CN103333277B - Two amidino groups methoxyl group bridged binuclear Zr catalyst and its preparation method and application - Google Patents
Two amidino groups methoxyl group bridged binuclear Zr catalyst and its preparation method and application Download PDFInfo
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- CN103333277B CN103333277B CN201310250771.1A CN201310250771A CN103333277B CN 103333277 B CN103333277 B CN 103333277B CN 201310250771 A CN201310250771 A CN 201310250771A CN 103333277 B CN103333277 B CN 103333277B
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- catalyst
- methoxyl group
- amidino groups
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Abstract
The invention provides a kind of two amidino groups methoxyl group bridged binuclear Zr catalyst and preparation method thereof, specifically on the basis of two guanyl binuclear zirconium complex, the amidinate ligand double-core zirconium complex with N-C-N feature two zirconium atoms linked together by the Sauerstoffatom in two methoxyl groups.Preparation method: under nitrogen protection, with SiMe
2[NC (Ph) N (Bu
t) H]
2as starting raw material, utilize n-Butyl Lithium to be two amidine lithium salts by its lithiumation, afterwards two amidine lithium salt solution is slowly added and two amidine ligand two times of molar weight ZrCl are housed
4reaction flask in, next add and ZrCl
4the AlMe of equimolar amount
3, then add and ZrCl
4the H of equimolar amount
2o, can obtain object product through process after reaction terminates.This synthetic method has reaction conditions gentleness, materials are simple and easy to get, cheap, and step is simple, and productive rate is higher, and this catalysts towards ethylene polyreaction has good catalytic activity.
Description
Technical field
The present invention relates to vinyl polymerization transition-metal catalyst, in particular to a kind of two amidino groups methoxyl group bridged binuclear Zr catalysts with N-C-N skeleton and its preparation method and application.
Background technology
The exploitation of olefin polymerization catalysis is a focus of current polymer science area research.The research and development of ethylene rolymerization catalyst experienced by Ziegler-Natta catalyst, metallocene catalyst and non-luxuriant transition metal complex catalyst three developmental stage.In order to realize to the design of polymer molecule with cut out the structure accurately controlling polymkeric substance, be developed the metallocene catalyst with single-activity center, but because metallocene catalyst is to the susceptibility of oxygen and functional group unsuitable catalyzed ethylene and polar monomer copolymerization by force, and it is on the contrary, the oxytropism that late transition metal catalyst is more weak and to the inertia of functional group can make ethene under mild conditions with polar monomer copolymerization, therefore development research goes out the study hotspot that novel non-luxuriant transition-metal catalyst is olefin polymerization catalysis researcher both at home and abroad at present all the time.
Our experimental group is then for research direction with the synthesis of the two amidino groups transition metal complex of bridging and catalysis thereof, by to modify on the two amidinate ligand of bridging substituting group kind and position or change coordination center metal ion, to obtaining higher activity in the application of olefinic polymerization catalysis.It is advantageous that substituting group pattern conversion is various, reaction conditions milder, be easy to preserve, there are two active centers, have by two of methoxyl group bridging zirconium metal coordination centers simultaneously, so this kind of new and effective two amidino groups methoxyl group bridged binuclear Zr catalysts of R and D, there is practical value.
Summary of the invention
The object of the present invention is to provide a kind of two amidino groups methoxyl group bridged binuclear Zr catalyst, this process for synthetic catalyst is simple, and reaction conditions is gentle, and raw material is easy to get, for the catalytic activity that vinyl polymerization has had.
The two amidino groups methoxyl group bridged binuclear Zr catalyst of one provided by the invention, its structural formula is:
Present invention also offers the preparation method of a kind of pair of amidino groups methoxyl group bridged binuclear Zr catalyst, comprise the steps:
Under nitrogen protection and ice-water bath, by two for neutrality amidine ligand SiMe
2[NC (Ph) N (Bu
t) H]
2with n-Butyl Lithium according to mol ratio 1: 1 hybrid reaction, solvent is tetrahydrofuran (THF), its volume is 20-25 times of n-Butyl Lithium volume, stir, naturally room temperature is warmed up to, keep stirring reaction after 2-4 hour, under ice-water bath condition, will obtain lithiated product solution and slowly add couple amidine ligand two times of molar weight ZrCl are housed
4reactor in, be naturally warmed up to room temperature, keep stirring reaction after 5-6 hour, slowly add and ZrCl under acetone bath condition
4the AlMe of equimolar amount
3, stirring reaction 5-6 hour after clear-cutting forestland to room temperature, reaction terminates to continue to add and ZrCl under ice-water bath condition
4the H of equimolar amount
2o, reacts 5-6 hour after clear-cutting forestland to room temperature, condensing crystal, obtains two amidino groups methoxyl group bridged binuclear Zr catalyst.
This pair of amidino groups methoxyl group bridged binuclear Zr catalyst can be applied in vinyl polymerization, and its most high polymerization activity can reach 5.96 × 10
4gmol (Zr)
-1h
-1.
Compared with prior art advantage of the present invention and effect: synthetic catalyst of the present invention is raw materials used simple and easy to get, cheap, preparation method is simple, and productive rate is higher, there are two active centers, have by two of methoxy group bridging zirconium metal coordination centers simultaneously; Catalyzer is used for vinyl polymerization higher catalytic activity.
Accompanying drawing explanation
The Single Crystal X-ray structure iron of the two amidino groups methoxyl group bridged binuclear Zr catalyst of Fig. 1 the present invention
Embodiment
Below be only and describe the present invention and the specific embodiment that provides in detail, these embodiments are not for limiting the scope of the invention.
The preparation and characterization of embodiment 1 catalyzer
(1) preparation of two amidino groups methoxyl group bridged binuclear Zr catalyst
Under the protection and ice-water bath of nitrogen, by the part SiMe prepared
2[NC (Ph) N (Bu
t) H]
2(1.022g, 2.5mmol) is dissolved in tetrahydrofuran (THF) (30cm
3) in, under agitation, add the hexane solution (2.2moldm of butyllithium at leisure
-3, 2.27cm
3, 5mmol), question response mixed solution continues stirring 4 hours after returning to room temperature, after reaction solution being cooled to 0 ° of C, slowly being proceeded to by reaction solution and two amidine ligand qdx ZrCl is housed
4(1.17g, in reaction flask 5mmol), question response mixed solution stirs after 6 hours after returning to room temperature, tetrahydrofuran (THF) is drained, change methylene dichloride and make solvent, after removing lithium chloride precipitation, filtrate draining is changed toluene and do reaction solvent, under acetone bath condition, reaction solution is cooled to-78 ° of C, adds AlMe at leisure
3toluene solution (2moldm
-3, 2.5cm
3, 5mmol), question response mixed solution continues stirring 6 hours after returning to room temperature, add the H of existing system afterwards under ice-water bath condition
2diethyl ether solution (the 0.7682moldm of O
-3, 6.51cm
3, 5mmol), reaction terminates rear direct condensing crystal, can obtain the two amidino groups methoxyl group bridged binuclear Zr catalyst of clear crystal shape.Productive rate is 89%.
Part bond distance
with bond angle (°)
Crystal parameter: chemical formula C
26h
40cl
4n
4o
2siZr
2, oblique system, spacer P2 (1)/c, unit cell parameters a=21.0599 (11) A, b=11.2162 (6) A, c=15.9718 (9) A. α=90 °, β=109.8580 (10) °, γ=90 °,
d
c=1.484g/cm
3, and Z=4, μ (Mo-K α)=0.950mm
-1, R
1=0.0373, wR
2=0.1010.Fig. 1 is shown in by Single Crystal X-ray structure iron.
Embodiment 2
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 30 ° of C, add the toluene solution of catalyzer (3.97mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 3.75ml) and make Al/Zr=1500, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 30 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out, seasoning after filtering.Obtain product 0.0778 gram, polymerization activity: 3.112 × 10
4gmol (Zr)
-1h
-1.
Embodiment 3
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 50 ° of C, add the toluene solution of catalyzer (4.0mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 3.75ml) and make Al/Zr=1500, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 50 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Seasoning after filtering.Obtain product 0.0866 gram, polymerization activity: 3.464 × 10
4gmol (Zr)
-1h
-1.
Embodiment 4
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 70 ° of C, add the toluene solution of catalyzer (3.98mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 3.75ml) and make Al/Zr=1500, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 70 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Seasoning after filtering.Obtain product 0.0025 gram, polymerization activity: 0.1 × 10
4gmol (Zr)
-1h
-1.
Embodiment 5
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 70 ° of C, add the toluene solution of catalyzer (4.0mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 5ml) and make Al/Zr=2000, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 70 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Seasoning after filtering.Obtain product 0.0738 gram, polymerization activity: 2.952 × 10
4gmol (Zr)
-1h
-1.
Embodiment 6
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 50 ° of C, add the toluene solution of catalyzer (4.0mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 5ml) and make Al/Zr=2000, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 50 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Seasoning after filtering.Obtain product 0.1490 gram, polymerization activity: 5.96 × 10
4gmol (Zr)
-1h
-1.
Embodiment 7
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple are housed vacuumized and uses nitrogen replacement 3 times, then replacing 2 times with ethene.After being warmed up to 50 ° of C, add the toluene solution of catalyzer (3.99mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (2mol/L, 6.25ml) and make Al/Zr=2500, the cumulative volume finally adding a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, vigorous stirring 30 minutes under 50 ° of C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Seasoning after filtering.Obtain product 0.0704 gram, polymerization activity: 2.816 × 10
4gmol (Zr)
-1h
-1.
Claims (3)
1. a two amidino groups methoxyl group bridged binuclear Zr catalyst, is characterized in that structural formula is:
2. the preparation method of a kind of pair of amidino groups methoxyl group bridged binuclear Zr catalyst as claimed in claim 1, is characterized in that, comprise the steps:
Under nitrogen protection and ice-water bath, by two for neutrality amidine ligand SiMe
2[NC (Ph) N (Bu
t) H]
2with n-Butyl Lithium according to mol ratio 1: 2 hybrid reaction, solvent is tetrahydrofuran (THF), stirs, naturally is warmed up to room temperature, keeps stirring reaction after 2-4 hour, under ice-water bath condition, will obtain lithiated product solution and slowly add couple amidine ligand two times of molar weight ZrCl are housed
4reactor in, be naturally warmed up to room temperature, keep stirring reaction after 5-6 hour, under acetone bath condition, reaction solution is cooled to-78 DEG C, slowly adds and ZrCl
4the AlMe of equimolar amount
3, stirring reaction 5-6 hour after clear-cutting forestland to room temperature, reaction terminates to continue to add and ZrCl under ice-water bath condition
4the H of equimolar amount
2o, reacts 5-6 hour after clear-cutting forestland to room temperature, condensing crystal, obtains two amidino groups methoxyl group bridged binuclear Zr catalyst.
3. the two application of amidino groups methoxyl group bridged binuclear Zr catalyst in vinyl polymerization as claimed in claim 1.
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| CN105837716B (en) * | 2016-04-07 | 2018-02-02 | 山西大学 | One kind mixing amidino groups amido IV races metallic catalyst and its preparation method and application |
| CN106519088B (en) * | 2016-11-04 | 2019-06-28 | 山西大学 | Oxygen bridge double-core allyl silicon bridge amino Zr catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
| US7799878B2 (en) * | 2005-11-28 | 2010-09-21 | Lg Chem, Ltd. | Dinuclear transition metal compound, catalyst composition comprising the same, method of preparing olefin polymer, and olefin polymer produced using the method |
| CN102603935A (en) * | 2012-02-24 | 2012-07-25 | 山西大学 | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799878B2 (en) * | 2005-11-28 | 2010-09-21 | Lg Chem, Ltd. | Dinuclear transition metal compound, catalyst composition comprising the same, method of preparing olefin polymer, and olefin polymer produced using the method |
| CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
| CN102603935A (en) * | 2012-02-24 | 2012-07-25 | 山西大学 | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof |
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