CN103145754A - Group IVB complex containing N-n-propyl-(5-methyl-3-tertbutyl) salicylaldiminato and preparation and application thereof - Google Patents
Group IVB complex containing N-n-propyl-(5-methyl-3-tertbutyl) salicylaldiminato and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a group IVB complex containing N-n-propyl-(5-methyl-3-tertbutyl) salicylaldiminato and the preparation and application thereof. The invention aims to obtain a novel polyolefin catalyst by tailing molecules of a Schiff base group IVB transitional metal complex. The structure of the group IVB complex containing N-n-propyl-(5-methyl-3-tertbutyl) salicylaldiminato is described in the description, wherein M is titanium or zirconium. The complex is a highly active catalyst polymerized by ethylene, wherein the catalytic polymerization activity of the titanium complex at normal temperature and normal pressure is 0.280-0.343*10 to the power of 6 g PE/mol.hr.atm, and the catalytic polymerization activity of the zirconium complex at normal temperature and normal pressure is 1.605-5.571*10 to the power of 6 g PE/mol.hr.atm. The viscosity average molecular weight of the obtained polymer is 2933-218365.
Description
Technical field
The present invention relates to a kind of IVB family's title complex and preparation and application.
Background technology
The application potential of macromolecular material is the diversity of its structure and the multifarious performance of following.The rapid growth of polyolefin industry comes from the widespread use of polyolefine material in the productive life field, and the core of polyolefin industry and power are high performance olefin polymerization catalysis.Theoretical investigation and practical application prove, the key factor of the technological change that polyolefin field is with rapid changepl. never-ending changes and improvements is the application of transition-metal catalyst, comprising Ziegler-Natta catalyst, the SHOP catalyzer, metallocene catalyst, nineteen ninety-five Brookhart study group finds that nickelous and palladium complex that neutral diimine is part are the catalyzer of the high branch high-molecular weight polymer of preparation, thereafter iron and the cobalt complex energy catalyzed polymerization of finding pyridine diimine obtain high-density linear polyethylene, within 1998, find the nickel complex as catalyst agent of high-order resistance type salicylic alidehyde imine, the Schiff's base of developing in 1999 is all joined type IVB group 4 transition metal olefin polymerization catalysis, the disclosed content of Chinese patent 200310122945.2 is mainly to contain catalyzer and the macromolecule loading thereof of allyl group and isobutyl-on the nitrogen of Schiff's base.
Summary of the invention
The objective of the invention is to obtain the new type polyolefin catalyzer by the molecule cutting to Schiff's base IVB group 4 transition metal complexes, IVB family title complex and preparation and the application of a class containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine are provided.
IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present invention is characterized in that the structure of such title complex is as follows:
IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present invention helps catalysis to form olefin polymerization catalysis by methylaluminoxane or methylaluminoxane containing triisobutyl aluminium;
The preparation method of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present invention carries out as follows:
One, by constant pressure funnel to the diethyl ether solution that splashes into monobromethane in the reaction flask that fills magnesium, stir half an hour, obtain ethylmagnesium bromide solution;
Two, ethylmagnesium bromide solution 4-methyl-2-TBP obtained with step 1 mixes, and then mix with paraformaldehyde and triethylamine, take toluene solution after mixing as solvent, in temperature, be to stir 4～8 hours under 95～110 ℃ of conditions, under the ice-water bath cooling conditions, the hydrochloric acid soln that is 1N by concentration neutralization, collected organic layer, and use the extracted with diethyl ether water layer, merge organic layer, drying, obtain crude product after evaporating solvent, use SiO
2post/sherwood oil or SiO
2post/hexane wash-out obtains 5-methyl-3-tertiary butyl salicylic aldehyde;
Three, take dehydrated alcohol as solvent, will wait the Tri N-Propyl Amine of amount of substance to mix with the 5-methyl obtained in step 2-3-tertiary butyl salicylic aldehyde,
or
under the molecular sieve catalytic condition, stirring at room 15～20 hours, filter, and use the ethyl acetate washing precipitation, the merging organic phase, and evaporating solvent obtains crude product, the crude product SiO that flows through
2post, the hexane/ethyl acetate wash-out of the petrol ether/ethyl acetate that is 15:1 by volume ratio or 15:1 obtains N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine;
Four, by the N-n-propyl that obtains in step 3-(5-methyl-3-tertiary butyl) salicylic alidehyde imine and n-Butyl Lithium or KH solution according to amount of substance than mixing for 1:1.00～1.05, in temperature, be under-72 ℃～25 ℃ conditions, to react within 1.5～2.5 hours, to generate salts solution, then add titanium tetrachloride or zirconium tetrachloride in salts solution under-72 ℃, the titanium tetrachloride wherein added or zirconium tetrachloride and salts solution the ratio of amount of substance be 1:2, under room temperature, stir 15～18 hours, through desalination, washing, vacuum-drying, obtain the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine,
Wherein the ratio of the amount of substance of 4-methyl-2-TBP, ethylmagnesium bromide, paraformaldehyde and the triethylamine described in step 2 is 1:(1.0～1.1): 2.5:1.5.
IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present invention carries out according to following steps as vinyl polymerization:
Under the anhydrous and oxygen-free condition, to adding successively toluene or alkane, methylaluminoxane or modified methylaluminoxane in the ethylene polymerization system and containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine, pass into ethylene gas under normal pressure, in temperature, be to react 0.25～1 hour under 25～80 ℃ of conditions, stop passing into ethene, by the ethanolic soln termination reaction that is 2% hydrochloric acid containing the quality percentage composition, filter collecting precipitation, use washing with alcohol, vacuum-drying obtains the polyethylene pressed powder, completes ethylene polymerization.Wherein said alkane is pentane, hexane or heptane.
The present invention comprises following beneficial effect:
N-n-propyl-(5-methyl-3-tertiary butyl) the IVB family title complex of salicylic alidehyde imine that contains of the present invention structurally adopts ［ the N of organic ligand, O-］ the bidentate chelating, these atoms form Octahedral Complexes with IVB group 4 transition metal Atomic coordinate together with two chlorine atoms, on the imines nitrogen of n-propyl in Schiff's base, two chlorine atoms are in cis position.Such title complex, under the methylaluminoxane effect, can form the catalytic active center containing growing chain and coordination room, forms highly active ethylene rolymerization catalyst.Title complex of the present invention helps catalysis to form the ethylene polymerization activity center by methylaluminoxane (MMAO) or the methylaluminoxane (MAO) containing triisobutyl aluminium, be the high activated catalyst of vinyl polymerization, under normal temperature and pressure, titanium complex catalyzed polymerization activity is 0.280～0.343 * 10
6g PE/molhratm, zirconium complex catalyzed polymerization activity is 1.605～5.571 * 10
6gPE/molhratm, the viscosity-average molecular weight of the polymkeric substance of gained is: 2933～218365.
The accompanying drawing explanation
The monocrystalline molecular structure of the dichloride N-n-propyl that Fig. 1 is preparation in embodiment 2-(5-methyl-3-tertiary butyl) salicylic alidehyde imine network Zr catalyst, in figure, except the tracer atom, all the other unmarked atoms are carbon atom, and hydrogen atom omits.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the structure of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of present embodiment is as follows:
Embodiment two: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of present embodiment helps catalysis to form olefin polymerization catalysis by methylaluminoxane or methylaluminoxane containing triisobutyl aluminium;
Embodiment three: the preparation method of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of present embodiment carries out as follows:
One, by constant pressure funnel to the diethyl ether solution that splashes into monobromethane in the reaction flask that fills magnesium, stir half an hour, obtain ethylmagnesium bromide solution;
Two, ethylmagnesium bromide solution 4-methyl-2-TBP obtained with step 1 mixes, and then mix with paraformaldehyde and triethylamine, take toluene solution after mixing as solvent, in temperature, be to stir 4～8 hours under 95～110 ℃ of conditions, under the ice-water bath cooling conditions, the hydrochloric acid soln that is 1N by concentration neutralization, collected organic layer, and use the extracted with diethyl ether water layer, merge organic layer, drying, obtain crude product after evaporating solvent, use SiO
2post/sherwood oil or SiO
2post/hexane wash-out obtains 5-methyl-3-tertiary butyl salicylic aldehyde;
Three, take dehydrated alcohol as solvent, will wait the Tri N-Propyl Amine of amount of substance to mix with the 5-methyl obtained in step 2-3-tertiary butyl salicylic aldehyde,
or
under the molecular sieve catalytic condition, stirring at room 15～20 hours, filter, and use the ethyl acetate washing precipitation, the merging organic phase, and evaporating solvent obtains crude product, the crude product SiO that flows through
2post, the hexane/ethyl acetate wash-out of the petrol ether/ethyl acetate that is 15:1 by volume ratio or 15:1 obtains N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine;
Four, by the N-n-propyl that obtains in step 3-(5-methyl-3-tertiary butyl) salicylic alidehyde imine and n-Butyl Lithium or KH solution according to amount of substance than mixing for 1:1.00～1.05, in temperature, be under-72 ℃～25 ℃ conditions, to react within 1.5～2.5 hours, to generate salts solution, then add titanium tetrachloride or zirconium tetrachloride in salts solution under-72 ℃, the titanium tetrachloride wherein added or zirconium tetrachloride and salts solution the ratio of amount of substance be 1:2, under room temperature, stir 15～18 hours, through desalination, washing, vacuum-drying, obtain the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine,
Wherein the ratio of the amount of substance of 4-methyl-2-TBP, ethylmagnesium bromide, paraformaldehyde and the triethylamine described in step 2 is 1:(1.0～1.1): 2.5:1.5.
Embodiment four: the application of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of present embodiment is characterized in that being used as vinyl polymerization containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine.
Embodiment five: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of present embodiment carries out according to following steps as vinyl polymerization:
Under the anhydrous and oxygen-free condition, to adding successively toluene or alkane, methylaluminoxane or modified methylaluminoxane in the ethylene polymerization system and containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine, pass into ethylene gas under normal pressure, in temperature, be to react 0.25～1 hour under 25～80 ℃ of conditions, stop passing into ethene, by the ethanolic soln termination reaction that is 2% hydrochloric acid containing the quality percentage composition, filter collecting precipitation, use washing with alcohol, vacuum-drying obtains the polyethylene pressed powder, completes ethylene polymerization.
Embodiment six: present embodiment is different from embodiment five: to the alkane added in the ethylene polymerization system, be pentane, hexane or heptane.Other is identical with embodiment five.
Verify beneficial effect of the present invention by following examples:
Embodiment 1: the dichloride of the present embodiment { N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine } network titanium (IV) preparation process (T1) is as follows:
One, be added with MAGNESIUM METAL and the magnetic stir bar of 1.848g in the there-necked flask of the preparation of ethylmagnesium bromide solution: 100ml, assembling constant pressure funnel, reflux condensing tube and protection airbag, through standard Schlenk system charge, exhaust three times.Then add the 50ml anhydrous diethyl ether in constant pressure funnel, and add 10ml anhydrous diethyl ether wherein by constant pressure funnel in there-necked flask.Add the anhydrous monobromethane of 7.630g again in constant pressure funnel, shake constant pressure funnel the diethyl ether solution of monobromethane is mixed evenly.Start magnetic agitation, open reflux condensation mode water, the rate of addition of controlling the diethyl ether solution of monobromethane makes reaction maintain gentle reflux, maintains after dripping and stirs half an hour, obtains black transparent liquid, i.e. ethylmagnesium bromide solution.
Two, the preparation of 5-methyl-3-tertiary butyl salicylic aldehyde: to the 4-methyl-2-TBP and the magnetic stir bar that add 9.840g in the 250ml there-necked flask, assembling constant pressure funnel, reflux condensing tube and protection airbag, through standard Schlenk system charge, exhaust three times; Add the 40ml anhydrous tetrahydro furan in there-necked flask, through the Schlenk system, shift prepared ethylmagnesium bromide solution in constant pressure funnel, and wash with the 20ml anhydrous diethyl ether, the supernatant liquor after washing is transferred in constant pressure funnel; Open reflux condensation mode water, at room temperature by constant pressure funnel, drip ethylmagnesium bromide solution to there-necked flask, 45min adds, and maintains reaction 2hr, the gas of wanting intermittently discharged to produce in this reinforced process; Then add the 100ml dry toluene in there-necked flask, extract the low-boiling point materials such as tetrahydrofuran (THF), ether under vacuum, to volume of mixture 100ml in there-necked flask; System re-fills rare gas element, in there-necked flask, adds paraformaldehyde, 9.090g triethylamine and the 50ml toluene that 4.700g quality percentage composition is 95%, then is heated to 100 ± 5 ℃ of lower stirring reaction 4hr; After reaction mixture is cooled to room temperature, under the ice-water bath cooling conditions, the hydrochloric acid neutralization that to pour 300ml concentration into be 1N is also fully stirred; Demixing, collect the upper strata organic layer, and till colourless to the organic layer after phase-splitting with the extracted with diethyl ether water; Merge organic layer, eliminate solvent with anhydrous sodium sulfate drying, filtration, evaporation and obtain crude product, use SiO
2post/sherwood oil wash-out, the solution of the orange band of collection the first layer, it is 5-methyl-3-tertiary butyl salicylic aldehyde 9.907g that evaporating solvent obtains orange red oil, productive rate 86%.
Wherein the results of FT-IR of 5-methyl-3-tertiary butyl salicylic aldehyde is as follows: FT-IR (KBr, cm
-1): 3504,3405,2999,2957,2914,2868,2739,1649,1618,1597,1467,1440,1392,1362,1322,1265,1229,1207,1160,1027,970,929,863,795,769,747,710,575,541,518,476.
1HNMR(CDCl
3)：δ1.411（s，9H，t-Bu），2.324（s，3H，CH
3），7.174-7.179（d，1H，aromatic-H），7.326-7.333（d，1H，aromatic-H），9.827（s，1H，CHO），11.601（s，1H，OH）；
Three, the preparation of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine: with the 100ml there-necked flask, take 5-methyl-3-tertiary butyl salicylic aldehyde 3.840g, add magnetic stir bar, assembling constant pressure funnel and protection airbag, open magnetic agitation, with the vacuum argon system, fills exhaust three times; Add dry
molecular sieve 3.077g, 30ml dehydrated alcohol, at room temperature by constant pressure funnel to the mixing solutions that adds 20ml dehydrated alcohol and 1.220g Tri N-Propyl Amine in there-necked flask, 30min adds, then stirring reaction 15hr at room temperature, filter, by ethyl acetate, wash filter residue, collect filtrate and washing lotion, evaporation obtains crude product except desolventizing, uses SiO
2the sherwood oil (or hexane) that post, volume ratio are 15:1/eluent ethyl acetate, collect the solution of the orange colour band of the first layer, evaporation obtains 4.101g yellow oily semisolid except desolventizing, is N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine, productive rate 88%.
Wherein the results of FT-IR of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is as follows: FT-IR (KBr, cm
-1): 3530-3402,3080,2997,2960,2918,2869,2737,2614,1634,1598,1471,1443,1391,1361,1322,1268,1230,1178,1075,1026,981,932,863,798,772,765,753,710,692,600,584,570,555,519,469.
1HNMR(CDCl
3)：0.962～0.999(t，3H，J=7.4Hz，CH
3)，1.430（s，9H，-C(CH
3)
3），1.679～1.769(m，2H，J=7.4Hz，CH
2)，2.279（s，3H，ring-CH
3），3.515～3.551（t，2H，J=6.6Hz，-CH
2-），6.889～6.894（d，1H，aromatic-H），7.110～7.115（d，1H，aromatic-H），8.278（s，1H，CH=N），13.913（s，1H，OH）。
Four, dichloride { N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine } network titanium (IV) preparation (T1): under anhydrous and oxygen-free and high-purity argon gas protection, accurately take N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine 0.350g with the ampere bottle of a 50ml, add the 20ml anhydrous diethyl ether to dissolve with magnetic agitation, be cooled to-72 ℃ with ethanol/the dry ice bath, obtain solution, then measure the hexane solution 0.95ml of the n-Butyl Lithium that concentration is 1.6M with syringe, slowly be injected in above-mentioned solution, naturally be warming up to reaction 2.5hr under room temperature and become lithium salts, this process produces gas, then this lithium salt solution is cooled to-72 ℃ with ethanol/the dry ice bath, accurately take titanium compound (TiCl
44THF) powder 0.359g, under agitation slowly be added to taken titanium compound powder in the lithium salt solution of above-mentioned part by the glass three-way pipe, obtains red suspension liquid, add the rear room temperature that naturally is warming up to, stirring reaction 15hr then is concentrated into dryly under vacuum, add the 20ml methylene dichloride and stir 15min, then vacuum concentration is to dry, with 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrated this supernatant liquor, precipitate to obtain 0.254g scarlet prism-shaped crystal with normal hexane, be dichloride { N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine } network titanium (IV) (T1), productive rate is 58%.
Wherein dichloride { N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine } network titanium (IV) the results of FT-IR (T1) is as follows: FT-IR (KBr, cm
-1): 3024,2957,2909,2869,1612,1559,1474,1455,1437,1412,1393,1380,1361,1330,1288,1268,1239,1212,1175,1008,974,934,892,852,773,740,717,610,585,520.
1HNMR(CDCl
3):0.970～1.006(t，3H，J=7.4Hz，CH
3)，1.587（s，9H，-C(CH
3)
3），1.688～1.776(m，2H，J=7.4Hz，CH
2)，2.341（s，3H，ring-CH
3），3.525～3.560（t，2H，J=6.6Hz，-CH
2-），7.019～7.023（d，2H，aromatic-H），7.104～7.122（d，2H，aromatic-H），8.045（s，2H，CH=N）。
Embodiment 2: the present embodiment dichloride { N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine } network zirconium (IV) preparation process (Z1), above-mentioned preparation process is from different in embodiment 1: step 4 is under anhydrous and oxygen-free and high-purity argon gas protection, accurately take N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine 0.350g with the reaction flask of a 50ml, add the 20ml anhydrous tetrahydro furan to dissolve with magnetic agitation, be cooled to-72 ℃ with ethanol/the dry ice bath, obtain solution, then measure the hexane solution 0.95ml of the n-Butyl Lithium of 1.6M with syringe, slowly be injected in the solution of above-mentioned imines, add the rear reaction 2.5hr that naturally is warming up under room temperature and become lithium salts, this process produces gas, then this lithium salt solution is cooled to-72 ℃ with ethanol/the dry ice bath, accurately take 98% zirconium tetrachloride powder 0.179g, under agitation by the glass three-way pipe, taken white zirconium tetrachloride powder slowly is added in the lithium salt solution of above-mentioned part, obtain yellow suspension liquid, add the rear room temperature that naturally is warming up to, stirring reaction 15hr, then be concentrated into dryly under vacuum, add the 20ml methylene dichloride and stir 15min, then vacuum concentration is to dry.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrated this supernatant liquor, precipitate to obtain the yellow square piece shape of 0.338g crystal with normal hexane, be dichloride N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine network zirconium, productive rate 71.9%.
Wherein the results of FT-IR of dichloride N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine network zirconium is as follows: FT-IR (KBr, cm
-1): 3011,2961,2910,2870,1611,1561,1473,1456,1440,1416,1391,1379,1361,1331,1291,1272,1240,1211,1175,1150,1111,1044,1032,1005,982,934,896,887,862,846,804,777,742,716,612,557,513.1HNMR (CDCl
3): 0.968～1.006(t, 6H, 2CH
3), 1.552(s, 18H, 2C (CH
3)
3), 1.773～1.827(m, 4H, 2CH
2), 2.318(s, 6H, 2CH
3), 3.630～3.664(t, 4H, CH
2), 5.298(s, 2H, CH
2cl
2), 6.995(s, 2H, aromatic-H), 7.364(s, 2H, aromatic-H), 8.079(s, 2H, CH=N), as shown in Figure 1, the relevant molecular linkage data of selection are the monocrystalline molecular structure of dichloride N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine network Zr catalyst: bond distance: Zr-O=
zr-N=
zr-Cl=
n=C=
n-C=
c-C=1.5263～
c=C=1.3917～
bond angle (°): O-Zr-O=169.41, N-Zr-N=75.031, Cl-Zr-Cl=103.04, O-Zr-N=77.77, O-Zr-N '=93.756, O-Zr-Cl=91.207～95.378, N-Zr-Cl=162.18, N-Zr-Cl=92.004, C-O-Zr=145.94～146.8, O-Zr – Cl=91.207～95.378.From single crystal structure figure and bond parameter data, catalyzer of the present invention structurally adopts ［ N, the O of Schiff's base
-bidentate chelating and ［ Cl
-and IVB family element coordination formation Octahedral Complexes, wherein two chlorine atoms are in cis position.
Embodiment 3: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as vinyl polymerization, concrete operations are as follows: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 1.2umolT1 and 10ml toluene, polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter, by the resulting polymers washing with alcohol, filter, and in 40 ℃ of lower vacuum-dryings 24 hours, obtain vinyl polymerization product 0.103g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.343 * 10
6g PE/molTihratm.The poly viscosity-average molecular weight of gained is: 111403.
Embodiment 4: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as vinyl polymerization, concrete operations are as follows: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.5mlMMAO (2.5M), 1.2umolT1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter, the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filtration, and in 40 ℃ of lower vacuum-dryings 24 hours, obtain vinyl polymerization product 0.093g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.310 * 10
6gPE/molTihratm.The poly viscosity-average molecular weight of gained is: 91850.
Embodiment 5: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as vinyl polymerization, concrete operations are as follows: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 0.5mlMMAO (2.5M), 1.2umolT1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of lower vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.084g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.280 * 10
6gPE/molTihratm.The poly viscosity-average molecular weight of gained is: 127318.
Embodiment 6: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as vinyl polymerization, concrete operations are as follows: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), (1.2umolT1 catalyst solution was deposited after two weeks) and 10ml toluene, polyase 13 0min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter, the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and in 40 ℃ of lower vacuum-dryings 24 hours, obtain vinyl polymerization product 0.040g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.067 * 10
6g PE/molTihratm.The poly viscosity-average molecular weight of gained is: 145416.
Embodiment 7: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 1.2umolT1 (catalyst solution was deposited after two weeks) and 10ml toluene.Polymerization 60min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of lower vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.054g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.045 * 10
6g PE/molTihratm.The poly viscosity-average molecular weight of gained is: 218365.
Embodiment 8: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 2.0mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.712g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 4.885 * 10
6gPE/molZrhratm.The poly viscosity-average molecular weight of gained is: 2083.
Embodiment 9: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure.Then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.812g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 5.571 * 10
6gPE/molZrhratm.The poly viscosity-average molecular weight of gained is: 3094.
Embodiment 10: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 3.0mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.677g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 4.645 * 10
6gPE/molZrhratm.The poly viscosity-average molecular weight of gained is: 2675.
Embodiment 11: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 0.5mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene.Polymerization 15min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.234g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 1.605 * 10
6gPE/molZrhratm.The poly viscosity-average molecular weight of gained is: 4205.
Embodiment 12: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, 50 ℃ of heating in water bath for reaction bottles, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene.In 50 ℃ of lower polymerization 15min, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtain a small amount of polymkeric substance.
Embodiment 13: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, 50 ℃ of heating in water bath for reaction bottles, pass in advance argon gas, then pass into the normal pressure ethylene gas, add successively again 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 0.58umolZ1 and 10ml toluene, in 50 ℃ of lower polymerization 15min, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter, the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and in 40 ℃ of vacuum-dryings 24 hours, obtain a small amount of polymkeric substance.
Embodiment 14: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 0.58umolZ1 (catalyst solution was deposited after two weeks) and 10ml toluene.Polyase 13 0min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.250g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.862 * 10
6g PE/molZrhratm.The poly viscosity-average molecular weight of gained is: 3280.
Embodiment 15: the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine of the present embodiment is as follows as the vinyl polymerization concrete operations: 200ml glass reaction bottle is toasted under vacuum in advance, pass into ethylene gas, ethene air pressure is normal pressure, then add 40ml toluene, under agitation add successively 1.0mlMMAO (2.5M), 0.58umolZ1 (catalyst solution was deposited after two weeks) and 10ml toluene.Polymerization 60min under room temperature, then stop the input of ethylene gas, stop stirring, in the acidic ethanol that impouring 200ml volumn concentration is 2%, filter the ethanolic soln that is 70% with volumn concentration by resulting polymers washing, filter, and, in 40 ℃ of vacuum-dryings 24 hours, obtaining vinyl polymerization product 0.214g, the catalytic activity that contains the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine is: 0.369 * 10
6g PE/molZrhratm.The poly viscosity-average molecular weight of gained is: 2933.
Claims (6)
1. containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine, it is characterized in that the structure of such title complex is as follows:
2. the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine according to claim 1, is characterized in that such title complex helps catalysis to form olefin polymerization catalysis by methylaluminoxane or methylaluminoxane containing triisobutyl aluminium.
3. the method for preparing the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine as claimed in claim 1 is characterized in that described method carries out as follows:
One, by constant pressure funnel to the diethyl ether solution that splashes into monobromethane in the reaction flask that fills magnesium, stir half an hour, obtain ethylmagnesium bromide solution;
Two, ethylmagnesium bromide solution 4-methyl-2-TBP obtained with step 1 mixes, and then mix with paraformaldehyde and triethylamine, take toluene solution after mixing as solvent, in temperature, be to stir 4～8 hours under 95～110 ℃ of conditions, under the ice-water bath cooling conditions, the hydrochloric acid soln that is 1N by concentration neutralization, collected organic layer, and use the extracted with diethyl ether water layer, merge organic layer, drying, obtain crude product after evaporating solvent, use SiO
2post/sherwood oil or SiO
2post/hexane wash-out obtains 5-methyl-3-tertiary butyl salicylic aldehyde;
Three, take dehydrated alcohol as solvent, will wait the Tri N-Propyl Amine of amount of substance to mix with the 5-methyl obtained in step 2-3-tertiary butyl salicylic aldehyde,
or
under the molecular sieve catalytic condition, stirring at room 15～20 hours, filter, and use the ethyl acetate washing precipitation, the merging organic phase, and evaporating solvent obtains crude product, the crude product SiO that flows through
2post, the hexane/ethyl acetate wash-out of the petrol ether/ethyl acetate that is 15:1 by volume ratio or 15:1 obtains N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine;
Four, by the N-n-propyl that obtains in step 3-(5-methyl-3-tertiary butyl) salicylic alidehyde imine and n-Butyl Lithium or KH solution according to amount of substance than mixing for 1:1.00～1.05, in temperature, be under-72 ℃～25 ℃ conditions, to react within 1.5～2.5 hours, to generate salts solution, then add titanium tetrachloride or zirconium tetrachloride in salts solution under-72 ℃, the titanium tetrachloride wherein added or zirconium tetrachloride and salts solution the ratio of amount of substance be 1:2, under room temperature, stir 15～18 hours, through desalination, washing, vacuum-drying, obtain the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine,
Wherein the ratio of the amount of substance of 4-methyl-2-TBP, ethylmagnesium bromide, paraformaldehyde and the triethylamine described in step 2 is 1:(1.0～1.1): 2.5:1.5.
4. the application of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine as claimed in claim 1, is characterized in that being used as vinyl polymerization containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine.
5. the application of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine according to claim 4 is characterized in that according to following steps, carrying out as vinyl polymerization containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine:
Under the anhydrous and oxygen-free condition, add successively toluene or alkane in the ethylene polymerization system, methylaluminoxane or be added with the methylaluminoxane of triisobutyl aluminium and containing the IVB family title complex of N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine, pass into ethylene gas under normal pressure, in temperature, be to react 0.25～1 hour under 25～80 ℃ of conditions, stop passing into ethene, by the ethanolic soln termination reaction that is 2% hydrochloric acid containing mass percent, filter collecting precipitation, the ethanolic soln that is 70% with volumn concentration washing, vacuum-drying obtains the polyethylene pressed powder, complete ethylene polymerization.
6. the application of the IVB family title complex containing N-n-propyl-(5-methyl-3-tertiary butyl) salicylic alidehyde imine according to claim 5, is characterized in that the alkane added in the ethylene polymerization system is pentane, normal hexane or heptane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030060584A1 (en) * | 2001-09-18 | 2003-03-27 | Coates Geoffrey W. | Bis(salicylaldiminato)titanium complex catalysts, highly syndiotactic polypropylene by a chain-end control mechanism, block copolymers containing this |
| CN1554677A (en) * | 2003-12-29 | 2004-12-15 | 复旦大学 | IVB family schiff base olefin polymerization catalyst and its preparing method |
| CN1644593A (en) * | 2004-12-16 | 2005-07-27 | 复旦大学 | Olefin hydrocarbon polymerization catalyst of IVB group with Xifo alkali coordination and its preparation and use |
| JP2006342106A (en) * | 2005-06-09 | 2006-12-21 | Mitsui Chemicals Inc | Transition metal compound |
-
2013
- 2013-03-29 CN CN2013101082998A patent/CN103145754A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030060584A1 (en) * | 2001-09-18 | 2003-03-27 | Coates Geoffrey W. | Bis(salicylaldiminato)titanium complex catalysts, highly syndiotactic polypropylene by a chain-end control mechanism, block copolymers containing this |
| CN1554677A (en) * | 2003-12-29 | 2004-12-15 | 复旦大学 | IVB family schiff base olefin polymerization catalyst and its preparing method |
| CN1644593A (en) * | 2004-12-16 | 2005-07-27 | 复旦大学 | Olefin hydrocarbon polymerization catalyst of IVB group with Xifo alkali coordination and its preparation and use |
| JP2006342106A (en) * | 2005-06-09 | 2006-12-21 | Mitsui Chemicals Inc | Transition metal compound |
Non-Patent Citations (3)
| Title |
|---|
| KAORI MATOISHI等: "Value-added olefin-based materials originating from FI catalysis: Production of vinyl- and Al-terminated PEs, end-functionalized PEs, and PE/polyethylene glycol hybrid materials", 《CATALYSIS TODAY》 * |
| M. YU. MALINSKAYA等: "Catalytic Activity of Systems Based on Titanium Bis(phenoxy Imine) Complexes: Effect of the Ligand Structure", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》 * |
| SHIGEKAZU MATSUI等: "A Family of Zirconium Complexes Having Two Phenoxy-Imine Chelate Ligands for Olefin Polymerization", 《J. AM. CHEM. SOC.》 * |
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