CN105482007A - Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof - Google Patents

Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof Download PDF

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CN105482007A
CN105482007A CN201610011656.2A CN201610011656A CN105482007A CN 105482007 A CN105482007 A CN 105482007A CN 201610011656 A CN201610011656 A CN 201610011656A CN 105482007 A CN105482007 A CN 105482007A
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bis
catalyst
diimines
lithium
silicon bridge
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CN105482007B (en
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袁世芳
李�杰
孙文华
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Shanxi University
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Shanxi University
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention provides a bis-diimine silicon-bridged zirconium catalyst and relates to a vinyl polymerization IVB transition metal catalyst, in particular to an imine silicon-bridged ligand zirconium complex catalyst with an N-C-C-C-N-Si-N-C-C-C-N framework. A preparation method of the bis-diimine silicon-bridged zirconium catalyst includes the steps that under protection of nitrogen, lithium diisopropylamide (LDA) is used for conducting dehydrogenation on a ketimine compound, ligand lithium salt is obtained, an equivalent mole of tertiary butyl nitrile is added to obtain a diimine lithium salt compound, a proper quantity of silane compound is added, and a bis-diimine silicon-bridged lithium salt compound is obtained through secondary dehydrogenation; finally, the bis-diimine silicon-bridged lithium salt compound reacts with a transition metal halide to obtain the bis-diimine silicon-bridged zirconium catalyst. The preparation method is simple, adopted materials are easy to obtain, price is low, and the yield is high. The catalyst is used for vinyl polymerization to show high catalytic activity, and polyethylene with the ultra-high molecular weight is obtained.

Description

Bis diimines silicon bridge Zr catalyst and preparation method thereof
Technical field
The present invention relates to vinyl polymerization IVB transition-metal catalyst, in particular to a kind of imines silicon bridge zirconium complex catalyst with N-C-C-C-N-Si-N-C-C-C-N skeleton, it is more particularly a kind of bis diimines silicon bridge Zr catalyst and its preparation method and application.
Background technology
Polyvinyl resin is the kind that in general synthetic resin, output is maximum, because of features such as its price are low, performance is good, quite extensive in the application of China, as film, injection-molded item, electric wire, hollow piece etc. all occupy larger ratio in its consumption structure.Industrialized olefin polymerization catalysis has the catalyzer such as Ziegler-Natta type catalyzer, Phillips type catalyzer and metallocene-type, and these catalyzer can reach control to catalytic activity and polymer performance by regulating the structure of part.Wherein the report of bis diimines silicon bridge metallic compound class catalyzer is very rare, and there is raw materials complex process, productive rate is low, and catalytic activity is low, the shortcomings such as polymer resin molecule amount is low, limit the application of this type of bis diimines silicon bridge metal compound as catalyst.
Summary of the invention
The object of the present invention is to provide a kind of bis diimines silicon bridge Zr catalyst and preparation method thereof, and the application of this catalyzer in vinyl polymerization.
A kind of bis diimines silicon bridge Zr catalyst provided by the invention, has following structural formula:
Wherein:
R 1, R 2be selected from hydrogen independently of one another, the one in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxyl group; R 3, R 4be selected from the one in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxyl group independently of one another;
R 1, R 2preferred from hydrogen independently of one another, methyl, ethyl, the one in sec.-propyl and methoxyl group.
X is halogen, preferred chlorine or bromine.
Present invention also offers a kind of preparation method of bis diimines silicon bridge Zr catalyst, comprise the steps:
(1) preparation of lithium salts: under the protection of nitrogen, under acetone bath, by kitimine compound and lithium diisopropyl amido reaction with same mole, solvent is tetrahydrofuran (THF), react after 4-6 hour, after solution is warmed up to room temperature naturally, keeps stirring reaction 8-10 hour, obtain the tetrahydrofuran solution of lithium salts L1; Under the protection of nitrogen, under ice-water bath, equimolar tertiary butyl nitrile is slowly added wherein, after solution is warmed up to room temperature naturally, keep stirring reaction 10-12 hour, obtain imine lithium salt compound L2 with toluene extraction; Then, under the protection of nitrogen, under ice-water bath, appropriate silane compound is added, keep reaction 3-4 hour, by equimolar lithium diisopropyl amido lithiumation again, keep stirring reaction 8-10 hour, obtain colourless diimine silicon bridge lithium ligand compound L3 with toluene extractive crystallization;
(2) preparation of catalyzer: under the protection of nitrogen, under acetone bath, transition metal halide ZrX 4join in the tetrahydrofuran solution of bis diimines silicon bridge lithium L3, ZrX 4be 1-2 ﹕ 1 with the mol ratio of L3, after solution is warmed up to room temperature naturally, keep stirring reaction 20-24 hour, vacuum is drained, and adds methylene dichloride, filters, and obtains bis diimines silicon bridge Zr catalyst C by concentrated for filtrate.Concrete synthetic route is as follows:
The application of bis diimines silicon bridge Zr catalyst in vinyl polymerization.In the experiment of vinyl polymerization, polymerization catalyst activity reaches as high as: 1.05 × 10 6gmol (Zr) -1h -1, molecular weight of polyethylene can reach: 3.26 × 10 6gmol -1.
Compared with prior art advantage of the present invention and effect: synthetic catalyst is raw materials used to be easy to get, cheap, preparation method is simple, and productive rate is higher; Catalyzer is used for vinyl polymerization high catalytic activity, can obtain the polyethylene with ultra-high molecular weight.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of catalyzer C;
In the crystalline structure of Fig. 1, coordination structure is the octahedral structure of distortion.
Embodiment
Be only below and illustrate and the embodiment that provides, these embodiments are not for limiting the scope of the invention.
Embodiment 1
(1) preparation of lithium salts
Under the protection of nitrogen, under acetone bath, by lithium diisopropyl amido (0.21g; 2mmol) join N-methyl-2; in the tetrahydrofuran solution of 6-diethylbenzene imines (0.42g, 2mmol), react after 3 hours; after solution is warmed up to room temperature naturally; keep stirring reaction 8 hours, vacuum is drained, n-hexane; recrystallization obtains the tetrahydrofuran (THF) title complex L1 of 2,6-diethyl-methylphenylamine base lithium salts.Under the protection of nitrogen; under ice-water bath; by tertiary butyl nitrile (0.2ml; 2mmol) slowly add in the tetrahydrofuran solution of L1; after solution is warmed up to room temperature naturally; keep stirring reaction 6 hours, obtain N-methyl-2, the 6-Diethyl Aniline imine lithium salt compound L2 of oily with toluene extraction.Then under the protection of nitrogen; again ligand compound L2 is dissolved in tetrahydrofuran (THF); dimethyldichlorosilane(DMCS) (0.3ml, 2mmol) is added, stirring reaction 3-4 hour under ice-water bath; add lithium diisopropyl amido (0.21g; 2mmol) carry out secondary dehydrogenation, keep stirring reaction 10 hours, extract with toluene; concentrated, recrystallization obtains bis diimines silicon bridge lithium salt compound L3.
The productive rate of intermediate L1, L2 and L3 and the data of sign as follows:
L1: colorless crystalline thing, productive rate 98%. 1HNMR(300MHzC 6D 6):δ1.21-1.25(d,6H,CH 2CH 3),2.28(s,3H,CH 3),2.60–2.64(m,4H,CH 2CH 3),4.03,4.43(d,2H,CH 2),6.85–6.89(m,3H,Aryl). 13CNMR(75MHzC 6D 6):δ24.58(CH 2CH 3),26.63(CH 3),28.95(CH 2CH 3),83.55(CH 2),118.12(p-Ar),122.29(m-Ar),126.12(ipso-C Ar),145.77(ipso-C Ar-N),149.29(N＝C).
L2: colorless crystalline thing, productive rate: 98%. 1HNMR(300MHzC 6D 6)δ0.90-0.93(m,9H,C(CH 3) 3),1.22-1.25(m,6H,CH 2CH 3),2.27(s,3H,CH 3),2.58(m,4H,CH 2CH 3),6.05(d,1H,CH),6.89-6.93(m,3H,m,p-Ar). 13CNMR(75MHzC 6D 6)δ20.56(CH 3,Et),22.30(CH 3),23.68(CH 2,Et),28.98-29.28(CH 3, tBu),42.70(C, tBu),119.50(p-Ar),122.51(m-Ar),125.94(ipso-C Ar),145.54(ipso-C Ar-N),148.92(N-C-CH 3),164.64(N-C- tBu).
L3: colorless crystalline thing, productive rate: 95%. 1hNMR (300MHzC 6d 6) δ 0.18-0.21 (d, 6H, Si (CH 3) 2), 0.70-0.73 (m, 9H, C (CH 3) 3), 1.12-1.15 (m, 6H, CH 2cH 3), 2.26 (s, 3H, CH 3), 2.54 (m, 4H, CH 2cH 3), 6.10 (d, 1H, CH), 6.87-6.93 (m, 3H, m, p-Ar). 13cNMR (75MHzC 6d 6) δ 14.53 (Si (CH 3) 2), 21.76 (CH 3, Et), 22.40 (CH 3), 23.80 (CH 2, Et), 28.80-29.28 (CH 3, tbu), 41.70 (C, tbu), 118.50 (p-Ar), 122.41 (m-Ar), 125.95 (ipso-C ar), 145.34 (ipso-C ar-N), 148.90 (N-C-CH 3), 164.60 (N-C- tbu) .C 38h 58li 2n 4si Elemental Analysis theory: C, 74.47; H, 9.54; N, 9.14%. measured value: C, 74.42; H, 9.51; N, 9.22.
(2) preparation of catalyzer C: Schlenk bottle is vacuumized logical N 2replace after three times, add L3 (0.61g, 1mmol) and tetrahydrofuran (THF) 25ml, add ZrCl at-78 DEG C 4(0.46g, 2mmol) stirs lower recovery room temperature reaction 24 hours, and vacuum is drained and added methylene dichloride 50 milliliters, filters, and concentrated, n-hexane, crystallization in methylene dichloride, obtains pale yellow crystals Compound C 0.47 gram, productive rate: 62%.Decomposition temperature: 159 – 161 DEG C.Elemental Analysis theory C 38h 58cl 2n 4siZr:C, 59.97; H, 7.68; N, 7.36%. measured value: C, 60.02; H, 7.71; N, 7.28. 1hNMR (300MHzCDCl 3) δ 0.62-0.64 (d, 6H, Si (CH 3) 2), 1.17-1.27 (m, 6H, CH 2cH 3), 1.29-1.31 (m, 9H, C (CH 3) 3), 1.82 (s, 3H, CH 3), 2.50-2.65 (m, 4H, CH 2cH 3), 5.98 (d, 1H, CH), 7.10-7.24 (m, 3H, m, p-Ar). 13cNMR (75MHzC 6d 6) δ 5.72 (Si (CH 3) 2), 13.61-14.63 (CH 3, Et), 24.99 (CH 3), 26.36-26.66 (CH 2, Et), 31.17 (CH 3, tbu), 41.29 (C, tbu), 109.79 (CH), 124.96 (p-Ar), 126.26-126.59 (m-Ar), 135.17,137.63 (ipso-C ar), 152.36 (ipso-C ar-N), 174.57 (N-C-CH 3), 179.26 (N-C- tbu). crystalline structure is shown in Fig. 1.
Embodiment 2
1. the preparation of catalyzer C is with embodiment 1.
2. vinyl polymerization: by 250 milliliters of polymerization bottles that magnetic stick is housed 130 DEG C of successive dryings 6 hours, vacuumize while hot and use N 2gas replaces 3 times.Add catalyzer C (3.8mg, 5 μm of ol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.6ml) with syringe, then add methylaluminoxane (1.46mol/L, 3.4ml) and make Al/Zr=1000, at 50 DEG C, keep 1 atmospheric ethylene pressure, vigorous stirring 30 minutes.In reaction solution, add the ethanol solution hydrochloride neutralization of 5%, have a small amount of white solid to separate out.Filter final vacuum dry 3 hours.Obtain product 0.028g, polymerization activity: 1.12 × 10 4gmol (Zr) -1h -1, the fusing point of polymkeric substance: 133.9 DEG C.
Embodiment 3
1. the preparation of catalyzer C 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.Be cooled to after 30 DEG C, add the toluene solution of catalyzer C (3.8mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (1.46mol/L, 3.4ml) make Al/Zr=1000, 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 at 30 DEG C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Filter final vacuum dry 3 hours.Obtain product 1.04 grams, polymerization activity: 4.16 × 10 5gmol (Zr) -1h -1, the fusing point of polymkeric substance: 132.7 DEG C, molecular weight: 1.32 × 10 6gmol -1, molecular weight distribution: 6.54.
Embodiment 4
1. the preparation of catalyzer C 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.Be cooled to after 50 DEG C, add the toluene solution of catalyzer C (3.8mg, 5 μm of ol) and a certain amount of toluene successively, then add methylaluminoxane (1.46mol/L, 3.4ml) make Al/Zr=1000, 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 at 50 DEG C.Poured out by reaction solution, add the ethanol solution hydrochloride neutralization of 5%, adularescent solid is separated out.Filter final vacuum dry 3 hours.Obtain product 2.03 grams, polymerization activity: 8.12 × 10 5gmol (Zr) -1h -1, the fusing point of polymkeric substance: 134.1 DEG C.
Embodiment 5
1. the preparation of catalyzer C 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.Add catalyzer C (3.8mg successively, 5 μm of ol) toluene solution and a certain amount of toluene, be warming up to 70 DEG C, finally add a certain amount of methylaluminoxane (1.46mol/L, 3.4ml) make Al/Zr=1000, the cumulative volume of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, at 70 DEG C, vigorous stirring 30 minutes, adds the ethanol solution hydrochloride of 5%, has a large amount of polymkeric substance to swim in above container after static.Filtration drying, obtains white polymer 2.63g, polymerization activity: 1.05 × 10 6gmol (Zr) -1h -1, the fusing point of polymkeric substance: 133.6 DEG C, molecular weight: 3.26 × 10 6gmol -1, molecular weight distribution: 7.22.
Embodiment 6
1. the preparation of catalyzer C 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.Add catalyzer C (3.8mg successively, 5 μm of ol) toluene solution and a certain amount of toluene, be warming up to 80 DEG C, finally add a certain amount of methylaluminoxane (1.46mol/L, 3.4ml) make Al/Zr=1000, the cumulative volume of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, at 70 DEG C, vigorous stirring 30 minutes, adds the ethanol solution hydrochloride of 5%, has a large amount of polymkeric substance to swim in above container after static.Filtration drying, obtains white polymer 2.53g, polymerization activity: 1.01 × 10 6gmol (Zr) -1h -1, the fusing point of polymkeric substance: 132.8 DEG C.

Claims (4)

1. a bis diimines silicon bridge Zr catalyst, is characterized in that, has following structural formula:
Wherein:
R 1, R 2be selected from hydrogen independently of one another, the one in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxyl group; R 3, R 4be selected from the one in the alkyl of 1-10 carbon atom, aryl, alkaryl, aralkyl and alkoxyl group independently of one another;
X is chlorine or bromine.
2. a kind of bis diimines silicon bridge Zr catalyst as claimed in claim 1, is characterized in that, described R 1, R 2be selected from hydrogen independently of one another, methyl, ethyl, the one in sec.-propyl and methoxyl group.
3. the preparation method of a kind of bis diimines silicon bridge Zr catalyst as claimed in claim 1 or 2, is characterized in that, comprise the steps:
(1) preparation of lithium salts: under the protection of nitrogen, under acetone bath, by kitimine compound and lithium diisopropyl amido reaction with same mole, solvent is tetrahydrofuran (THF), react after 4-6 hour, after solution is warmed up to room temperature naturally, keeps stirring reaction 8-10 hour, obtain the tetrahydrofuran solution of lithium salts; Under the protection of nitrogen, under ice-water bath, equimolar tertiary butyl nitrile is slowly added wherein, after solution is warmed up to room temperature naturally, keep stirring reaction 10-12 hour, obtain imine lithium salt compound with toluene extraction; Then, under the protection of nitrogen, under ice-water bath, appropriate silane compound is added, keep reaction 3-4 hour, by equimolar lithium diisopropyl amido lithiumation again, keep stirring reaction 8-10 hour, obtain colourless diimine silicon bridge lithium ligand compound with toluene extractive crystallization;
(2) preparation of catalyzer: under the protection of nitrogen, under acetone bath, transition metal halide ZrX 4join in the tetrahydrofuran solution of bis diimines silicon bridge lithium, ZrX 4be 1-2 ﹕ 1 with the mol ratio of bis diimines silicon bridge lithium, after solution is warmed up to room temperature naturally, keep stirring reaction 20-24 hour, vacuum is drained, and adds methylene dichloride, filters, and obtains bis diimines silicon bridge Zr catalyst by concentrated for filtrate.
4. a kind of bis diimines silicon bridge Zr catalyst as claimed in claim 1 or 2 application in olefin polymerization.
CN201610011656.2A 2016-01-08 2016-01-08 Bis diimines silicon bridge Zr catalyst and preparation method thereof Expired - Fee Related CN105482007B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1393450A (en) * 2001-06-28 2003-01-29 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
CN101274939A (en) * 2008-05-16 2008-10-01 华东理工大学 Novel beta-diketiminato zirconium compound, preparation thereof and application thereof
CN101786018A (en) * 2010-02-09 2010-07-28 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1393450A (en) * 2001-06-28 2003-01-29 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
CN101274939A (en) * 2008-05-16 2008-10-01 华东理工大学 Novel beta-diketiminato zirconium compound, preparation thereof and application thereof
CN101786018A (en) * 2010-02-09 2010-07-28 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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