CN1247597C - Preparation method of aluminium methide oxyalkane - Google Patents
Preparation method of aluminium methide oxyalkane Download PDFInfo
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- CN1247597C CN1247597C CN 03157353 CN03157353A CN1247597C CN 1247597 C CN1247597 C CN 1247597C CN 03157353 CN03157353 CN 03157353 CN 03157353 A CN03157353 A CN 03157353A CN 1247597 C CN1247597 C CN 1247597C
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- preparation
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- halomethane
- decane
- methylaluminoxane
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Abstract
The present invention provides a preparation method of a metallocene cocatalyst, namely methylaluminoxane, for olefinic polymerization. Methyl bromide carried with steam is directly adopted to react with high-grade alkylaluminium to obtain the metallocene cocatalyst. Compared with a conventional method, the present invention has high synthesis yield of the target product (favorably up to 60%) and simple technological process. The cocatalyst is used for a metallocene catalysis system and has favorable co-catalytic performance.
Description
Technical field
The present invention relates to the preparation method of alkylaluminoxane, particularly the preparation method of metallocene promotor-methylaluminoxane.
Background technology
The synthetic method of methylaluminoxane that is used to do the metallocene promotor is a lot, is summarised as two classes substantially: directly water conservancy project skill and water conservancy project skill indirectly.Directly the yield of water conservancy project skill target product is higher, but production process danger is bigger, simultaneously, in order to solve the danger of production process, often need to design various specific installations, make the construction investment of full scale plant increase (US4924018 greatly, US4772736, US4937363, US4908463, US5087713, US5041585).
General crystalline hydrate and the trimethyl aluminium of adopting of water conservancy project skill reacts indirectly.The synthetic method of existing bibliographical information all is that crystalline hydrate and solvent are mixed with suspension in reactor, the synthetic method of under constantly stirring trimethyl aluminium solution being reacted while adding.Its main drawback is: owing to be that trimethyl aluminium solution is added in the suspension of crystalline hydrate gradually, the initial trimethyl aluminium overwhelming majority that adds is Al (OH) by water transform excessive relatively in the system
3, have only when the free-water concentration in the system is reduced to a certain degree, generate Al (OH)
3Side reaction just be reduced to accessory degree.Therefore, the yield of this synthesis technique target product is lower, causes the cost of the finished product higher; Adopt this technology, the yield of target product generally be no more than 40% (US5099050, US5041583, EP393358A2, EP383255A2, EP208561A2, US5248801).
US5003095 provide a kind of with the senior alkyl aikyiaiurnirsoxan beta (as: the ethyl aikyiaiurnirsoxan beta, EAO) with monobromethane in the presence of catalyzer, by transalkylation reaction, generate the synthetic method of methylaluminoxane (MAO).But this method needs at first to make senior alkyl aikyiaiurnirsoxan beta (EAO) with senior alkyl aluminium by direct water or indirect water conservancy project skill, makes the senior alkyl aikyiaiurnirsoxan beta generate methylaluminoxane (MAO) with monobromethane generation transalkylation reaction then in the presence of catalyzer.Therefore, the technical process of this method is still quite complicated.
Summary of the invention
The present invention provides a kind of improving one's methods of methylaluminoxane that prepare on the basis of above-mentioned prior art.
Be raw material with the aluminum alkyls among the present invention, in the presence of catalyzer by with the halomethane reaction that is entrained with water vapor, can obtain the methylaluminoxane of high yield.
Used aluminum alkyls triethyl aluminum preferably among the present invention, but beyond the triethyl aluminum as aluminium isobutyl, aluminum alkylss such as tertiary butyl aluminium also should belong to scope disclosed by the invention.
Used catalyzer is this technical field halogenation bismuth, particularly Trichlorobismuthine commonly used.Understand and " catalytic amount " of the present invention is that those skilled in the art are common, can play katalysis and obtain higher product yield.
The acquisition mode of the halomethane of water entrainment steam can be multiple, and the present invention does not do special qualification, but discloses a kind of better suited method among the present invention.Promptly be to realize that by the import of the airway of halomethane is inserted in the distilled water at this moment, the outlet of halomethane airway should place the water container top.Adopt this mode, the temperature of the distilled water that the ratio of halomethane and water vapour can be inserted by the import of airway of control halomethane, and measures such as pipeline is incubated are realized.The ratio of water vapour and halomethane is counted in molar ratio and can be preferably between 1～5 between 1～7 among the present invention.But suitable molar ratio can have bigger variation with the insulation situation of operational condition and equipment etc. to a great extent between water vapour and the halomethane.
The present invention also adds organic solvent as required, is that boiling point is lower than the reaction desired reaction temperature to the requirement of solvent, as: decane, toluene, benzene or hexanaphthene etc. are preferably decane and toluene.
Thus, the present invention proposes complete and suitable methylaluminoxane preparation method, specifically be that reaction unit is through behind the sufficient inert gas replacement, in the disposable adding reactor of decane solution of the triethyl aluminum that the First Astronautic Research Institute for Measurement and Test is needed, under constantly stirring, the Trichlorobismuthine of catalytic amount is added in the reactor, treat the abundant complexing of Trichlorobismuthine and triethyl aluminum after, beginning feeds the methyl bromide gas that is entrained with water vapour in reactor, finish reaction when no gas produces.
The concentration of triethyl aluminum of the present invention/decane solution can be arbitrarily.But consider that from the angle of safety the triethyl aluminum/decane solution that generally can select 0.1～4.5mol/L is preferably 1.5～3.0mol/L as the initial action material.Its temperature of reaction can be 50 ℃～140 ℃, is preferably 80～120 ℃.
Method provided by the invention is owing to be that the monobromethane that will be entrained with water vapour feeds in the trialkylaluminium solution, in feeding the process of halomethane, it is simultaneous generating the transalkylation reaction that generates methylaluminoxane between the hydrolysis reaction that generates methylaluminoxane between hydrolysis reaction, trimethyl aluminium and the water that generates alkylaluminoxane between transalkylation reaction, trialkylaluminium and the water of trimethyl aluminium and alkylaluminoxane and the monobromethane etc. between trialkylaluminium and the monobromethane.Although reaction process is very complicated,, the net result of transalkylation reaction and hydrolysis reaction all is to have generated methylaluminoxane.Therefore simplified the aftertreatment of the complexity in the existing preparation methylaluminoxane process greatly.This technology makes target product methylaluminoxane (MAO) obtain higher reaction yield simultaneously, can reach preferably (mole number by the trialkylaluminium that feeds intake calculates) more than 60%.
Another tangible advantage is because reaction is to carry out in the decane solution of trialkylaluminium, the decane solution of trialkylaluminium that can adopt any concentration in the reaction process is as starting raw material, thereby guarantee to avoid in the reaction process using dense aluminum alkyls, thereby can avoid effectively in the synthetic trimethyl aluminium process, especially the danger of dense trimethyl aluminium involuntary ignition in the rectifying has solved the safety issue of alkylaluminoxane and synthesis material production process thereof effectively.Above-mentioned these 2 compared with prior art have tangible difference and obvious improvement.
Embodiment
Below by concrete example the present invention is done better explanation, should not only limit to this but understand the present invention.
To use following notion among the present invention, explain especially at this:
Embodiment 1
Reaction flask adds 50ml2mol.L through behind sufficient vacuum-nitrogen replacement
-1Triethyl aluminum (TEA) decane solution starts stirring, and the inertia protection adds 2gBiCl down
3, slowly be warmed up to 120 ℃.By behind 30 ℃ of distilled water, the monobromethane that will be entrained with water vapour feeds in the reaction flask with methyl bromide gas.When the mole number for the treatment of methyl bromide gas amounts to 0.4mol, stop to feed monobromethane, when continuing to be stirred to no gas and producing, stopped reaction.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 3.1g.Mole number by the triethyl aluminum that feeds intake calculates, and the yield of purpose product methylaluminoxane is 53.5%.
Above-mentioned methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 584 gram polyethylene.
Embodiment 2
Reaction flask adds 50ml2mol.L through behind sufficient vacuum-nitrogen replacement
-1Triethyl aluminum (TEA) decane solution starts stirring, and the inertia protection adds 2gBiCl down
3, slowly be warmed up to 120 ℃.By behind 50 ℃ of distilled water, the monobromethane that will be entrained with water vapour feeds in the reaction flask with methyl bromide gas.When the mole number for the treatment of methyl bromide gas amounts to 0.45mol, stop to feed monobromethane, when continuing to be stirred to no gas and producing, stopped reaction.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 3.5g.Mole number by the triethyl aluminum that feeds intake calculates, and the yield of purpose product methylaluminoxane is 60.3%.
Above-mentioned methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 651 gram polyethylene.
Embodiment 3
Reaction flask adds 50ml2mol.L through behind sufficient vacuum-nitrogen replacement
-1Triethyl aluminum (TEA) toluene solution starts stirring, and the inertia protection adds 2gBiCl down
3, slowly be warmed up to 100 ℃.By behind 50 ℃ of distilled water, the monobromethane that will be entrained with water vapour feeds in the reaction flask with methyl bromide gas.When the mole number for the treatment of methyl bromide gas amounts to 0.5mol, stop to feed monobromethane, when continuing to be stirred to no gas and producing, stopped reaction.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 2.9g.Mole number by the triethyl aluminum that feeds intake calculates, and the yield of purpose product methylaluminoxane is 50%.
Above-mentioned methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 604 gram polyethylene.
Embodiment 4
Reaction flask adds 50ml2mol.L through behind sufficient vacuum-nitrogen replacement
-1Triethyl aluminum (TEA) toluene solution starts stirring, and the inertia protection adds 2gBiCl down
3, slowly be warmed up to 120 ℃.By behind 20 ℃ of distilled water, the monobromethane that will be entrained with water vapour feeds in the reaction flask with methyl bromide gas.When the mole number for the treatment of methyl bromide gas amounts to 0.6mol, stop to feed monobromethane, when continuing to be stirred to no gas and producing, stopped reaction.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 2.85g.Mole number by the triethyl aluminum that feeds intake calculates, and the yield of purpose product methylaluminoxane is 49%.
Above-mentioned methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 526 gram polyethylene.
Claims (11)
1, the preparation method of methylaluminoxane is characterized in that with triethyl aluminum, aluminium isobutyl or tertiary butyl aluminium be raw material, in the presence of 50 ℃～140 ℃ and halogenation bismuth catalyst by obtaining with the halomethane reaction that is entrained with water vapor.
2, preparation method according to claim 1 is characterized in that reaction is to carry out under 80～120 ℃ of temperature.
3, preparation method according to claim 2 is characterized in that also adding organic solvent in the reaction, and it is temperature required that solvent boiling point should be lower than reaction.
4. preparation method according to claim 3 is characterized in that solvent is decane, toluene, benzene or hexanaphthene.
5. preparation method according to claim 4 is characterized in that solvent is a decane.
6. preparation method according to claim 5 is characterized in that the aluminum alkyls/decane strength of solution as the initial action material is 0.1～4.5mol/L.
7. preparation method according to claim 6 is characterized in that aluminum alkyls/decane strength of solution is 1.5～3.0mol/L.
8. the preparation method one of described according to claim 1-7, the halomethane that it is characterized in that water entrainment steam is to realize by the airway import of halomethane is inserted in the distilled water.
9. preparation method according to claim 8 is characterized in that the ratio of water vapour and halomethane is counted between 1～7 in molar ratio.
10. preparation method according to claim 9 is characterized in that the ratio of water vapour and halomethane is counted between 1～5 in molar ratio.
11. preparation method according to claim 10, it is characterized in that reaction unit is through behind the sufficient inert gas replacement, in the disposable adding reactor of decane solution of the triethyl aluminum that the First Astronautic Research Institute for Measurement and Test is needed, under constantly stirring, the Trichlorobismuthine of catalytic amount is added in the reactor, after treating the abundant complexing of Trichlorobismuthine and triethyl aluminum, beginning feeds the methyl bromide gas that is entrained with water vapour in reactor, finishes reaction when no gas produces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03157353 CN1247597C (en) | 2003-09-19 | 2003-09-19 | Preparation method of aluminium methide oxyalkane |
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|---|---|---|---|
| CN 03157353 CN1247597C (en) | 2003-09-19 | 2003-09-19 | Preparation method of aluminium methide oxyalkane |
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| CN1597685A CN1597685A (en) | 2005-03-23 |
| CN1247597C true CN1247597C (en) | 2006-03-29 |
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| CN 03157353 Expired - Fee Related CN1247597C (en) | 2003-09-19 | 2003-09-19 | Preparation method of aluminium methide oxyalkane |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993452B (en) * | 2009-08-12 | 2012-10-17 | 中国石油天然气股份有限公司 | Method for preparing anti-gelling methylaluminoxane solution |
| CN102675494B (en) * | 2012-01-15 | 2014-08-13 | 河南科技大学 | Preparation method of alkylaluminoxane promoter |
| CN109942611B (en) * | 2017-12-21 | 2021-08-03 | 中国石油化工股份有限公司 | Preparation method of trimethylaluminum |
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