
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 40ml toluene then, under agitation add 0.5mlMMAO, 0.833umolPSCZ3 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.189g, and catalytic activity is 0.454 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 92624.
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 40ml toluene then, under agitation add 1.5mlMMAO, 0.833umolPSCZ3 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.471g, and catalytic activity is 1.130 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 32056.
Embodiment 21: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 70 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.833umolPSCZ3 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 2.373g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 2.849 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 57860.Differential scanning calorimetric analysis (DSC): Tm=130.351 ℃, Δ Hm=240.678J/g.
Embodiment 22: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 30 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 0.833umolPSCZ3 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 7.024g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 8.432 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 120547.Differential scanning calorimetric analysis (DSC): Tm=133.336 ℃, Δ Hm=232.455J/g.
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 40ml toluene then, under agitation add 1.0mlMMAO, 1.180umolPSCZ4 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 2.136g, and catalytic activity is 3.620 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 624883.Differential scanning calorimetric analysis (DSC): Tm=125.537 ℃, Δ Hm=226.160J/g.
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 40ml toluene then, under agitation add 2.0mlMMAO, 1.180umol PSCZ4 and 10ml toluene successively.Polyase 13 0min under room temperature stops the input of ethylene gas then, stops stirring, and in the acidic ethanol of impouring 200ml2%, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 2.494g, and catalytic activity is 4.227 * 10
6G PE/molZr.hr.The poly viscosity-average molecular weight of gained is: 360230.Differential scanning calorimetric analysis (DSC): Tm=124.599 ℃, Δ Hm=215.597J/g.
Embodiment 25: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 45 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMAO, 1.180umolPSCZ4 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 6.214g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 5.266 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 221460.Differential scanning calorimetric analysis (DSC): Tm=132.137 ℃, Δ Hm=238.774J/g.
Embodiment 26: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 45 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1.023umolPSCT1 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 3.636g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 3.554 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 1121460.
Embodiment 27: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 45 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1.544umolPSCT1 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 9.777g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 6.332 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 751863.
Embodiment 28: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 45 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMAO, 1.461umolPSCT2 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 8.455g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 5.775 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 1215463.
Embodiment 29: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 45 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1.117umolPSCT3 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 acidic ethanol of impouring 200ml2%, filter, with resulting polymers washing with alcohol, filtration, and, getting 8.358g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 7.483 * 10
6GPE/molZr.hr.The poly viscosity-average molecular weight of gained is: 994775.
Claims (2)
1, the IVB family title complex of the Schiff's base that contains-oxyl of a class loaded by polystyreneization has following structure:
N=1 wherein, 2 or 3, R
1During for the tertiary butyl, R
2Be hydrogen or methyl; R
1During for phenyl, R
2Be hydrogen; M is titanium or zirconium;
Expression polystyrene segment; They help catalysis to form the olefin polymerizating activity center by methylaluminoxane that contains triisobutyl aluminium or methylaluminoxane;
Preparation of catalysts
Under the anhydrous and oxygen-free condition, the title complex 0.1-0.5mmol of IVB family that will contain the Schiff's base of olefin group, Diisopropyl azodicarboxylate 0.1-0.5g, vinylbenzene 3-10ml, 30-50ml toluene join in the reaction flask that a magnetic stir bar is housed successively, stirred 20-48 hour down at 60-80 ℃ then, through desolventize, toluene/normal hexane repeated washing, drying is the high molecular catalyzer under the vacuum, metal content 1.86-30.7mg/g, Mn=9483-24772, Mw/Mn=1.3384-1.6375.
2, the IVB family title complex of the Schiff's base that contains-oxyl of the described class loaded by polystyreneization of claim 1 is used for the purposes of vinyl polymerization, and title complex has following structure:
N=1 wherein, 2 or 3, R
1During for the tertiary butyl, R
2Be hydrogen or methyl; R
1During for phenyl, R
2Be hydrogen; M is titanium or zirconium;
Expression polystyrene segment; They help catalysis to form the olefin polymerizating activity center by methylaluminoxane that contains triisobutyl aluminium or methylaluminoxane;
Preparation of catalysts
Under the anhydrous and oxygen-free condition, the title complex 0.1-0.5mmol of IVB family that will contain the Schiff's base of olefin group, Diisopropyl azodicarboxylate 0.1-0.5g, vinylbenzene 3-10ml, 30-50ml toluene join in the reaction flask that a magnetic stir bar is housed successively, stirred 20-48 hour down at 60-80 ℃ then, through desolventize, toluene/normal hexane repeated washing, drying is the high molecular catalyzer under the vacuum, metal content 1.86-30.7mg/g, Mn=9483-24772, Mw/Mn=1.3384-1.6375;
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, in reaction system, add toluene, methylaluminoxane successively or contain methylaluminoxane, the catalyzer of triisobutyl aluminium, ethylene gas under normal pressure or high pressure is depressed in room temperature to 75 ℃ following reaction 0.5-1hr, the input of termination ethene, with the ethanolic soln termination reaction that contains 2% hydrochloric acid, products therefrom is filtered, use washing with alcohol, vacuum-drying gets the polyethylene pressed powder, catalytic activity 0.454-15.696 * 10
6G PE/molZr.hr, the viscosity-average molecular weight scope 6374-1215463 of resulting polymers.
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