CN1919829A - Preparation method for alkyl substituent aromatic diamine - Google Patents
Preparation method for alkyl substituent aromatic diamine Download PDFInfo
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- CN1919829A CN1919829A CN 200610116075 CN200610116075A CN1919829A CN 1919829 A CN1919829 A CN 1919829A CN 200610116075 CN200610116075 CN 200610116075 CN 200610116075 A CN200610116075 A CN 200610116075A CN 1919829 A CN1919829 A CN 1919829A
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Abstract
The invention discloses a preparing method of aromatic diamin of substituted alkyl, which comprises the following steps: (1) reacting formaldehyde and 2, 6-diisopropyl benzeneamine with molar rate at 1:2.0-2.8 based on water as solvent acted by acid catalyst at 30-60 deg.c for 3-10 h; heating to 90-100 deg.c for 4-10h; (2) cooling the solution in the step (1) to 0-10 deg.c; dripping alkaline solution; evolving product; filtering; washing; drying; immersing through alcohol solvent; filtering; drying to obtain 3,3',5,5'-quaisopropyl-4,4'-diaminodiphenylmethane.
Description
Technical field
The present invention relates to a kind of preparation method of alkyl substituent aromatic diamine, particularly relate to a kind of 3,3 ', 5,5 '-tetra isopropyl-4, the preparation method of 4 '-diaminodiphenylmethane.
Background technology
Alkyl substituent aromatic diamine is a preparation fire resistant polyimide resin, high temperature resistant multifunctional glycidyl amine type epoxy resin, liquid crystal aligning is arranged agent, the low water absorbable carbon fiber strengthens the advanced composite material matrix resin, bimaleimide resin, the high impact-resistant epoxy curing agent, polyurethane chain extender, the electronic devices and components packaged material, insulating material, the important raw and processed materials of super large-scale integration passivating coating and alpha-particle blocking layer coating material and printed electronics board substrate matrix resin or tackiness agent.
The clear 63-284150 of Japanese Patent discloses a kind of 3,3 '-dimethyl-4, the preparation method of 4 '-diaminodiphenylmethane, be primarily characterized in that: Ortho Toluidine and formalin carry out condensation reaction in the presence of sulfide or sulfohydrate, and then with hydrazine hydrate processing reaction liquid, obtain 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, chemical equation is as follows:
The clear 61-98727 of Japanese Patent discloses a kind of 3,3 ', 5,5 '-tetraethyl--4, the preparation method of 4 '-diaminodiphenylmethane is primarily characterized in that: with 1, the 4-dioxane is a solvent, 2,6-Diethyl Aniline and formaldehyde react under 90 ℃ acidic conditions and obtain 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, chemical equation is as follows:
This method adopts 1, and the 4-dioxane is a solvent, has not only increased cost, and organic solvent constitutes a threat to HUMAN HEALTH, serious three wastes, and intractability is big, the expense height.
3,3 '-dimethyl-4 has two methyl, 3,3 ', 5 in 4 '-diaminodiphenylmethane molecular structure, and 5 '-tetraethyl--4 has four ethyls in 4 '-diaminodiphenylmethane molecular structure.These alkyl substituents have certain space steric effect to its adjacent amino, the activity that influence is amino, and the substituting group volume is big more, and space steric effect is remarkable more; In addition, the existence of alkyl substituent also can improve some performances by the polymkeric substance of above-mentioned diamines preparation, as dielectric properties, optical property and moisture-resistance etc.
In the benzene ring structure of aromatic diamine, introduce the alkyl substituent of large volume, will help improving moisture resistance and optical transparence, reduction specific inductivity and the dielectric loss etc. of its phase emergencing copolymer more.In addition, as epoxy curing agent the time, can improve the package stability of whole system; When arranging agent, help improving the tilt angle of liquid crystal aligning as polyimide liquid crystal direct action.
The sec.-propyl substituting group is bigger than the volume of methyl, ethyl, and consequent space steric effect is remarkable more, and its dielectric properties to emergencing copolymer, moisture resistance and optical transparence will be better.Therefore, contain the substituent aromatic diamine of sec.-propyl in the molecular structure and will have comprehensive performance.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of alkyl substituent aromatic diamine, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of alkyl substituent aromatic diamine comprises the steps:
(1) mol ratio is 1: 2.0～2.8 formaldehyde and 2,6-diisopropyl aniline (26DIPA), with water is solvent, under the effect of an acidic catalyst, in 30 ℃～60 ℃ down reactions after 3～10 hours, heat temperature raising to 90 ℃～100 ℃, and 90 ℃～100 ℃ reactions 4～10 hours, wherein, 2,6-diisopropyl aniline (26DIPA) is 1: 1.0～3.0 with the mol ratio of an acidic catalyst; 2,6-diisopropyl aniline (26DIPA) is 1: 2.0～6.0 with the weight ratio of water;
(2) with step (1) to solution be cooled to 0 ℃～10 ℃, drip alkaline aqueous solution, separate out product, filter washing, oven dry, alcoholic solvent soaks, and filters, and drying obtains 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane (3355TIPDDM).
As optimized technical scheme: described an acidic catalyst is one or more in Hydrogen bromide, hydrochloric acid, sulfuric acid, the phosphoric acid, preferred hydrochloric acid.
Alkali in the alkaline aqueous solution described in the step (2) is one or more in lithium hydroxide, potassium hydroxide, sodium hydroxide, the calcium hydroxide.Preferred aqueous sodium hydroxide solution.
Described alcoholic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, methyl cellosolve, the ethoxy ethanol.Preferred alcohol.
In the step (2) be with alcoholic solvent run the method wash make highly purified 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane (3355TIPDDM).
Chemical equation of the present invention is as follows:
The invention has the beneficial effects as follows: (1) preparation method of the present invention produces 3,3 ', 5,5 '-tetra isopropyl-4, the commercial run of 4 '-diaminodiphenylmethane (3355TIPDDM); (2) operation steps of the present invention is simple, can finish the synthesis and preparation process process in same reactor; (3) reaction is a solvent with water, convenient sources, and cost is lower, and the three wastes are few, handle easily, and Working environment is better; (4) good product quality, yield is higher, and 3,3 ', 5,5 '-tetra isopropyl-4, the purity of 4 '-diaminodiphenylmethane (3355TIPDDM) reaches 99%, yield 96%.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
With 35.4 gram (0.2 moles) 2,6-diisopropyl aniline (26DIPA) and 141.6 gram water are put into round-bottomed flask, stir under the room temperature, the aqueous hydrochloric acid that adds 39.5 grams 37%, after stirring 1.0 hours under 30 ℃, begin to drip the formalin of 7.4 grams 38.5%, drip off in 1 hour.At 50 ℃～60 ℃ temperature range internal reactions after 6 hours, improve temperature of reaction gradually, rise to 90 ℃～100 ℃, at 90 ℃～100 ℃ temperature range internal reactions after 8 hours, cooling reaction solution to 10 ℃, aqueous sodium hydroxide solution 240 grams of dropping 10% are separated out a large amount of solid products, filter, wash, dry, use alcohol immersion, filtration, drying again, obtain 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane (3355TIPDDM), according to the charging capacity and the product flow measurement of formaldehyde, yield 96% (purity 99%).
Embodiment 2
With 35.4 gram (0.2 moles) 2,6-diisopropyl aniline (26DIPA) and 212.4 gram water are put into round-bottomed flask, stir under the room temperature, the aqueous hydrochloric acid that adds 59.3 grams 37%, after stirring 1.5 hours under 30 ℃, begin to drip the formalin of 6.6 grams 38.5%, drip off in 1 hour.At 50 ℃～60 ℃ temperature range internal reactions after 4 hours, improve temperature of reaction gradually, rise to 90 ℃～100 ℃, at 90 ℃～100 ℃ temperature range internal reactions after 6 hours, cooling reaction solution to 5 ℃, potassium hydroxide aqueous solution 448 grams of dropping 10% are separated out a large amount of solid products, filter, wash, dry, again with methyl cellosolve immersion, filtration, drying, obtain 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane (3355TIPDDM), according to the charging capacity and the product flow measurement of formaldehyde, yield 86% (purity 96%).
Embodiment 3
With 35.4 gram (0.2 moles) 2,6-diisopropyl aniline (26DIPA) and 212.4 gram water are put into round-bottomed flask, stir under the room temperature, the aqueous sulfuric acid that adds 98.0 grams 20%, after stirring 1.5 hours under 30 ℃, begin to drip the formalin of 7.4 grams 38.5%, drip off in 1 hour.At 50 ℃～60 ℃ temperature range internal reactions after 3 hours, improve temperature of reaction gradually, rise to 90 ℃～100 ℃, at 90 ℃～100 ℃ temperature range internal reactions after 10 hours, cooling reaction solution to 0 ℃, aqueous sodium hydroxide solution 300 grams of dropping 10% are separated out a large amount of solid products, filter, wash, dry, again with methyl cellosolve immersion, filtration, drying, obtain 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane (3355TIPDDM), according to the charging capacity and the product flow measurement of formaldehyde, yield 85% (purity 94%).
Claims (7)
1, a kind of preparation method of alkyl substituent aromatic diamine is characterized in that, comprises the steps:
(1) mol ratio is 1: 2.0～2.8 formaldehyde and 2, the 6-diisopropyl aniline, with water is solvent, under the effect of an acidic catalyst, in 30 ℃～60 ℃ down reactions after 3～10 hours, heat temperature raising to 90 ℃～100 ℃, and 90 ℃～100 ℃ reactions 4～10 hours, wherein, 2, the mol ratio of 6-diisopropyl aniline and an acidic catalyst is 1: 1.0～3.0; 2, the weight ratio of 6-diisopropyl aniline and water is 1: 2.0～6.0;
(2) with step (1) to solution be cooled to 0 ℃～10 ℃, drip alkaline aqueous solution, separate out product, filter, washing, oven dry, alcoholic solvent soaks, and filters, drying obtains 3,3 ', 5,5 '-tetra isopropyl-4,4 '-diaminodiphenylmethane.
2, preparation method according to claim 1 is characterized in that, described an acidic catalyst is one or more in Hydrogen bromide, hydrochloric acid, sulfuric acid, the phosphoric acid.
3, preparation method according to claim 1 and 2 is characterized in that, described an acidic catalyst is a hydrochloric acid.
4, preparation method according to claim 1 is characterized in that, the alkali in the alkaline aqueous solution described in the step (2) is one or more in lithium hydroxide, potassium hydroxide, sodium hydroxide, the calcium hydroxide.
According to claim 1 or 4 described preparation methods, it is characterized in that 5, the alkali in the alkaline aqueous solution described in the step (2) is sodium hydroxide.
6, preparation method according to claim 1 is characterized in that, described alcoholic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, methyl cellosolve, the ethoxy ethanol.
7, according to claim 1 or 6 described preparation methods, it is characterized in that described alcoholic solvent is an ethanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101160751A CN100503552C (en) | 2006-09-15 | 2006-09-15 | Preparation method for alkyl substituent aromatic diamine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649174B (en) * | 2009-07-10 | 2012-12-12 | 东华大学 | Preparation method of high temperature resistant single-component solventless epoxy adhesive |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
-
2006
- 2006-09-15 CN CNB2006101160751A patent/CN100503552C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649174B (en) * | 2009-07-10 | 2012-12-12 | 东华大学 | Preparation method of high temperature resistant single-component solventless epoxy adhesive |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
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| CN100503552C (en) | 2009-06-24 |
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Assignee: Goldenmax International Technology Co., Ltd. Assignor: Donghua University Contract record no.: 2010310000136 Denomination of invention: Preparation method for alkyl substituent aromatic diamine Granted publication date: 20090624 License type: Exclusive License Open date: 20070228 Record date: 20100803 |
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