CN1161956A - Method for preparation of ortho-alkyl aromatic diamine - Google Patents
Method for preparation of ortho-alkyl aromatic diamine Download PDFInfo
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- CN1161956A CN1161956A CN 96102856 CN96102856A CN1161956A CN 1161956 A CN1161956 A CN 1161956A CN 96102856 CN96102856 CN 96102856 CN 96102856 A CN96102856 A CN 96102856A CN 1161956 A CN1161956 A CN 1161956A
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Abstract
A method for preparing orthoalkyl aromatic diamine is with aluminium powder as catalyst, after activation of aromatic amine to make aromatic diamine occur orthoakylation reaction to prepare orthoalkyl aromatic diamine. The said method features low reaction temp., low pressure and low stirring revolution speed, cheap price of the catalyst selected, small used quantity, good selectivity and no corrosion on equipment. The prepared orthoalkyl aromatic diamine may be used as curing agent for epoxy resin, oil antioxidant, intermediate in dye industry and chain extender for reaction injection moulding of amine.
Description
The present invention relates to the ortho-alkylated method for preparing aromatic diamines of a kind of alkylation process of arylamine, particularly aromatic diamines.
In U.S.P.3.275.690, be catalyzer with the Friedel-Crafts compound, catalysis arylamine alkylation process, used F-C compound is compounds such as aluminum chloride, aluminum boride, iron(ic) chloride, boron fluoride, zinc chloride, its reaction is 200-300 ℃ in temperature normally, and pressure is to carry out under the 15-25MPa.
In U.S.P.4.219.502, use expensive aluminum alkyls to make catalyzer, the alkylated reaction of catalysis aromatic diamines and alkene.
In E.P.422.590, use Al, Zn and AlCl
3Mixture make catalyzer, the ortho-alkylated process of catalysis aromatic diamines, stirring velocity is: 1500rpm.
Though more than three kinds of methods all be ortho-alkylated about aromatic diamines, but employed catalyzer is all different with the present invention, existing shortcoming is: catalyzer has cost an arm and a leg, have dangerous big, have equipment is had corrosion, and synthesis temperature, pressure and stirring velocity height.
The objective of the invention is to adopt the catalyzer of a kind of cheapness, safety to make the synthetic mild condition, and reach preferable alkylation result.
The present invention is to be the ortho-alkylated technological process of catalyst aromatic diamines with the aluminium powder, comprises catalyzer aluminium powder and activation method thereof.The ortho-alkylated reaction of aluminium powder catalysis aromatic diamines after the arylamine activation.Adopt this catalyzer to be issued to preferable ortho-alkylated effect at less catalyst levels, lower synthesis temperature and synthesis pressure and lower stirring velocity.
When implementing aromatic diamines alkylation process of the present invention, alkylation temperature is 150-300 ℃, is more preferably 180-270 ℃; Pressure is 1.0-8.0MPa, more preferably 2.0-6.0MPa; Mixing speed is 80-700rpm, more preferably 80-500rpm.
Alkylation process of the present invention has higher speed of response, and ortho-alkylated arylamine is had higher selectivity and high yield, and selectivity of catalyst is 96%, and reaction yield can reach 96%.
The alkylation aromatic amine that is made by the present invention has been widely used.Alkylating phenylenediamine can be used as epoxy curing agent, oil plant oxidation inhibitor, dyestuffs industries intermediate and reaction injection moulding amine chainextender.
The arylamine of deactivated catalyst is class fragrance monoamine (claiming the activation arylamine) among the present invention.For example, aniline and substituted aniline.The arylamine that is used for alkylated reaction is aromatic diamines (a title alkylation aromatic amine), has following molecular structure:
Wherein, X-sulphur, oxygen or-(CR3R4) n-(R3 wherein, R4 is hydrogen, low molecular weight alkyl, n is 1～3) R1, R2-alkyl, cycloalkyl, aralkyl a, b-0～3
Metallic aluminium as catalyzer can be aluminium bits, aluminum shot or aluminium powder, and aluminium powder is better.It is better that the aluminium powder particle diameter is controlled at 75-850 μ m, and the too big reaction of particle diameter is slow, the too little dust problem that exists when then operating.
The reactivation process of catalyzer is: add activation arylamine and aluminium powder in reactor, the add-on of aluminium powder is 2-6% for the 1-10% of activation arylamine weight preferably.Along with the release of hydrogen, aluminium powder forms a kind of pulpous state liquid, finishes when hydrogen discharges, and the activation of catalyzer is finished.The activation of catalyzer and alkylated reaction can carry out in a reactor; Also can first deactivated catalyst, catalyzer is shifted and preserves, be used for independently alkylation process then.
Alkylation process of the present invention is applicable to the ortho-alkylated of amine.It is aromatic diamines that alkylating amine takes place, particularly with the synthetic diethyl toluene diamine (DETDA) of tolylene diamine (TDA).The activation of catalyzer and alkylated reaction can adopt intermittent type or continuous process.
Alkene among the present invention is to contain 2-6 carbon atom, and best is to contain 2-4 carbon atom, as ethene, propylene, butylene, particularly ethene.
The selection of alkylation reaction condition will partly depend on and be used for alkylating alkene.For example, alkylating reaction pressure, temperature of reaction and stirring velocity change with the variation of alkene.No matter be intermittence or successive reaction, the selection of other parameter is decided by specific requirement with definite.
With the synthetic ortho-alkyl aromatic diamine of the present invention, the transformation efficiency of aromatic diamines is 100%, and yield can reach 96%, and selectivity of catalyst is 96%.
Adopt present method to prepare ortho-alkyl aromatic diamine, have the following advantages than the method that background technology adopted: used catalyzer low price, the consumption of the first lacks, selectivity is good, yield is high, equipment is not had corrosion.It two is that temperature of reaction and reaction pressure are low, and particularly stirring velocity is far below the speed that background technology adopted, and easy handling helps realizing industrialization.
Below be the embodiment of the ortho-alkylated prepared in reaction DETDA of TDA
Embodiment 1
2000g aniline and 100g aluminium powder are added in the reactor, and logical nitrogen replacement goes out wherein air, and stirring is warmed up to 250 ℃ and begins to have gas to produce, and behind about 15min, gas release finishes, and cools to below 100 ℃ overbottom pressure emptying.
Add 3000gTDA in reactor, use nitrogen replacement, be warmed up to 240 ℃, add ethene and make pressure be raised to 3.5-4.5MPa, ethene is absorbed rapidly, constantly adds fresh ethylene to keep pressure, and the 210min reaction finishes overbottom pressure emptying, discharging.Sample is through efficient liquid phase chromatographic analysis, and synthesis yield is 96%.The transformation efficiency of TDA is 100%.
Embodiment 2
Technology is with embodiment 1, and the alkylated reaction temperature changes 300 ℃ into, and reaction pressure is 7.0MPa.Analyzing synthetic result gets: synthesis yield is 79.9%, and wherein the transformation efficiency of TDA is 100%.
Embodiment 3
Technology is with embodiment 1, but the alkylated reaction temperature is 260 ℃, and reaction pressure is 3.0MPa.Analyzing synthetic result gets: synthesis yield is 94.3%.
Embodiment 4
Technology is with embodiment 1, but the alkylated reaction temperature is 330 ℃, and reaction pressure is 8.0MPa.Analyzing synthetic result gets: synthesis yield is 68.7%.
Embodiment 5
Technology is with embodiment 1, but the alkylated reaction temperature is 150 ℃, and reaction pressure is 8.0MPa.Analyzing synthetic result gets: synthesis yield is 42.3%.
Embodiment 6
Technology is with embodiment 1, but the alkylated reaction temperature is 280 ℃, and reaction pressure is 1.0MPa.Analyzing synthetic result gets: synthesis yield is 57.2%.
Claims (8)
1. the preparation method of an ortho-alkyl aromatic diamine, this method is that aromatic amine makes with alkene generation alkylation under catalyst action, it is characterized in that, the present invention selects for use aluminium powder to make catalyzer, after the arylamine activation, make aromatic diamines generation alkylated reaction, be reflected at temperature 150-300 ℃, pressure 1.0-8.0MPa carries out under the condition of mixing speed 80-700rpm.
2. preparation method according to claim 1, preferable ortho-alkylated temperature of reaction is 180-270 ℃.
3. preparation method according to claim 1, preferable reaction pressure are 2.0-6.0MPa.
4. preparation method according to claim 1, preferable mixing speed is 80-500rpm.
5. preparation method according to claim 1, being used to activate the arylamine that aluminium powder uses is aniline and substituted aniline.
6. preparation method according to claim 1, used aromatic diamines is tolylene diamine, ethylbenzene diamines and propyl benzene diamines.
7. preparation method according to claim 1, used alkene is the alkene that contains 2-6 carbon atom.
8. preparation method according to claim 1, the consumption of aluminium powder is the 2-6% of arylamine consumption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96102856 CN1161956A (en) | 1996-04-11 | 1996-04-11 | Method for preparation of ortho-alkyl aromatic diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96102856 CN1161956A (en) | 1996-04-11 | 1996-04-11 | Method for preparation of ortho-alkyl aromatic diamine |
Publications (1)
| Publication Number | Publication Date |
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| CN1161956A true CN1161956A (en) | 1997-10-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 96102856 Pending CN1161956A (en) | 1996-04-11 | 1996-04-11 | Method for preparation of ortho-alkyl aromatic diamine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417953A (en) * | 2007-10-25 | 2009-04-29 | 杭州崇舜化学有限公司 | Synthesis method of diethyl toluene diamine |
| CN106946714A (en) * | 2017-03-16 | 2017-07-14 | 安阳工学院 | A kind of synthesis technique of diethyl toluene diamine |
-
1996
- 1996-04-11 CN CN 96102856 patent/CN1161956A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417953A (en) * | 2007-10-25 | 2009-04-29 | 杭州崇舜化学有限公司 | Synthesis method of diethyl toluene diamine |
| CN106946714A (en) * | 2017-03-16 | 2017-07-14 | 安阳工学院 | A kind of synthesis technique of diethyl toluene diamine |
| CN106946714B (en) * | 2017-03-16 | 2022-03-22 | 安阳工学院 | Synthesis process of diethyltoluenediamine |
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