CN100413870C - Method for producing alkylaluminoxane - Google Patents
Method for producing alkylaluminoxane Download PDFInfo
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- CN100413870C CN100413870C CNB2005100711023A CN200510071102A CN100413870C CN 100413870 C CN100413870 C CN 100413870C CN B2005100711023 A CNB2005100711023 A CN B2005100711023A CN 200510071102 A CN200510071102 A CN 200510071102A CN 100413870 C CN100413870 C CN 100413870C
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Abstract
The present invention provides a method for preparing alkylaluminoxane by direct water technology. The temperature of a reaction device is controlled from 3 to 8 DEG C. Solid ice blocks are added into solution of alkyl aluminium/inert solvent by solid feeder protected by inert gas step by step to have a reaction. The process of the reaction is easy to control, special reaction equipment does not need, and the reaction yield of the target product is high. The obtained product is used for a metallocene or metallocene/ post transition metal catalytic system for alkene polymerization. The present invention has good auxiliary catalytic performance.
Description
Technical field
The present invention relates to the preparation method of alkylaluminoxane, particularly direct water conservancy project skill prepares the method for alkylaluminoxane.
Background technology
The preparation method of alkylaluminoxane is a lot, can be summarized as direct water conservancy project skill and indirect water conservancy project skill two big classes.
The water conservancy project skill adopts the reaction of crystalline hydrate and aluminum alkyls usually indirectly.The preparation method of existing bibliographical information generally is mixed with suspension with crystalline hydrate and solvent in reactor, the preparation method who under constantly stirring alkyl aluminum solutions is reacted while adding.Its main drawback is: owing to be that alkyl aluminum solutions is added in the suspension of crystalline hydrate gradually, the initial aluminum alkyls 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 synthetic method target product is lower, cause the cost of the finished product higher (US5099050, US5041583, EP393358A
2, EP383255 A
2, EP208561 A
2, US5248801).
Directly the water conservancy project skill is meant the control certain process conditions, the water under the various existences (ice, liquid water, water vapour) is introduced the solution reaction of reactor and aluminum alkyls/inert solvent by suitable mode.In directly water conservancy project is planted, introducing mode as the water of one of raw material can be diversified, such as: with static mixer with water-dispersion in organic solvent and introduce (USP4924018, USP4908463), by atomising unit water is become vaporific form and introduce (USP4772736, USP5041585), with the ultrasonic dispersing method with water-dispersion in organic solvent and introduce (EP513808A
2), carry the way of a small amount of water vapor secretly with noble gas and introduce (USP4937363), with the machinery emulsification method with water-dispersion in organic solvent and introduce (USP4730072, USP4968827, EP257695A
2) etc.
In USP5087713, people such as Hansjoerg Sinn have invented a kind of under extremely low temperature (33 ℃-53 ℃), make aluminum alkyls directly act on the surface of ice and the method for synthesis of alkyl aikyiaiurnirsoxan beta.The principle of this method is: under extremely low temperature, ice cube and aluminum alkyls/inert solvent dilute solution is reacted to each other under the effect of mechanical force or the fluid impact power that produces owing to vigorous stirring, generate alkylaluminoxane.This synthetic method is very high to the requirement of equipment, and especially, for guaranteeing the extremely low reaction environment of security needs temperature, the facility investment of production equipment is bigger, and, react also bad control, cause security incident easily.
The common feature of existing direct water conservancy project technology is: aluminum alkyls be in solid-state, liquid state or gasiform water direct reaction, on the one hand, water is to introduce in the alkyl aluminum solutions by suitable mode, thereby can suppress the side reaction that taken place in the indirect water conservancy project skill process effectively, the yield of target product is higher; On the other hand, because the reaction of aluminum alkyls and water is very violent, react restive, therefore control and the synthesizer to reaction all has high requirement.In addition, to the add-on of the concentration of the aluminum alkyls that enters reactor and water under the prerequisite that guarantees the building-up reactions yield, must strict control, otherwise cause security incident easily.
In brief, above-mentioned direct water conservancy project skill can make target product obtain higher reaction yield, but production process danger is bigger, simultaneously, in order to solve the danger of production process, often need to design various specific installations, this makes the investment cost of plant construction increase greatly.
Summary of the invention
The present invention provides a kind of improved synthesis of alkyl aikyiaiurnirsoxan beta direct water conservancy project technology on the basis of above-mentioned prior art.
Method provided by the invention comprises following key points for operation: reaction unit is through sufficient inertia displacement; In the disposable adding reaction unit of aluminum alkyls/inert solvent solution that the First Astronautic Research Institute for Measurement and Test is needed and begin to reduce the material in reactor temperature to below-10 ℃; Progressively add solid ice in the reactor by the feeder for solid materials that can realize the inertia protection under the agitation condition; When waiting not have the bubble generation behind reinforced the finishing, progressively be warming up to 25～100 ℃, continue to stir 2～5 hours.
Shape and size to solid ice among the present invention are not done special qualification, but consider the steady control and the reinforced process complexity of reaction process, and preferred solid ice is shaped as sphere.The control of solid ice feed rate is subjected to the influence of solid ice shape, size and factors such as alkyl aluminum solutions initial reaction, temperature.The solid ice feed rate control benchmark that the present invention recommends is: according to the difference of reaction scale, with temperature rise in initial reaction temperature is compared reaction unit less than 8 ℃.
In the method for the present invention, the temperature of solid ice adition process can be to be lower than any temperature of-10 ℃.But take all factors into consideration the feed rate of solid ice, the throughput of device and the factors such as energy expenditure of operating process, the solid ice charge temperature is preferably-15 ℃～-25 ℃; After reaction finishes, progressively heat up and be preferably 25 ℃～80 ℃.
Aluminum alkyls as raw material among the present invention is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1～C
20Alkyl, be preferably methyl.
By the method for the invention synthetic alkylaluminoxane product is the various alkylaluminoxanes corresponding with above-mentioned alkyl, is preferably methylaluminoxane (MAO).
The concentration of the aluminum alkyls/inert solvent solution among the present invention can be any concentration that is lower than 4mol/L, is preferably between 1～3mol/L; Along with the concentration difference of the alkyl aluminum solutions that feeds intake, require the size of solid ice and feed rate, solution initial reaction temperature to want respective change.
In the method for the present invention, aluminum alkyls can be 0.1～1.0 with the ratio of the amount of substance of solid ice, is preferably 0.3～0.8.
Reaction unit of the present invention can be common stirring tank, and the common feeder for solid materials of feeder for solid materials recommendation employing of noble gas protection fits into tracheae respectively again and blow-down pipe both can.
Method provided by the invention is connected as if the two stills of employing, aluminum alkyls continuously feeding in the reaction process, and solid ice is intermittently added in good time, is reacted to the continuous discharging of reaction mixture to a certain degree, also can realize serialization production.
The present invention compared with prior art, have several big advantages: (1) solid ice is progressively to add, and can control " temperature runaway " phenomenon of reaction process effectively by the feed rate of control solid ice, therefore needn't make the solution of the aluminum alkyls/inert solvent in the reactor be in very rare state, its concentration is reached about 3.0mol/L, thereby solved the safety problem of direct water conservancy project skill synthesis of alkyl aikyiaiurnirsoxan beta effectively, and can improve the throughput of device greatly, reduced the solvent treatment amount of last handling process simultaneously to a great extent; (2) owing to can control " temperature runaway " of reaction process effectively, therefore do not need to use the low temperature environment of-40 ℃ even-80 ℃ to react (certainly under such low temperature, reaction of the present invention also can be carried out), get final product and only need reacting liquid temperature to be lower than-10 ℃; (3) of the present invention being reflected under the higher relatively temperature carried out, and be therefore low relatively to the requirement of equipment, can significantly reduce the facility investment of production equipment.
The alkylaluminoxane yield of being produced by method of the present invention reaches as high as more than 85%, when being used for compounded catalyst such as olefinic polymerization metallocene or metallocene/rear transition metal, has good promoting catalysis.
The following example can further strengthen the understanding of the present invention, but can not be interpreted as it is limitation of the invention.
Embodiment
Embodiment 1
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 3.2molL through behind sufficient vacuum-nitrogen replacement
-1Trimethyl aluminium (TMA)/toluene solution, start stirring, when solution temperature is reduced to-20 ℃ in the question response bottle, in 5 hours, add in the reaction flask gradually 14.4g ice (spherical, diameter is about 3mm) by feeder for solid materials (being equipped with nitrogen pipeline and blow-down pipe); When no tangible bubble is emitted in the question response bottle, be warmed up to 40 ℃ gradually, continue to stir stopped reaction 3 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white methylaluminoxane solid 53.8g.
Embodiment 2
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 250ml 3.5molL through behind sufficient vacuum-nitrogen replacement
-1Triisobutyl aluminium/toluene solution starts stirring, when solution temperature is reduced to-25 ℃ in the question response bottle, by feeder for solid materials 7.0g ice (powdery) is added in the reaction flask in 4 hours gradually.Reinforced finishing is warmed up to 75 ℃ gradually, continues to stir stopped reaction 3 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white isobutyl aluminium alkoxide solid 42.9g.
Embodiment 3
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 2.5molL through behind sufficient vacuum-nitrogen replacement
-1The TMA/ toluene solution starts stirring, when solution temperature is reduced to-20 ℃ in the question response bottle, by feeder for solid materials 5.6g ice (shape and size distribution inequality) is added in the reaction flask in 3 hours gradually.Reinforced finishing is warmed up to 25 ℃ gradually, continues to stir stopped reaction 4 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white methylaluminoxane solid 21.8g.
Embodiment 4
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 2molL through behind sufficient vacuum-nitrogen replacement
-1The triethyl aluminum toluene solution starts stirring, when solution temperature is reduced to-25 ℃ in the question response bottle, by feeder for solid materials 12.0g ice (spherical, diameter is about 3mm) is added in the reaction flask in 3 hours gradually.Reinforced finishing is warmed up to 65 ℃ gradually, continues to stir stopped reaction 3 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white ethyl aikyiaiurnirsoxan beta solid 49g.
Embodiment 5
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 1.5molL through behind sufficient vacuum-nitrogen replacement
-1The TMA toluene solution starts stirring, when solution temperature is reduced to-18 ℃ in the question response bottle, by feeder for solid materials 12g ice (spherical, diameter is about 2mm) is added in the reaction flask in 2 hours gradually.Reinforced finishing is warmed up to 60 ℃ gradually, continues to stir stopped reaction 2 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white methylaluminoxane solid 37g.
Embodiment 6
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 1.0molL through behind sufficient vacuum-nitrogen replacement
-1Triisobutylaluminum toluene solution is started stirring, when solution temperature is reduced to-15 ℃ in the question response bottle, by feeder for solid materials 9.0g ice (spherical, diameter is about 3mm) is added in the reaction flask in 1.5 hours gradually.Reinforced finishing is warmed up to 50 ℃ gradually, continues to stir stopped reaction 3 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white isobutyl aluminium alkoxide solid 32.5g.
Embodiment 7
The 2 liter reaction flasks that are equipped with nitrogen, emptying and cooling system add 500ml 1.0molL through behind sufficient vacuum-nitrogen replacement
-1The triethyl aluminum toluene solution starts stirring, when solution temperature is reduced to-26 ℃ in the question response bottle, by feeder for solid materials 6.3g ice (spherical, diameter is about 2mm) is added in the reaction flask in 1 hour gradually.Reinforced finishing is warmed up to 35 ℃ gradually, continues to stir stopped reaction 3 hours.Adopt G
4The core filtering reacting liquid, removal of solvent under reduced pressure gets white ethyl aikyiaiurnirsoxan beta solid 25.9g.
The alkylaluminoxane that the foregoing description makes is used for vinyl polymerization and the results are shown in Table
*
* polymerizing condition:, under the 0.8Mpa, made vinyl polymerization 1 hour at 80 ℃
Claims (11)
1. the preparation method of alkylaluminoxane as synthesis material, is characterized in that comprising successively following steps with solid ice and aluminum alkyls:
A) reaction unit is through sufficient inertia displacement;
B) the disposable adding reaction unit of aluminum alkyls/inert solvent solution that the First Astronautic Research Institute for Measurement and Test is needed, and be cooled to and be lower than-10 ℃;
C) under agitation condition, solid ice is progressively added in the reaction unit, the adding speed control of solid ice reacting liquid temperature and initial reaction temperature mutually specific temperature rise less than 8 ℃, when waiting not have bubble behind reinforced the finishing and producing;
D) progressively be warming up to 25～100 ℃, continue to stir 2～5 hours.
2. preparation method according to claim 1, the adding that it is characterized in that solid ice is to realize by the feeder for solid materials of noble gas protection.
3. preparation method according to claim 2 is characterized in that assembling respectively on the feeder for solid materials admission line and blow-down pipe.
4. preparation method according to claim 3 is characterized in that solid ice is shaped as sphere.
5. preparation method according to claim 1 is characterized in that aluminum alkyls is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1～C
20Alkyl.
6. preparation method according to claim 5 is characterized in that aluminum alkyls is a trimethyl aluminium.
7. preparation method according to claim 1 is characterized in that the concentration of aluminum alkyls/inert solvent solution is lower than 4mol/L.
8. preparation method according to claim 7, the concentration that it is characterized in that aluminum alkyls/inert solvent solution is 1～3mol/L.
9. preparation method according to claim 8 is characterized in that the aluminum alkyls and the ratio of the amount of substance of solid ice are 0.1～1.0.
10. preparation method according to claim 9 is characterized in that the aluminum alkyls and the ratio of the amount of substance of solid ice are 0.3～0.8.
11. the preparation method one of described according to claim 1 or 3-10 is characterized in that comprising successively following steps:
A) reaction unit is through sufficient inertia displacement;
B) the disposable adding reaction unit of aluminum alkyls/inert solvent solution that the First Astronautic Research Institute for Measurement and Test is needed, and be cooled to-15 ℃～-25 ℃;
C) feeder for solid materials by noble gas protection progressively adds solid ice in the reaction unit under agitation condition, the adding speed control of solid ice reacting liquid temperature and initial reaction temperature mutually specific temperature rise less than 8 ℃, when waiting not have the bubble generation behind reinforced the finishing;
D) progressively be warming up to 25～80 ℃, continue to stir 2～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100711023A CN100413870C (en) | 2005-05-20 | 2005-05-20 | Method for producing alkylaluminoxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100711023A CN100413870C (en) | 2005-05-20 | 2005-05-20 | Method for producing alkylaluminoxane |
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|---|---|
| CN1865262A CN1865262A (en) | 2006-11-22 |
| CN100413870C true CN100413870C (en) | 2008-08-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190677B (en) * | 2010-03-03 | 2013-07-31 | 中国石油天然气股份有限公司 | Atomization synthesizer and application thereof in synthesis of alkylaluminoxane |
| CN102190678B (en) * | 2010-03-16 | 2015-07-01 | 大庆石油学院 | Method for preparing modification aluminoxane |
| CN102286012B (en) * | 2010-06-21 | 2013-10-16 | 中国石油天然气股份有限公司 | Preparation method of alkylaluminoxane solution |
| SG11201506224UA (en) | 2013-02-08 | 2015-09-29 | Mitsui Chemicals Inc | Solid polyaluminoxane composition, olefin polymerization catalyst, olefin polymer production method and solid polyaluminoxane composition production method |
| CN111647012B (en) * | 2020-04-24 | 2021-09-24 | 浙江大学 | Method for preparing alkylaluminoxane by using microreactor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087713A (en) * | 1987-09-20 | 1992-02-11 | Schering Ag | Process for producing aluminum oxanes, in particular methylaluminum oxane, from water and organoaluminum compounds, in particular trimethylaluminum, in inert hydrocarbons |
| JP2000256366A (en) * | 1999-03-09 | 2000-09-19 | Nippon Alkyl Alum Kk | Production of alkylaluminoxane |
| CN1523027A (en) * | 2003-02-20 | 2004-08-25 | 中国石油天然气股份有限公司 | Synthetic process for alkyl aluminum oxane |
-
2005
- 2005-05-20 CN CNB2005100711023A patent/CN100413870C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087713A (en) * | 1987-09-20 | 1992-02-11 | Schering Ag | Process for producing aluminum oxanes, in particular methylaluminum oxane, from water and organoaluminum compounds, in particular trimethylaluminum, in inert hydrocarbons |
| JP2000256366A (en) * | 1999-03-09 | 2000-09-19 | Nippon Alkyl Alum Kk | Production of alkylaluminoxane |
| CN1523027A (en) * | 2003-02-20 | 2004-08-25 | 中国石油天然气股份有限公司 | Synthetic process for alkyl aluminum oxane |
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| CN1865262A (en) | 2006-11-22 |
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