CN105482007B - Bis diimines silicon bridge Zr catalyst and preparation method thereof - Google Patents
Bis diimines silicon bridge Zr catalyst and preparation method thereof Download PDFInfo
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- CN105482007B CN105482007B CN201610011656.2A CN201610011656A CN105482007B CN 105482007 B CN105482007 B CN 105482007B CN 201610011656 A CN201610011656 A CN 201610011656A CN 105482007 B CN105482007 B CN 105482007B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a kind of bis diimines silicon bridge Zr catalyst, is related to vinyl polymerization IVB transition-metal catalysts, specifically a kind of imines silicon bridge part zirconium complex catalyst with N C C C N Si N C C C N skeletons.Its preparation method：Under the protection of nitrogen; with lithium diisopropyl amido (LDA) by kitimine compound dehydrogenation, part lithium salts is obtained, the tert-butyl group nitrile for adding equivalent mole obtains diimine lithium salt compound; appropriate silane compound is added, bis diimines silicon bridge lithium salt compound is obtained through secondary dehydrogenation；Finally react to obtain bis diimines silicon bridge Zr catalyst with transition metal halide.The preparation method is simple, and materials are easy to get, are cheap, and yield is higher；Catalyst shows high catalytic activity for vinyl polymerization, and has obtained the polyethylene of super high molecular weight.
Description
Technical field
The present invention relates to vinyl polymerization IVB transition-metal catalysts, have N-C-C-C-N-Si- in particular to one kind
The imines silicon bridge zirconium complex catalyst of N-C-C-C-N skeletons, more specifically a kind of bis diimines silicon bridge Zr catalyst and
Its preparation method and application.
Background technology
Polyvinyl resin is the kind that yield is maximum in general synthetic resin, because of the features such as its price is low, performance is good, at me
The application of state is quite extensive, and such as film, injection-molded item, electric wire, hollow product all occupy larger in its consumption structure
Ratio.Industrialized olefin polymerization catalysis has Ziegler-Natta types catalyst, Phillips types catalyst and metallocene
The catalyst such as type, these catalyst can reach the control to catalytic activity and polymer performance by adjusting the structure of part
System.The report of wherein bis diimines silicon bridge metal compound species catalyst is very rare, and preparing raw material complex process be present,
Low yield, catalytic activity is low, the low shortcoming of polymer resin molecule amount, limits such bis diimines silicon bridge metallic compound and urges
The application of agent.
The content of the invention
It is an object of the invention to provide a kind of bis diimines silicon bridge Zr catalyst and preparation method thereof, and the catalyst
Application in vinyl polymerization.
A kind of bis diimines silicon bridge Zr catalyst provided by the invention, have following structural formula：
Wherein：
R1、R2Hydrogen is each independently selected from, in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxy
One kind；R3、R4One be each independently selected from alkyl, aryl, alkaryl, aralkyl and the alkoxy of 1-10 carbon atom
Kind；
R1、R2It preferably is selected from hydrogen independently of one another, methyl, ethyl, one kind in isopropyl and methoxyl group.
X is halogen, preferably chlorine or bromine.
Present invention also offers a kind of preparation method of bis diimines silicon bridge Zr catalyst, comprise the following steps：
(1) preparation of lithium salts：Under the protection of nitrogen, under acetone bath, by kitimine compound and diisopropyl amido
Lithium reaction with same mole, solvent are tetrahydrofuran, after reacting 4-6 hours, after solution is warming up to room temperature naturally, are kept stirring for anti-
8-10 hours are answered, obtain lithium salts L1 tetrahydrofuran solution；Under the protection of nitrogen, under ice-water bath, by the equimolar tert-butyl group
Nitrile is slowly added thereto, and after solution is warming up to room temperature naturally, is kept stirring for reacting 10-12 hours, is obtained by extraction with toluene
Imines lithium salt compound L2；Then under the protection of nitrogen, under ice-water bath, appropriate silane compound is added, keeps reaction 3-4
Hour, with equimolar lithium diisopropyl amido lithiumation again, it is kept stirring for reacting 8-10 hours, is obtained with toluene extractive crystallization
Colourless diimine silicon bridge lithium ligand compound L3；
(2) preparation of catalyst：Under the protection of nitrogen, under acetone bath, transition metal halide ZrX4It is added to
In bis diimines silicon bridge lithium L3 tetrahydrofuran solution, ZrX4Mol ratio with L3 is 1-2 ﹕ 1, when solution is warming up to room temperature naturally
After, it is kept stirring for reacting 20-24 hours, vacuum is drained, and is added dichloromethane, filtering, filtrate is concentrated to give into bis diimines
Silicon bridge Zr catalyst C.Specific synthetic route is as follows：
Application of the bis diimines silicon bridge Zr catalyst in vinyl polymerization.Polymerization catalyst is lived in the experiment of vinyl polymerization
Property reaches as high as：1.05×106g·mol(Zr)-1·h-1, molecular weight of polyethylene is reachable：3.26×106g·mol-1。
Advantages of the present invention and effect compared with prior art：Synthetic catalyst is raw materials used to be easy to get, is cheap, prepares
Method is simple, and yield is higher；Catalyst, which is used for vinyl polymerization, high catalytic activity, can obtain having the poly- of super high molecular weight
Ethene.
Brief description of the drawings
Fig. 1 is catalyst C crystal structure figure；
In Fig. 1 crystal structure, coordination structure is the octahedral structure of distortion.
Embodiment
It is only the embodiment for illustrating and providing below, these embodiments are not intended to limit protection scope of the present invention.
Embodiment 1
(1) preparation of lithium salts
Under the protection of nitrogen, under acetone bath, lithium diisopropyl amido (0.21g, 2mmol) is added to N- methyl -2,
In the tetrahydrofuran solution of 6- diethylbenzenes imines (0.42g, 2mmol), after reacting 3 hours, when solution is warming up to room temperature naturally
Afterwards, reaction 8 hours is kept stirring for, vacuum is drained, and n-hexane washing, is recrystallized to give 2,6- diethyl-methylphenylamine base lithium
The tetrahydrofuran complex L1 of salt.Under the protection of nitrogen, under ice-water bath, tert-butyl group nitrile (0.2ml, 2mmol) is slowly added to
In L1 tetrahydrofuran solution, after solution is warming up to room temperature naturally, reaction 6 hours is kept stirring for, is obtained by extraction with toluene
N- methyl -2,6- diethylaniline imines lithium salt compounds L2 of oily.Then under the protection of nitrogen, again by part chemical combination
Thing L2 is dissolved in tetrahydrofuran, and dimethyldichlorosilane (0.3ml, 2mmol) is added under ice-water bath, stirring reaction 3-4 hours, is added
Enter lithium diisopropyl amido (0.21g, 2mmol) and carry out secondary dehydrogenation, be kept stirring for reaction 10 hours, extracted with toluene, concentrate,
It is recrystallized to give bis diimines silicon bridge lithium salt compound L3.
Intermediate L1, L2 and L3 yield and its data of sign are as follows：
L1:Colorless crystalline thing, yield 98%.1H NMR(300MHz C6D6):δ1.21-1.25(d,6H,CH2CH3),2.28
(s,3H,CH3),2.60–2.64(m,4H,CH2CH3),4.03,4.43(d,2H,CH2),6.85–6.89(m,3H,Aryl).13C
NMR(75MHz C6D6):δ24.58(CH2CH3),26.63(CH3),28.95(CH2CH3),83.55(CH2),118.12(p-Ar),
122.29(m-Ar),126.12(ipso-CAr),145.77(ipso-CAr- N), 149.29 (N=C)
L2：Colorless crystalline thing, yield：98%.1H NMR(300MHz C6D6)δ0.90-0.93(m,9H,C(CH3)3),
1.22-1.25(m,6H,CH2CH3),2.27(s,3H,CH3),2.58(m,4H,CH2CH3),6.05(d,1H,CH),6.89-6.93
(m,3H,m,p-Ar).13C NMR(75MHz C6D6)δ20.56(CH3,Et),22.30(CH3),23.68(CH2,Et),28.98-
29.28(CH3,tBu),42.70(C,tBu),119.50(p-Ar),122.51(m-Ar),125.94(ipso-CAr),145.54
(ipso-CAr-N),148.92(N-C-CH3),164.64(N-C-tBu).
L3：Colorless crystalline thing, yield：95%.1H NMR(300MHz C6D6)δ0.18-0.21(d,6H,Si(CH3)2),
0.70-0.73(m,9H,C(CH3)3),1.12-1.15(m,6H,CH2CH3),2.26(s,3H,CH3),2.54(m,4H,
CH2CH3),6.10(d,1H,CH),6.87-6.93(m,3H,m,p-Ar).13C NMR(75MHz C6D6)δ14.53(Si
(CH3)2),21.76(CH3,Et),22.40(CH3),23.80(CH2,Et),28.80-29.28(CH3,tBu),41.70(C,tBu),118.50(p-Ar),122.41(m-Ar),125.95(ipso-CAr),145.34(ipso-CAr-N),148.90(N-C-
CH3),164.60(N-C-tBu).C38H58Li2N4Si Elemental Analysis theories：C,74.47；H,9.54；N, 9.14%. measured value：
C,74.42；H,9.51；N,9.22.
(2) catalyst C preparation：Schlenk bottles are vacuumized into logical N2After displacement three times, addition L3 (0.61g,
1mmol) with tetrahydrofuran 25ml, ZrCl are added at -78 DEG C4(0.46g, 2mmol) stirring is lower to recover room temperature reaction 24 hours, very
Sky, which is drained, adds 50 milliliters of dichloromethane, filters, concentration, n-hexane washing, is crystallized in dichloromethane, obtains pale yellow crystals
0.47 gram of compound C, yield：62%.Decomposition temperature：159–161℃.Elemental Analysis theory C38H58Cl2N4SiZr：C,
59.97；H,7.68；N, 7.36%. measured value:C,60.02；H,7.71；N,7.28.1H NMR(300MHz CDCl3)δ0.62-
0.64(d,6H,Si(CH3)2),1.17-1.27(m,6H,CH2CH3),1.29-1.31(m,9H,C(CH3)3),1.82(s,3H,
CH3),2.50-2.65(m,4H,CH2CH3),5.98(d,1H,CH),7.10-7.24(m,3H,m,p-Ar).13C NMR(75MHz
C6D6)δ5.72(Si(CH3)2),13.61-14.63(CH3,Et),24.99(CH3),26.36-26.66(CH2,Et),31.17
(CH3,tBu),41.29(C,tBu),109.79(CH),124.96(p-Ar),126.26-126.59(m-Ar),135.17,
137.63(ipso-CAr),152.36(ipso-CAr-N),174.57(N-C-CH3),179.26(N-C-tBu) crystal structures are shown in
Fig. 1.
Embodiment 2
1. catalyst C preparation is the same as embodiment 1.
2. vinyl polymerization：250 milliliters of polymerization bottles equipped with magnetic stick are continuous drying 6 hours at 130 DEG C, take out while hot true
Sky simultaneously uses N2Gas is replaced 3 times.Catalyst C (3.8mg, 5 μm of ol) is added, then vacuumizes and is replaced 2 times with ethene again.With injection
Device injects a certain amount of toluene (26.6ml), and adding MAO (1.46mol/L, 3.4ml) makes Al/Zr=1000,
At 50 DEG C, the ethylene pressure of 1 atmospheric pressure is kept, is stirred vigorously 30 minutes.In to reaction solution plus in 5% ethanol solution hydrochloride
With there is a small amount of white solid to separate out.It is dried in vacuo 3 hours after filtering.Obtain product 0.028g, polymerization activity：1.12×
104g·mol(Zr)-1·h-1, the fusing point of polymer：133.9℃.
Embodiment 3
1. catalyst C preparation is the same as embodiment 1.
2. vinyl polymerization：250 milliliters of the stainless steel kettle equipped with mechanical agitation and thermocouple is vacuumized and put with nitrogen
Change 3 times, then replaced 2 times with ethene.Be cooled to after 30 DEG C, sequentially add catalyst C (3.8mg, 5 μm of ol) toluene solution and
A certain amount of toluene, adding MAO (1.46mol/L, 3.4ml) makes Al/Zr=1000, is eventually adding a certain amount of first
The cumulative volume of benzene is 100 milliliters.Immediately by the pressure rise of ethene to 10 atmospheric pressure, it is stirred vigorously at 30 DEG C 30 minutes.Will
Reaction solution is poured out, and adds 5% ethanol solution hydrochloride neutralization, there is white solid precipitation.It is dried in vacuo 3 hours after filtering.
To 1.04 grams of product, polymerization activity：4.16×105g·mol(Zr)-1·h-1, the fusing point of polymer：132.7 DEG C, molecular weight：
1.32×106g·mol-1, molecular weight distribution：6.54.
Embodiment 4
1. catalyst C preparation is the same as embodiment 1.
2. vinyl polymerization：250 milliliters of the stainless steel kettle equipped with mechanical agitation and thermocouple is vacuumized and put with nitrogen
Change 3 times, then replaced 2 times with ethene.Be cooled to after 50 DEG C, sequentially add catalyst C (3.8mg, 5 μm of ol) toluene solution and
A certain amount of toluene, adding MAO (1.46mol/L, 3.4ml) makes Al/Zr=1000, is eventually adding a certain amount of first
The cumulative volume of benzene is 100 milliliters.Immediately by the pressure rise of ethene to 10 atmospheric pressure, it is stirred vigorously at 50 DEG C 30 minutes.Will
Reaction solution is poured out, and adds 5% ethanol solution hydrochloride neutralization, there is white solid precipitation.It is dried in vacuo 3 hours after filtering.
To 2.03 grams of product, polymerization activity：8.12×105g·mol(Zr)-1·h-1, the fusing point of polymer：134.1℃.
Embodiment 5
1. catalyst C preparation is the same as embodiment 1.
2. vinyl polymerization：250 milliliters of the stainless steel kettle equipped with mechanical agitation and thermocouple is vacuumized and put with nitrogen
Change 3 times, then replaced 2 times with ethene.Catalyst C (3.8mg, 5 μm of ol) toluene solution and a certain amount of toluene are sequentially added, is risen
For temperature to 70 DEG C, being eventually adding a certain amount of MAO (1.46mol/L, 3.4ml) makes Al/Zr=1000, the totality of toluene
Product is 100 milliliters.Immediately by the pressure rise of ethene to 10 atmospheric pressure, it is stirred vigorously at 70 DEG C 30 minutes, adds 5% salt
Sour ethanol solution, there is substantial amounts of polymer to swim in above container after static.Filtration drying, white polymer 2.63g is obtained, gathered
Close activity：1.05×106g·mol(Zr)-1·h-1, the fusing point of polymer：133.6 DEG C, molecular weight：3.26×106g·mol-1,
Molecular weight distribution：7.22.
Embodiment 6
1. catalyst C preparation is the same as embodiment 1.
2. vinyl polymerization：250 milliliters of the stainless steel kettle equipped with mechanical agitation and thermocouple is vacuumized and put with nitrogen
Change 3 times, then replaced 2 times with ethene.Catalyst C (3.8mg, 5 μm of ol) toluene solution and a certain amount of toluene are sequentially added, is risen
For temperature to 80 DEG C, being eventually adding a certain amount of MAO (1.46mol/L, 3.4ml) makes Al/Zr=1000, the totality of toluene
Product is 100 milliliters.Immediately by the pressure rise of ethene to 10 atmospheric pressure, it is stirred vigorously at 70 DEG C 30 minutes, adds 5% salt
Sour ethanol solution, there is substantial amounts of polymer to swim in above container after static.Filtration drying, white polymer 2.53g is obtained, gathered
Close activity：1.01×106g·mol(Zr)-1·h-1, the fusing point of polymer：132.8℃.
Claims (3)
1. a kind of bis diimines silicon bridge Zr catalyst, it is characterised in that have following structural formula：
Wherein：
R1、R2It is each independently selected from hydrogen, methyl, ethyl, one kind in isopropyl and methoxyl group；R3、R4It is each independently selected from
One kind in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxy；
X is chlorine.
2. a kind of preparation method of bis diimines silicon bridge Zr catalyst as claimed in claim 1, it is characterised in that including as follows
Step：
(1) preparation of lithium salts：Under the protection of nitrogen, under acetone bath, by kitimine compound and lithium diisopropyl amido etc.
Molar reactive, solvent are tetrahydrofuran, after reacting 4-6 hours, after solution is warming up to room temperature naturally, are kept stirring for reacting 8-
10 hours, obtain the tetrahydrofuran solution of lithium salts；It is under ice-water bath, equimolar tert-butyl group nitrile is slow under the protection of nitrogen
It is added thereto, after solution is warming up to room temperature naturally, is kept stirring for reacting 10-12 hours, imine lithium is obtained by extraction with toluene
Salt compound；Then under the protection of nitrogen, under ice-water bath, appropriate silane compound is added, is kept for reaction 3-4 hours, is used
Equimolar lithium diisopropyl amido lithiumation again, it is kept stirring for reacting 8-10 hours, is obtained with toluene extractive crystallization colourless
Diimine silicon bridge lithium ligand compound；
(2) preparation of catalyst：Under the protection of nitrogen, under acetone bath, transition metal halide ZrX4It is sub- to be added to double two
In the tetrahydrofuran solution of amine silicon bridge lithium, ZrX4Mol ratio with bis diimines silicon bridge lithium is 1-2 ﹕ 1, when solution is warming up to naturally
After room temperature, it is kept stirring for reacting 20-24 hours, vacuum is drained, and is added dichloromethane, filtering, filtrate is concentrated to give into double two
Imines silicon bridge Zr catalyst.
A kind of 3. application of bis diimines silicon bridge Zr catalyst in olefin polymerization as claimed in claim 1.
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| CN1164594C (en) * | 2001-06-28 | 2004-09-01 | 山西大学 | Beta-diimine metal match and its synthesizing process |
| CN1769314A (en) * | 2004-11-03 | 2006-05-10 | 中国石油化工股份有限公司 | Copolymer of olefin and omega-tolyl-alpha-olefin and its preparation method |
| CN101274939B (en) * | 2008-05-16 | 2012-05-09 | 华东理工大学 | Novel beta-diketiminato zirconium compound, preparation thereof and application thereof |
| CN101786018B (en) * | 2010-02-09 | 2013-04-10 | 山西大学 | Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof |
| CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
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