CN1138791C - Non-cyclopentadiene Zr metal compound, its preparing process and its application of olefine polymerization - Google Patents
Non-cyclopentadiene Zr metal compound, its preparing process and its application of olefine polymerization Download PDFInfo
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- CN1138791C CN1138791C CNB001151924A CN00115192A CN1138791C CN 1138791 C CN1138791 C CN 1138791C CN B001151924 A CNB001151924 A CN B001151924A CN 00115192 A CN00115192 A CN 00115192A CN 1138791 C CN1138791 C CN 1138791C
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 8
- 230000008569 process Effects 0.000 title abstract description 4
- 150000002736 metal compounds Chemical class 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 cyclopentadiene zirconium metal compound Chemical class 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000003755 zirconium compounds Chemical class 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000004458 analytical method Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000011160 research Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000001793 charged compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011980 kaminsky catalyst Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OKICHZSTRJQITD-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene zirconium(2+) Chemical compound [Zr++].C[c-]1cccc1.C[c-]1cccc1 OKICHZSTRJQITD-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a non-cyclopentadiene zirconium metal compound, a preparing process thereof and an application of the compound to olefine polymerization. In the present invention, zirconium is introduced into a precursor of the non-cyclopentadiene compound to synthesize the zirconium compound, and test results show that the activity of a zirconium catalyst is superior to that of titanium. Polyethylene obtained by catalysis has a highly branched structure, the product has favorable physical and processing performance and can meet various special requirements, and the structural formula of the polyethylene is disclosed in the drawing.
Description
Technical field
The invention belongs to the synthetic and high molecular polymer synthetic complex art field of orgnometallic catalyst, relate to a kind of non-luxuriant metal compound and preparation method thereof, and this compound is at ethene, the application of alpha-olefine polymerizing processes such as propylene and vinylbenzene.
Background technology
The beginning of the fifties, the discovery of ferrocene and Ziegler-Natta catalyst (G.Natta; P.Pino; U.Giannini, J.Am.Chem.Soc., 1954,79,2975) be applied to the success of vinyl polymerization, make organometallics obtain swift and violent development.Since nineteen sixty, being synthesized of numerous novel metal organic compound successes, and provide the new catalyst of a series of high reactivities, highly selective, be widely used in the polymerization of alpha-olefin and numerous organic synthesis, and also demonstrate huge vitality at the synthetic and life science of type material.
The beginning of the eighties, people such as Kaminsky (W.Kaminsky, M.Miri, H.Sinn, R.Woldt, Makromol.Commun., 1983,4,417.) find the homogeneous catalysis system that is dissolved in toluene that methylaluminoxane (MAO) and dimethyl zirconocene are formed, vinyl polymerization is had high catalytic activity, up to 40,000KgPE/ (gZrh), the discovery of this achievement is once to shock greatly for whole academia and industry member.Contemporary world, polyolefinic annual production is up to tens million of ton, and economic benefit is very considerable, becomes people's inseparable part of living.Therefore, the numerous and confused reasearch funds that drop into tens billion of dollars of each big industrial group of the world, as: Du Pont, BASF and Exxon etc., develop and develop the new type of metal organic catalyst.
The orgnometallic catalyst of olefinic polymerization comprises two kinds of metallocene catalyst and non-metallocene catalysts.Metallocene catalyst is the focus of various countries scientist research always, and each big famous transnational company of the world has also released one after another and has been rich in the alkene catalyst of own characteristic and applied for patent, as: EP-B 638,593,1995, WO-A92/12162,1992, EP-B 0416815,1990 etc.
Yet people find in the research to non-metallocene catalyst in recent years, and they also can be used for the polymerization of alkene, and non-metallocene catalyst is compared the many advantages with self with metallocene catalyst:
(1) because people are a lot of to the research of metallocene compound, applied for thousands of pieces patent, thereby limited the primitiveness creativity and innovation of metallocene compound, but not luxuriant then be a brand-new field, be in the evolution period after the rudiment.
(2) cyclopentadinyl compound is subjected to the restriction of cyclopentadienyl, no matter be the modification to luxuriant ring, still the modification to bridge atom all had been tending towards perfect already, and therefore the space that can study is more and more littler, but not cyclopentadinyl compound then is not subjected to the restriction of cyclopentadienyl group, thereby has wide research space.
(3) the synthetic aspect of part, synthesizing of non-cyclopentadienyl ligand is generally comparatively simple, not as good as the cyclopentadienyl ligand harshness.
Therefore, the prospect of non-cyclopentadiene compounds research makes us good, and many scientists also change their research field over to non-luxuriant field one after another.Entered since the nineties, emerge in an endless stream especially relevant for the report and the patent of non cyclopentadienyl catalyst.For example US P 5 026 789, and 1990 disclose a kind of structural formula non-luxuriant metalloid complex compound as follows, are used for the catalyzed polymerization of alkene.
And our domestic research to the Nonmetallocene organic catalyst is less relatively, and patent is phoenix feathers and unicorn horns especially.
The contriver has carried out long term studies to non cyclopentadienyl catalyst, has dropped into great amount of manpower and material resources, has successfully synthesized the alkene catalyst of a series of non-luxuriant titaniums, and has applied for that (number of patent application: 991,19984.7), its activity can reach 10 to Chinese patent
4～10
6GPE/molTih.
Along with science and technology development, it is higher that the contriver tries hard to the development research activity, and cost is lower, and purposes is the Nonmetallocene compound more widely, to satisfy the needs that olefinic polymerization is produced.
Summary of the invention
One of purpose of the present invention is to disclose a kind of non-cyclopentadiene Zr metallic compound.
Two of purpose of the present invention is to disclose the preparation method of said non-luxuriant Zr metal compound.
Three of purpose of the present invention is to disclose said non-luxuriant Zr metal compound as the application of catalyzer in olefin polymerization process.
Design of the present invention is such: studies show that, the catalytic activity of zirconium compounds is better than the catalytic activity of titanium compound, the activity of zirconium than the high order of magnitude of titanium about, therefore we have introduced zirconium the parent of non-cyclopentadiene compounds, synthesized a kind of and Chinese patent (number of patent application: 991,19984.7) zirconium compounds with identical ligands, test result shows that the activity of Zr catalyst is better than titanium.
The structural formula of the said non-cyclopentadiene Zr compound of the present invention is as follows:
Wherein: R
1, R
2Be hydrogen, C
1～C
4Alkyl, methoxyl group, a kind of in the halogen, R
3Be C
1～C
5Alkyl;
X is heteroatomss such as O or S;
Y is N or CH etc.
The catalyzer of gained is white solid.
The said non-cyclopentadiene Zr catalyzer of the present invention is preparation like this:
With Zr (OR
3)
4HOR
3Place solvent with ligand L, under Ar protection, stirring reaction, drain solvent after, obtain flaxen solid, with solvent recrystallization, washing for several times, just obtain analytically pure catalyzer.Wherein:
Said solvent is a tetrahydrofuran (THF), ether, normal hexane, toluene, benzene, chloroform, methylene dichloride, the organic solvent that sherwood oil etc. are conventional;
L is a part, has the schiff bases class formation, and its structural formula is as follows:
Wherein: R
1, R
2, X, Y are as previously mentioned.
Similar schiff bases titanium family complex compound also once had report (as: Patwaardhan, H.A.; Gopinathan, S.G., Indian Journal of Chemistry 1978,16A, 224-227; Chen H.; White, P.S.; Gagne, R.Organometallics, 1998,17,5358-5366), typical structure is as shown below:
But these compounds are not all almost having activity aspect the catalyzed polymerization alpha-olefin.This class complex compound has the structure of ortho position diamines or straight diamine, and the catalyzer of our design is by changing amino substituent position (position) dexterously, form a kind of structure of chelating type, just make prepared catalyzer that catalytic activity is preferably being arranged aspect the catalyzed polymerization alpha-olefin.The preparation of said part very is simple and easy to, and the many documents of preparation method are equal
Report is arranged, as: Lopez, J.; Liang, S.; Xiu, R.Bu; Tetrahedron Letters, 1998,39,4199-4202. repeats no more herein.Reaction formula is as follows:
The processing condition of reaction are such:
Zr (OR
3)
4HOR
3With the mol ratio of ligand L be 1: (1～3), preferred mol ratio is 1: 1～1.2;
Temperature of reaction is-20 ℃～100 ℃, and preferred temperature of reaction is 80～90 ℃;
Reaction times is 1～24 hour, and the preferred reaction times is 15～16 hours.
The said catalyzer of the present invention is a kind of alkene catalyst efficiently, can be used for ethene, propylene and cinnamic polyreaction, and using method is identical with the using method of existing olefin polymerization catalysis.
The present invention adopts document (W.Kaminsky, M.Miri, H.Sinn, R.Woldt, Makromol.Commun., 1983,4,417.) Bao Dao Kaminsky catalyst system is measured the catalytic activity of said catalyzer, find that this type of Zr catalyst has advantages of high catalytic activity to ethene, than high several times of the titanium catalyst of same type.The mensuration process is as follows:
The test of catalyzed ethylene polymerization reactive behavior:
Promotor is methylaluminoxane (MAO) or B (C
6F
5)
3
Test result is as follows:
Catalytic activity scope: 1 * 10
4～1 * 10
6GPE/molZrh.
The polyethylene of catalysis gained has the structure of high branching, and the polyethylene of high branching can pass through
13CNMR spectrogram product is identified.Product has good physics and processing characteristics, can satisfy various special needs, and product has wide application prospect in field of new.
According to above-mentioned disclosed technical scheme as seen, the advantage of the said Zr catalyst of the present invention is fairly obvious: the part preparation cost is cheap, and catalyst production is higher.And the titanium catalyst of prepared Zr catalyst and identical ligands (has been applied for Chinese patent, number of patent application: 991,19984.7) compare and have higher catalytic activity.
Embodiment
Embodiment 1
With mol ratio 1: 1 zirconium tetraisopropoxide (being with a crystallization Virahol) and ligand L [R
1, R
2Be H; X is O, and Y is CH] join in the toluene solution, under argon shield and 10 ℃ of temperature, reaction was stirred 24 hours, drained solvent, obtained faint yellow solid, with toluene recrystallization 3 times, obtained analytically pure catalyzer.The analytical test result is as follows:
Molecular formula: C
26H
28N
2O
4Zr, and mass spectrum demonstration molecular ion peak (522, M
+).
Infrared data (cm
-1): 2963,2857,1610,1587,1470.
Ultimate analysis calculated value: C:59.62% H:5.40% N:5.35%.
Measured value: C:59.27% H:5.24% N:5.49%
Embodiment 2
With mol ratio 1: 1 zirconium tetraisopropoxide (being with a crystallization Virahol) and ligand L [R
1, R
2Be H; X is O, and Y is CH] join in the solution of toluene, under argon shield and 50 ℃ of temperature of reaction, reaction was stirred 10 hours, drained solvent, obtained yellow solid, with the toluene recrystallization for several times, just obtained analytically pure catalyzer.Its analytical test result such as embodiment 1.
Embodiment 3
Under protection of inert gas, the adding mol ratio is 1: 1 ligand L (R in the Schlenk of 100ml bottle
1=H, R
2=OMe, X=O, Y=CH) and ZrCl
4, add 50mlCH
2Cl
2, under reflux state, stir 24h, drip the LiOCH (CH of 2mol amount then
3)
2Continue to stir after 24 hours, filter, reject LiCl precipitation extracts solvent with the filtrate vacuum, and head product ether recrystallization 3 times just obtain analytically pure catalyzer.The result is as follows for its analytical test:
Molecular formula: C
28H
32N
2O
6Zr, and mass spectrum demonstration molecular ion peak (582, M
+).
Infrared data (cm
-1): 2961,2834,1622,1587,1478.
Ultimate analysis calculated value: C:57.60% H:5.54% N:4.80%.
Measured value: C:57.29% H:5.31% N:5.00%
Embodiment 4
Under protection of inert gas, adding mol ratio in the Schlenk of 100ml bottle is 1: 1 ligand L (R
1=H, R
2=Br, Y=N X=O) with 4-isopropoxy zirconium (being with a crystallization Virahol), and adds excessive Et
3N and 50ml CH
2Cl
2, refluxing 24 hours, after vacuum extracted solvent, head product toluene recrystallization 3 times just obtained analytically pure catalyzer.The result is as follows for its analytical test:
Molecular formula: C
25H
25N
3O
4Br
2Zr, and mass spectrum demonstration molecular ion peak (679, M
+)
Infrared data (cm
-1): 2963,2926,1611,1588,1533.
Ultimate analysis calculated value: C:43.99% H:3.70% N:6.16%.
Measured value: C:43.63% H:3.56% N:6.23%
Embodiment 5
In the schlenk of 100ml bottle, add the ligand L (R of 1mol amount
1=H, R
2=C (CH
3)
3, X=S, Y=CH); the solution that adds 50ml toluene again under the temperature of reaction of protection of inert gas and 20 ℃, adds the n-BuLi of 2mol amount; soon the LiCl of adularescent generates, and filters, in filtrate, drip trimethylchlorosilane after; the zirconium tetraisopropoxide (being with a crystallization Virahol) that adds the 1mol amount; under argon shield and 20 ℃ of temperature of reaction, reaction was stirred 20 hours, obtained faint yellow solid; with methylene dichloride recrystallization 3 times, just obtain analytically pure catalyzer.The result is as follows for its analytical test:
Molecular formula: C
34H
44N
2O
2S
2Zr, and mass spectrum demonstration molecular ion peak (666, M
+).
Infrared data (cm
-1): 2960,2859,1617,1583,1543.
Ultimate analysis calculated value: C:61.11% H:6.65% N:4.19%.
Measured value: C:61.00% H:6.53% N:4.28%
Embodiment 6
In the Schlenk of 100ml bottle, add the ligand L (R of 1mol amount
1=CH
3, R
2=H, X=S; Y=N), add the solution of 50ml toluene again, under argon shield and 20 ℃ of temperature of reaction; reaction was stirred 20 hours, added the n-BuLi of 2mol amount, and the LiCl of adularescent generates soon; reaction was stirred after 3 hours; the zirconium tetraisopropoxide (being with a crystallization Virahol) that adds the 1mol amount, under argon shield and 20 ℃ of temperature of reaction, reaction was stirred 20 hours; extract solvent; obtain faint yellow solid, use toluene recrystallization 3 times, just obtain analytically pure catalyzer.
The result is as follows for its analytical test:
Molecular formula: C
26H
29N
3O
2S
2Zr, and mass spectrum demonstration molecular ion peak (569, M
+).
Infrared data (cm
-1): 2962,2857,1610,1546,1471.
Ultimate analysis calculated value: C:54.70% H:5.13% N:7.36%.
Measured value: C:54.53% H:4.98% N:7.52%
Embodiment 7 catalyzed ethylene polymerization reactive behavioies test (adopting the Kaminsky catalyst system), concrete operations are as follows:
With exsiccant 100ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to ethene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled the ethene cooling, and take out and fill three times.Drop into embodiment 1 said catalyzer 3.2mg, adding Al/Zr is 1: 1000～1500 MAO, adds 50ml toluene then, 50 ℃ of stirring reaction 30min.Reaction finishes, with the ethanolic soln termination reaction of hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Claim the weight of polymkeric substance and calculate catalytic activity.
Catalytic activity scope: 1.0 * 10
4～1.0 * 10
6(concentration of test catalyst system therefor is gPE/molZrh: 10
-4Mol/L)
Claims (5)
1. a non-cyclopentadiene Zr metallic compound is characterized in that, this structural general formula is as follows:
Wherein: R
1, R
2Be hydrogen, C
1～C
4Alkyl, methoxyl group, a kind of in the halogen, R
3Be C
1～C
5Alkyl;
X is O or S;
Y is N or CH.
2. the preparation method of compound as claimed in claim 1 is characterized in that comprising the steps:
With Zr (OR
3)
4HOR
3Place solvent with ligand L, under Ar protection, stirring reaction, drain solvent after, obtain flaxen solid, carry out purifying with the method for routine and can obtain said compound;
The structural formula of said ligand L is as follows:
The processing condition of reaction are such:
Zr (OR
3)
4HOR
3With the mol ratio of ligand L be 1: (1～3);
Temperature of reaction is-20 ℃～100 ℃;
Reaction times is 1～24 hour.
3. method as claimed in claim 2 is characterized in that, Zr (OR
3)
4HOR
3With the mol ratio of L be 1: 1.2; Temperature of reaction is 80～90 ℃; Reaction times is 15～16 hours.
4. application of compound as claimed in claim 1 is characterized in that, can be used as catalyzer, is used for the catalytic polymerization of alkene.
5. application of compound as claimed in claim 4 is characterized in that: can be used for ethene, propylene and cinnamic catalytic polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001151924A CN1138791C (en) | 2000-03-28 | 2000-03-28 | Non-cyclopentadiene Zr metal compound, its preparing process and its application of olefine polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001151924A CN1138791C (en) | 2000-03-28 | 2000-03-28 | Non-cyclopentadiene Zr metal compound, its preparing process and its application of olefine polymerization |
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| CN1315460A CN1315460A (en) | 2001-10-03 |
| CN1138791C true CN1138791C (en) | 2004-02-18 |
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| CNB001151924A Expired - Fee Related CN1138791C (en) | 2000-03-28 | 2000-03-28 | Non-cyclopentadiene Zr metal compound, its preparing process and its application of olefine polymerization |
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