CN1357556A - Chromium diimine olefine polymerizing catalyst - Google Patents
Chromium diimine olefine polymerizing catalyst Download PDFInfo
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- CN1357556A CN1357556A CN 01143496 CN01143496A CN1357556A CN 1357556 A CN1357556 A CN 1357556A CN 01143496 CN01143496 CN 01143496 CN 01143496 A CN01143496 A CN 01143496A CN 1357556 A CN1357556 A CN 1357556A
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- diimine
- methyl
- chromium
- ethyl
- polymerizing catalyst
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Abstract
The present invention discloses one kind of chromium diimine as olefine polymerizing catalyst. Under the action of methyl aluminium alkoxide, modified aluminium alkoxide and other neutral Lewis acid, the said catalyst may be used to catalyze ethylene polymerization to prepare high density polyethylene. The structural formula of invented catalyst is also disclosed.
Description
Technical field: the present invention relates to a kind of olefin polymerization catalysis, its preparation method and the application in catalysis in olefine polymerization.
Background technology: high density polyethylene(HDPE) (HDPE) is the important macromolecular material of a class, is widely used in industry, agricultural, national defence, communications and transportation and the daily life.Usually prepare HDPE with Ziegler-Natta catalyst or low price inorganic chromium catalyzer (also claiming the Philliphs catalyzer) catalyzed ethylene polymerization, wherein the polyethylene with the Philliphs Preparation of Catalyst accounts for 2/3rds of world HDPE output.The Philliphs catalyzer is a heterogeneous catalyst, and preparation process complexity, catalytic activity are subjected to the influence of preparation process very big.
Obtaining the clear and definite high reactivity homogeneous catalyst of structure is the direction that people make great efforts, but people such as Britain scientist Gibson had reported alpha-diimine chromium and the single imines chromium of pyrroles catalyzed ethylene polymerization (Chem.Commun. under the activation of organo-aluminium compound in 1998,1998,1651-1652), but catalytic activity is lower.
Summary of the invention: an object of the present invention is to provide a kind of chromium diimine olefine polymerizing catalyst; Another object of the present invention provides a kind of preparation method of chromium diimine olefine polymerizing catalyst; The 3rd purpose of the present invention provides the application of a kind of chromium diimine olefine polymerizing catalyst in catalysis in olefine polymerization, the application that concrete is in catalyzed ethylene polymerization.
This Preparation of Catalyst is convenient, has higher vinyl polymerization catalytic activity under the activation of neutral Lewis acid such as MAO, MMAO, uses MAO/AlEt
2Cl or MMAO/AlEt
2The Cl composite catalyst can further improve catalytic activity.
Imines chromium olefin polymerizing catalyst disclosed by the invention has following structure:
R wherein
1Be methyl, ethyl or propyl group; R
2And R
3Can be identical or different, be respectively H, methyl, ethyl or methoxyl group.
Chromium diimine olefine polymerizing catalyst disclosed by the invention prepares according to the following procedure:
Under the effect of phase-transfer catalysts such as four butyl bromation amine, the mixed solution of reflux sodium sulfide solution and o-chloronitrobenzene toluene solution gets 2,2 '-dinitrobenzene diphenyl sulfide; In the presence of small amount of hydrochloric acid, with iron powder reducing 2,2 '-dinitrobenzene diphenyl sulfide gets 2,2 '-two amido diphenyl sulfides; Under the acid catalysis, carry out the condensation reaction of 2,2 '-two amido diphenyl sulfides and arone, obtain the western Buddhist alkali shown in the following formula,
Under the condition of anhydrous and oxygen-free, carry out the reaction between above-mentioned western Buddhist alkali and the chromium trichloride tetrahydrofuran (THF) title complex, the chromium diimine olefine polymerizing catalyst that obtains being shown below,
R wherein
1Be methyl, ethyl or propyl group; R
2And R
3Can be identical or different, be respectively H, methyl, ethyl or methoxyl group.
Chromium diimine olefine polymerizing catalyst disclosed by the invention is under neutral Lewis acid such as MAO or MMAO effect, and catalyzed ethylene polymerization obtains ultra high molecular weight polyethylene.
Embodiment is as follows:
Embodiment 1
In the 500ml reaction flask, add Na
2S9H
2O 60g (0.25mol) and water 240ml after the stirring and dissolving, add the solution that four butyl bromation amine 4g (12mmol), 80g (0.51mmol) o-chloronitrobenzene and 320ml toluene are made into.Stirring, heating, back flow reaction 24 hours.Cooling separates, concentrates organic phase, adds the sherwood oil of 5 times of amounts, filters, and it is yellow 2 that the toluene recrystallization gets, 2 '-dinitrobenzene diphenyl sulfide 45g, yield 73%.
Embodiment 2
Add in the 500ml reaction flask that embodiment 1 obtains 2,2 '-dinitrobenzene diphenyl sulfide 34.5g (0.125mol), reduced iron powder 42.5g (0.76mol), 50% ethanol 50ml.Stir down, be heated to backflow, dripping hydrochloric acid aqueous ethanolic solution (1/5/5) 28ml in 1 hour continued back flow reaction 1 hour.The ethanolic soln 15ml that adds 15% potassium hydroxide, heat filtering, filter cake washs three times with hot ethanol, merging filtrate adds concentrated hydrochloric acid 200ml, filters, with throw out water dissolution, ammoniacal liquor alkalization, filtration, dry 2,2 '-two amido diphenyl sulfide 22g, the yield 81% of getting.
Embodiment 3
In the 150ml reaction flask, add 2,2 '-two amido diphenyl sulfide 5.4g (25mmol), methyl phenyl ketone 9g (75mmol), toluene 50ml, the dense H that embodiment 2 obtains
2SO
42, heating reflux reaction 3 days.Cooling, steaming desolventizes.Column chromatography gets faint yellow western Buddhist alkali 4.7g, yield 45%.
Embodiment 4
With the methyl phenyl ketone among 2-methyl acetophenone 10g (75mmol) the replacement embodiment 3, operation gets faint yellow western Buddhist alkali 4.4g, yield 39% with embodiment 3.
Embodiment 5
With 2,4-dimethyl acetophenone 11g (74mmol) replaces the methyl phenyl ketone among the embodiment 3, and operation gets faint yellow western Buddhist alkali 4.9g, yield 41% with embodiment 3.
Embodiment 6
With the methyl phenyl ketone among ethyl (4-ethylbenzene base) ketone 12g (75mmol) the replacement embodiment 3, operation gets faint yellow western Buddhist alkali 4.7g, yield 37% with embodiment 3.Embodiment 7
With the methyl phenyl ketone among 4-methoxyacetophenone 11g (73mmol) the replacement embodiment 3, operation gets faint yellow western Buddhist alkali 5.0g, yield 42% with embodiment 3.
Embodiment 8
With the methyl phenyl ketone among n-propyl phenyl ketone 11g (74mmol) the replacement embodiment 3, operation gets faint yellow western Buddhist alkali 4.5g, yield 38% with embodiment 3.
Embodiment 9
Under the argon atmospher, in exsiccant 100ml Schlenk bottle, add the western Buddhist alkali 0.84g (2.0mmol), the chromium trichloride tetrahydrochysene that obtain in the example 3 title complex (CrCl that mutters
32THF) 0.6g (2.0mmol), tetrahydrofuran (THF) 200ml, in 1 week of heating reflux reaction, cooling is filtered, and gets green crystalline solid 1.32g, yield 92%.
Embodiment 10
The western Buddhist alkali 0.90g (2.0mmol) that obtains with embodiment 4 replaces the western Buddhist alkali that obtains among the embodiment 3, and operation is with embodiment 9, green crystalline solid 1.37g, yield 91%.
Embodiment 11
The western Buddhist alkali 0.95g (2.0mmol) that obtains with embodiment 5 replaces the western Buddhist alkali that obtains among the embodiment 3, and operation is with embodiment 9, green crystalline solid 1.43g, yield 92%.
Embodiment 12
The western Buddhist alkali 1.0g (2.0mmol) that obtains with embodiment 6 replaces the western Buddhist alkali that obtains among the embodiment 3, and operation is with embodiment 9, green crystalline solid 1.41g, yield 88%.
Embodiment 13
The western Buddhist alkali 0.96g (2.0mmol) that obtains with embodiment 7 replaces the western Buddhist alkali that obtains among the embodiment 3, and operation is with embodiment 9, green crystalline solid 1.40g, yield 90%.
Embodiment 14
The western Buddhist alkali 0.95g (2.0mmol) that obtains with embodiment 8 replaces the western Buddhist alkali that obtains among the embodiment 3, and operation is with embodiment 9, green crystalline solid 1.38g, yield 89%.
Embodiment 15
Under the ethene atmosphere, in 0.5 liter of autoclave of exsiccant, add chromium diimine catalyzer 10 μ mol, the absolute toluene 200ml of embodiment 9 preparations, stirring and dissolving, be warming up to 50 ℃, modified methylaluminoxane (MMAO) 10ml that adds 2.3M, pressurization, polymerization 90min under the 1.0Mpa.Ethanol solution hydrochloride with 1% stops polyreaction, filters, and 60 ℃ of vacuum-drying 24h get polymkeric substance 16.5g, catalytic efficiency 1.1 * 10
6G PE/mol Crh.
Embodiment 16
The chromium diimine catalyzer that the chromium diimine catalyzer 10 μ mol that prepare with embodiment 10 replace embodiment 9 to prepare, operating process gets polymkeric substance 18g, catalytic efficiency 1.2 * 10 with embodiment 15
6G PE/mol Crh.
Embodiment 17
Used MMAO among chromium diimine catalyzer that replaces embodiment 9 preparations with the chromium diimine catalyzer 10 μ mol and the ethyl aikyiaiurnirsoxan beta of embodiment 11 preparation and the embodiment 15 respectively, operating process is with embodiment 15, polymkeric substance 15.3g, catalytic efficiency 1.0 * 10
6G PE/mol Crh.
Embodiment 18
Used MMAO among chromium diimine catalyzer that replaces embodiment 9 preparations with the chromium diimine catalyzer 10 μ mol and the methylaluminoxane of embodiment 12 preparation and the embodiment 15 respectively, operating process is with embodiment 15, polymkeric substance 14.6g, catalytic efficiency 9.7 * 10
5G PE/mol Crh.
Embodiment 19
The chromium diimine catalyzer that the chromium diimine catalyzer 10 μ mol that prepare with embodiment 13 replace embodiment 9 to prepare, operating process gets polymkeric substance 15.7g, catalytic efficiency 1.05 * 10 with embodiment 15
6G PE/mol Crh.
Embodiment 20
The chromium diimine catalyzer that the chromium diimine catalyzer 10 μ mol that prepare with embodiment 14 replace embodiment 9 to prepare, operating process gets polymkeric substance 18g, catalytic efficiency 1.2 * 10 with embodiment 15
6G PE/mol Crh.
Embodiment 21
With the MMAO among the mixture replacement embodiment 15 of MMAO (3ml) and diethylaluminum chloride (3ml), operating process gets polymkeric substance 29g, catalytic efficiency 1.9 * 10 with embodiment 15
6GPE/mol Crh.Embodiment 22
With the MMAO among the mixture replacement embodiment 15 of MAO (3ml) and diethylaluminum chloride (4ml), operating process gets polymkeric substance 32g, catalytic efficiency 2.1 * 10 with embodiment 15
6GPE/mol Crh.
Claims (6)
1. chromium diimine olefine polymerizing catalyst, it has following structure:
R wherein
1Be methyl, ethyl or propyl group; R
2And R
3Can be identical or different, be respectively H, methyl, ethyl or methoxyl group.
2. according to the described chromium diimine olefine polymerizing catalyst of claim 1, wherein, R
1It is methyl; R
2And R
3Identical or different, be respectively H, methyl, ethyl or methoxyl group.
3. according to the described chromium diimine olefine polymerizing catalyst of claim 1, wherein, R
1It is methyl; R
2Be H; R
3Be methyl or ethyl.
4. according to the described chromium diimine olefine polymerizing catalyst of claim 1, wherein, R
1It is methyl; R
2Be methyl or ethyl; R
3Be H.
5. method for preparing the described chromium diimine olefine polymerizing catalyst of claim 1:
Under the effect of four butyl bromation amine phase-transfer catalyst, the mixed solution of reflux sodium sulfide solution and o-chloronitrobenzene toluene solution gets 2,2 '-dinitrobenzene diphenyl sulfide; In the presence of small amount of hydrochloric acid, with iron powder reducing 2,2 '-dinitrobenzene diphenyl sulfide gets 2,2 '-two amido diphenyl sulfides; Under the acid catalysis, carry out the condensation reaction of 2,2 '-two amido diphenyl sulfides and arone, obtain the western Buddhist alkali shown in the following formula,
Under the condition of anhydrous and oxygen-free, carry out the reaction between above-mentioned western Buddhist alkali and the chromium trichloride tetrahydrofuran (THF) title complex, the chromium diimine olefine polymerizing catalyst that obtains being shown below,
R wherein
1Be methyl, ethyl or propyl group; R
2And R
3Can be identical or different, be respectively H, methyl, ethyl or methoxyl group.
6. the method for a synthesizing polyethylene is comprising using the described chromium diimine olefine polymerizing catalyst of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01143496 CN1357556A (en) | 2001-12-29 | 2001-12-29 | Chromium diimine olefine polymerizing catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01143496 CN1357556A (en) | 2001-12-29 | 2001-12-29 | Chromium diimine olefine polymerizing catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315573C (en) * | 2005-01-07 | 2007-05-16 | 吉林大学 | Beta-diimide nickel compound/alkyl aluminium catalyst system and its application |
| CN100362028C (en) * | 2005-07-29 | 2008-01-16 | 中国科学院上海有机化学研究所 | Ethene polymerization catalyst , synthesis method and uses |
| CN101402695B (en) * | 2008-11-13 | 2012-06-27 | 复旦大学 | Semi-sandwich alum-chromium olefin polymerizing catalyst, preparation and uses thereof |
-
2001
- 2001-12-29 CN CN 01143496 patent/CN1357556A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315573C (en) * | 2005-01-07 | 2007-05-16 | 吉林大学 | Beta-diimide nickel compound/alkyl aluminium catalyst system and its application |
| CN100362028C (en) * | 2005-07-29 | 2008-01-16 | 中国科学院上海有机化学研究所 | Ethene polymerization catalyst , synthesis method and uses |
| CN101402695B (en) * | 2008-11-13 | 2012-06-27 | 复旦大学 | Semi-sandwich alum-chromium olefin polymerizing catalyst, preparation and uses thereof |
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