CN1063751C - Synthetic process for alkyl aluminium - Google Patents
Synthetic process for alkyl aluminium Download PDFInfo
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- CN1063751C CN1063751C CN98106736A CN98106736A CN1063751C CN 1063751 C CN1063751 C CN 1063751C CN 98106736 A CN98106736 A CN 98106736A CN 98106736 A CN98106736 A CN 98106736A CN 1063751 C CN1063751 C CN 1063751C
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- iron
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- trimethyl aluminium
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Abstract
The present invention relates to a synthetic method of hydrocarbyl aluminum. In the method, under the existence of a catalytic system formed by iron bases, interaction of the iron-antimony base compounds, organic aluminum compounds and halogenated hydrocarbon, organic aluminum compounds react with halogenated hydrocarbon for preparing hydrocarbyl aluminum. The iron base or iron-antimony base catalytic system acts on hydrocarbyl aluminum at least comprising two carbon atoms in hydrocarbyl, and halogenated hydrocarbon for generating another kind of hydrocarbyl aluminum; particularly, the reaction of trimethyl aluminum has an excellent catalytic effect. The method has the advantages of low production cost, easy reaction product separation and high yield of target products.
Description
The present invention relates to a kind of synthetic method of alkyl aluminium, relate in particular to a kind of method that under iron-based or iron-antimony-based catalyst effect, prepares trimethyl aluminium by monobromethane and triethyl aluminum.
The method for preparing trimethyl aluminium is a lot, as:
(1) organoaluminum and mercury alkylide reaction.
(2) Organohalogen compounds and aluminium or magnesium-aluminum alloy reaction.
(3) aluminum halide and Green's reagent react.
(4) alkene and aluminum hydride or lithium aluminium hydride reaction.
(5) senior alkyl aluminium and iodo-methyl aluminium or CH
3The I reaction.
(6) trialkyl aluminium and idoalkane react in the presence of catalytic component based on vanadium.
The common issue with that above-mentioned these methods exist is: itself costs an arm and a leg reactant, and long reaction time and yield are low, and reaction end back distillation is purified time-consuming, is difficult to industrialization.
Early eighties, US364872 disclose a kind of trimethyl aluminium preparation method of relatively economical--alkyl exchange process, and soon reactant trialkyl aluminium, halomethane drop into airtight autoclave internal reaction with the bismuth compound as catalyzer and generate trimethyl aluminium.The subject matter that this method exists is that bismuth compound is very expensive, though the laboratory yield has raising, but industrialization is still very difficult, reason is to react in airtight autoclave and finishes, along with the carrying out of reaction, the ratio of halohydrocarbon and trialkyl aluminium raises gradually in the reactive system, and halohydrocarbon and trialkyl aluminium can react the various haloalkyl aluminium of generation, increased and separated the difficulty of purifying, and trialkyl aluminium and halohydrocarbon vigorous reaction have and cause the danger of exploding.
At above-mentioned defective, US4925962 has proposed a kind of improvement technology, promptly in control halomethane inlet amount, boils off halohydrocarbon from reactor, thereby these two kinds of simultaneous amounts of compound in the control reactor are avoided blast.But technology still uses bismuth compound to make catalyzer, and production cost is high, and product yield is also not very good.
The object of the present invention is to provide a kind of synthesis technique of alkyl aluminium, make in this technological process employed catalyzer cheap and easy to get, reduce the by product of reaction, and improve target product yield greatly.
The synthetic method of alkyl aluminium of the present invention is: the trialkyl aluminium and the halohydrocarbon prepared in reaction trialkyl aluminium under iron-based or iron-antimony base catalyst system effect that contain two carbon atoms in the alkyl at least.The catalytic mechanism of this catalyst system it be unclear that, but, need one regularly with inferring according to its catalysis, initiation reaction, the activity of such catalysts component may be a kind of middle transition complex compound that is formed by iron or iron-antimony, trialkyl aluminium and halohydrocarbon acting in conjunction, and this complex compound contains iron or iron-antimony, aluminium, alkyl and other possible group.
The forming process of iron-based of the present invention or iron-antimony-based catalyst is as follows: solvent-free or have under the condition that inertia aliphatic hydrocarbon or aromatic hydrocarbon solvent exist, add the mixture of iron cpd or iron, antimony compounds.Temperature is risen to 40 ℃-80 ℃, and constant temperature stirs down and adds halohydrocarbon gradually, drips alkyl aluminium simultaneously.Behind the several minutes, the temperature of observing total system begins to rise.This sign activity of such catalysts component forms, and reaction begins to cause.In above-mentioned preparation process, as do not add halohydrocarbon when dripping alkyl aluminium simultaneously, with after prolonging, add halohydrocarbon when then needing as reactant with Preparation of Catalyst, reaction ability is instant to be caused, and this explanation halohydrocarbon forms and reacts in the elicitation procedure and can play a driving role at catalyzer.In catalyst preparation process, used halohydrocarbon is halomethane or senior halohydrocarbon, wherein monobromethane most preferably.Suitable alkyl aluminium is trimethyl aluminium, triethyl aluminum, three-n-propyl aluminium, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum etc., and wherein best is that trimethyl aluminium and triethyl aluminum, hydrocarbylaluminum also can be used.Suitable iron cpd is first machine iron cpd or organoiron compound, as iron trichloride, ferric bromide, ferrocene etc., and iron trichloride most preferably wherein.Suitable antimony compounds can be butter of antimony, antimony pentachloride etc., wherein butter of antimony most preferably.
The building-up process of alkyl aluminium of the present invention needs to carry out under noble gas (as nitrogen, hydrogen etc.) protection, and used noble gas all needs strict deoxidation, the processed of process in advance, and used instrument all need be cleaned and thorough drying.After device connects.Through vacuum repeatedly--nitrogen replacement.Trialkyl aluminium of the present invention is the synthetic method of trimethyl aluminium especially.In the concrete operations following dual mode can be arranged:
(1) interruption method: prepare iron-based or iron-antimony-based catalyst earlier in reactor, add reactant halohydrocarbon and trialkyl aluminium then, reinforced finishing continues constant temperature stirring 4-5 hour, the reaction end.Analysis, detection reaction mixture.
2) continuous processing: the mixture that in reactor, adds a certain amount of iron cpd or iron-antimony compounds, add (or not adding) inertia aliphatic hydrocarbon or aromatic hydrocarbon and make solvent, be warming up to 40 ℃-80 ℃ gradually, add halohydrocarbon and alkyl aluminium, after the question response system temperature begins to rise gradually, homo(io)thermism reacted reinforced finishing within the specific limits after.Continuing constant temperature stirred 4-5 hour.Analysis, detection reaction mixture.
The control principle of above-mentioned temperature of reaction is: with initiation reaction and don't cause reactant and decomposition and the volatilization do not expect takes place product, adoptable temperature range is: 40 ℃-125 ℃, wherein, with 80 ℃-120 ℃ for the most suitable.If adopt higher alkyl aluminium and halomethane prepared in reaction trimethyl aluminium, because the halohydrocarbon molecular weight of used alkyl aluminium and generation is bigger, then Shi Yi temperature of reaction correspondingly can be higher than 80 ℃, but should not be higher than 125 ℃, volatilizees in order to avoid the trimethyl aluminium temperature that generates is too high.
The consumption of iron can be the 0.1-30% (mol) of the total charging capacity of alkyl aluminium in the mole number of ferro element, and suitable scope is 1-15% (mol), and most preferred scope is 2.5-10% (mol).The blending ratio of antimony and iron is: counts in molar ratio, and Sb/Fe=0-20, more preferably scope is 0.05-10.Most preferred scope is 0.2-3.5.
Alkyl aluminium synthetic method of the present invention is owing to employing iron-based or iron-antimony base catalyst system, thereby cost is low.When using the reaction of monobromethane and triethyl aluminum, the thick yield of trimethyl aluminium can reach 92%.The separation of reaction mixture obtains simplifying.
Embodiment 1
Reactor is the 500ml four-hole boiling flask, and wherein, a bite is plugged in thermometer, and its excess-three mouth is azine airway (charging of double as halohydrocarbon), constant pressure funnel and prolong respectively, and the prolong top is linked to each other with the condenser of collecting monobromethane and monobromethane.Device is carried out vacuum-nitrogen replacement, add 24g toluene and 0.012mol FeCl earlier
3, add the 20g triethyl aluminum again in the dropping funnel, start stirrings, intensification, constant temperature and begin to feed CH when thermometer rises to 60 ℃
3Br begins slowly to drip triethyl aluminum simultaneously, can be observed temperature behind the several minutes and begins to rise, and constant temperature continues to feed CH at 105 ℃
3Br dripped off triethyl aluminum in 2.5 hours.Continue to stir 4 hours.Cooling, the analytical reaction miscellany contains trimethyl aluminium 10.2g, and the reaction yield that with the triethyl aluminum is benchmark is 80.5%.
Embodiment 2
Use 0.009mol FeCl
3With 0.003mol SbCl
3Mixture replace 0.012molFeCl3 among the embodiment 1, all the other are with embodiment 1.After reaction finishes, getting trimethyl aluminium 11.24g, is that the reaction yield of benchmark is 92% with the triethyl aluminum.
Embodiment 3
With the monobromethane among the methyl chloride replacement embodiment 1, all the other are with embodiment 1.Reaction result generates trimethyl aluminium 8.4g, is 66.5% in the reaction yield of triethyl aluminum.
Embodiment 4
With the monobromethane among the methyl iodide replacement embodiment 1, all the other are with embodiment 1.Reaction result generates trimethyl aluminium 8.0g, is 63.3% in the reaction yield of triethyl aluminum.
Embodiment 5
Earlier with 24g toluene, 0.009mol FeCl
3With 0.003mol SbCl
3Mixture, 1.0g n-propylcarbinyl chloride and 0.9g tri-n-n-propyl aluminum drop in the reaction flask, stirred 10 minutes after being warming up to 60 ℃, begin to drip triethyl aluminum, feed CH simultaneously
3Br keeps temperature of reaction at 105 ℃.Reaction finishes to generate trimethyl aluminium 7.95g, is that the reaction yield of benchmark is 62.95% with the triethyl aluminum.
Embodiment 6
With 0.012mol ferrocene and SbCl
3Mixture replace FeCl among the embodiment 1
3, all the other are with embodiment 1.Reaction result generates trimethyl aluminium 7.8g, is 61.8% in the reaction yield of triethyl aluminum.
Embodiment 7
Earlier with 24g toluene, 0.012mol FeCl
3, 1.6g dimethyl aluminum bromide drops into reaction flask, warming while stirring to 60 ℃ feeds CH continuously
3Br begins to drip the 20g triethyl aluminum after 10 minutes.Reaction result generates trimethyl aluminium 8.89g, is 70.4% in the reaction yield of triethyl aluminum.
Comparative Examples 1
Use 0.012molSbCl
3Replace the FeCl among the embodiment 1
3All the other are with embodiment 1.Reaction result generates trimethyl aluminium hardly.
Comparative Examples 2
Temperature of reaction is maintained 40 ℃ from start to finish, and all the other are with embodiment 2.Reaction result generates trimethyl aluminium 4.87g, is 38.6% in the reaction yield of triethyl aluminum.
Claims (16)
1. method by trialkyl aluminium that contains two carbon atoms in the alkyl at least and methyl halide prepared in reaction trimethyl aluminium, it is characterized in that this reaction is to finish in the presence of iron-based or iron one antimony base catalyst system, reinforced finishing continues constant temperature and stirred 4～5 hours.
2. according to the described method for preparing trimethyl aluminium of claim 1, it is characterized in that described trialkyl aluminium is triethyl aluminum.
3. according to the described method for preparing trimethyl aluminium of claim 1, it is characterized in that described methyl halide is methyl chloride, monobromethane and methyl iodide.
4. according to the described method for preparing trimethyl aluminium of claim 1, it is characterized in that described methyl halide is a monobromethane.
5. according to the described method for preparing trimethyl aluminium of claim 1, it is characterized in that temperature of reaction is 40～125 ℃.
6. according to the described method for preparing trimethyl aluminium of claim 1; it is characterized in that described iron-based or iron-antimony-based catalyst are prepared by following method; under protection of inert gas; the mixture of iron cpd or iron, antimony compounds is added reactor; be warming up to 40～80 ℃ gradually; add halohydrocarbon and trialkyl aluminium, the question response temperature begins to rise and shows that this catalyst system forms.
7. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that described iron cpd comprises iron(ic) chloride, iron bromide and ferrocene, described antimony compounds is butter of antimony or antimony pentachloride.
8. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that described trialkyl aluminium comprises triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum and hydrocarbylaluminum.
9. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that described halohydrocarbon comprises methyl chloride, monobromethane, methyl iodide.
10. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that described halohydrocarbon is a monobromethane.
11., it is characterized in that the consumption of iron is counted 0.1～30% of the total charging capacity of alkyl aluminium with the mole number of ferro element according to the described method for preparing trimethyl aluminium of claim 6.
12., it is characterized in that the consumption of iron is counted 1～15% of the total charging capacity of alkyl aluminium with the mole number of ferro element according to the described method for preparing trimethyl aluminium of claim 6.
13., it is characterized in that the consumption of iron is counted 2.5～10% of the total charging capacity of alkyl aluminium with the mole number of ferro element according to the described method for preparing trimethyl aluminium of claim 6.
14. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that the blending ratio of iron, antimony, be calculated in molar ratio as Sb/Fe=0～20.
15. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that the blending ratio of iron, antimony, be calculated in molar ratio as Sb/Fe=0.05～10.
16. according to the described method for preparing trimethyl aluminium of claim 6, it is characterized in that the blending ratio of iron, antimony, be calculated in molar ratio as Sb/Fe=0.2～3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98106736A CN1063751C (en) | 1998-03-25 | 1998-03-25 | Synthetic process for alkyl aluminium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98106736A CN1063751C (en) | 1998-03-25 | 1998-03-25 | Synthetic process for alkyl aluminium |
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| Publication Number | Publication Date |
|---|---|
| CN1229797A CN1229797A (en) | 1999-09-29 |
| CN1063751C true CN1063751C (en) | 2001-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98106736A Expired - Lifetime CN1063751C (en) | 1998-03-25 | 1998-03-25 | Synthetic process for alkyl aluminium |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102103049B (en) * | 2011-02-22 | 2013-01-09 | 江苏南大光电材料股份有限公司 | Trimethyl aluminum hydrochloric acid (HCl) decomposer for analyzing trace impurities in trimethyl aluminum |
| CN109369697A (en) * | 2018-12-30 | 2019-02-22 | 江西石华精细化工科技协同创新有限公司 | A kind of production method preparing trimethyl aluminium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364873A (en) * | 1981-07-13 | 1982-12-21 | Ethyl Corporation | Method of making aluminum alkyls |
| US4925962A (en) * | 1988-10-24 | 1990-05-15 | Ethyl Corporation | Trimethylaluminum process |
| US4948906A (en) * | 1990-02-16 | 1990-08-14 | Ethyl Corporation | Trimethylaluminum process |
-
1998
- 1998-03-25 CN CN98106736A patent/CN1063751C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364873A (en) * | 1981-07-13 | 1982-12-21 | Ethyl Corporation | Method of making aluminum alkyls |
| US4925962A (en) * | 1988-10-24 | 1990-05-15 | Ethyl Corporation | Trimethylaluminum process |
| US4948906A (en) * | 1990-02-16 | 1990-08-14 | Ethyl Corporation | Trimethylaluminum process |
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| Publication number | Publication date |
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| CN1229797A (en) | 1999-09-29 |
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| CB02 | Change of applicant information |
Applicant after: China Petrochemical Group Corp. Applicant after: Lanzhou Chemical Industry Co.,China National Petroleum Corp. Applicant before: China Petrochemical Corporation Applicant before: Lanzhou Chemical Industry Co., China Petrochemical Corp. |
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| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: CHINA PETRO-CHEMICAL CORP.; CHINA PETROCHEMICAL, LANZHOU CHEMICAL INDUSTRY CO., LTD. TO: CHINA PETROCHEMICAL CORPORATION; LANZHOU CHEMICAL INDUSTRY CO., LTD., CHINA PETROCHEMICAL CORP. |
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Granted publication date: 20010328 |